POLYMER CONTAINING SULFUR, POLYMER CONTAINING SULFUR WITH TERMINAL MODIFICATION, COMPOSITION AND OPE

专利摘要:
abstract "sulfur-containing polymer, terminally modified sulfur-containing polymer, composition and opening sealed with a sealant" are disclosed multifunctional sulfur-containing polymers which are the reaction products of a sulfur-containing diol, a polyol containing at least three hydroxyl groups per molecule polyol, and an aldehyde, a ketone, and a combination thereof. sealing compositions comprising multifunctional sulfur-containing polymers are also disclosed. 1
公开号:BR112013023900B1
申请号:R112013023900-0
申请日:2012-03-16
公开日:2020-03-10
发明作者:Stephen J. Hobbs；Gregory J. McCollum；Juexiao Cai；Marfi Ito；Lawrence G. Anderson；Renhe Lin
申请人:Prc-Desoto International, Inc.；
IPC主号:

专利说明:

“POLYMER CONTAINING SULFUR, POLYMER CONTAINING SULFUR WITH TERMINAL MODIFICATION, COMPOSITION AND OPENING SEALED WITH A SEALER” Field [0001] This disclosure relates to sulfur-containing polymers, compositions comprising sulfur-containing polymers, and methods for using multifunctional polymers containing sulfur.
Background [0002] Thiol-terminated sulfur-containing polymers are well known for being well suited for use in various applications such as aerospace sealant compositions due in large part to their resistance to fuels. Other desirable properties in aerospace sealant compositions include flexibility at low temperatures, short cure times (the time required to achieve a predetermined resistance), and resistance at high temperatures, among others. Sealing compositions exhibiting at least some of these characteristics and thiol-terminated sulfur-containing polymers are described, for example, in US Patent Nos. 2,466,963, 4,366,307, 4,609,762, 5,225,472, 5,912,319, 5,959,071 , 6,172,179, 6,232,401, 6,372,849, and 6,509,418. In aerospace sealant applications, polysulfides are also used where they provide high tensile strength, high shear strength, thermal resistance at high temperatures, and resistance to fuels, as disclosed, for example, in US Patent No. 7,638,162 and in US publication No. 2005/0245695.
[0003] Polyethers that are liquid at room temperature and pressure and that have excellent flexibility at low temperatures and resistance to fuels, such as those disclosed in U.S. Patent No. 6,172,179, are also useful in aerospace seal applications. For example, difunctional polyethers having hydroxyl end groups prepared by reacting a hydroxyl-containing compound with an aldehyde are described in GB 850,178 and in U.S. Patent Nos. 3,290,382, 3,959,227, and 3,997,614. Polythioethers terminated or capped with isocyanates are also known and disclosed, for example, in GB 850,178, and in U.S. Patent Nos. 3,290,382, 3,959,227, and 3 + 997,614. However, difunctional, that is, linear polyethers often swell during prolonged exposure to combustible hydrocarbons and other lubricants. On the other hand, seals prepared using polyfunctional polyethers can exhibit good fuel resistance, toughness and flexibility, but often with compromised elongation and adhesion.
[0004] It is desirable to provide polyfunctional polyethers that are useful as fuel resistant and water resistant seals with improved elongation and tensile strength, and without compromising adhesion.
Summary [0005] Multifunctional polymers containing sulfur are provided having improved properties suitable for applications such as aerospace sealants.
[0006] In a first aspect of the present disclosure, terminally modified sulfur-containing polymers are provided comprising: (a) a sulfur-containing diol; (b) a polyol containing at least three hydroxyl groups per polyol molecule; and (c) a reagent selected from an aldehyde, a ketone, and a combination thereof.
[0007] In a second aspect of the present disclosure, polymers containing sulfur having the structure of Formula (I) are provided: in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor. [0008] In a third aspect of the present disclosure, terminally modified sulfur-containing polymers are provided comprising the reaction products of reagents comprising: (a) a sulfur-containing polymer of Formula (I): in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (b) a compound comprising a terminal group selected from a vinyl group, a silyl group, an epoxy group, and an isocyanate group; and a group that is reactive with the hydroxyl groups of the polymer of Formula (I).
[0009] In a fourth aspect of the present disclosure, amine-terminated sulfur-containing polymers are provided comprising the reagent products comprising (a) and (b), wherein: (a) comprises the reaction products of reagents comprising (i) and (ii), where: (i) it comprises a sulfur-containing polymer of Formula (I): in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1_6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6-12 cycloalkyl) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (ii) comprises a first compound selected from a diisocyanate, thio-urea, an activated ethylenically unsaturated monoisocyanate, and a tosylate; and (b) comprises a second compound mercapto comprising an amine group and a group selected from a group that is reactive with a group that is reactive with an isocyanate group, a group that is reactive with an ethylenically unsaturated group, and a group that it is reactive with a tosylate.
[0010] In a fifth aspect of the present disclosure, sulfur-containing polymers terminated with thiol are provided comprising (a) and (b), where: (a) comprises the reaction products of reagents comprising (i) and (ii), being that: (i) comprises a sulfur-containing polymer of Formula (I): in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (ii) comprises a first compound selected from a diisocyanate, thio-urea, an activated ethylenically unsaturated monoisocyanate, and a tosylate; and (b) comprises an alkanol mercapto when (ii) comprises a diisocyanate; a metal hydrogen sulfide when (ii) comprises thio-ureas; a dithiol when (ii) comprises an ethylenically unsaturated monoisocyanate; and a hydrogen metal sulfide when (ii) comprises a tosylate.
[0011] In a sixth aspect of the present disclosure, terminally modified sulfur-containing polymers comprising reaction products of reagents comprising (a) and (b), are provided: (a) comprises reaction products of reagents comprising ( i) and (ii), where: (i) it comprises a sulfur-containing polymer of Formula (I): where n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, 3 C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (ii) comprises a first compound selected from a diisocyanate, an ethylenically unsaturated activated monoisocyanate, and a tosylate; and (b) comprises a second compound comprising a terminal group selected from a vinyl group, a silyl group, and an epoxy group; and a group that is reactive selected from a group that is reactive with an isocyanate group, a group that is reactive with an ethylenically unsaturated group, and a group that is reactive with a tosylate.
[0012] In a seventh aspect of the present disclosure, polymers containing sulfur with terminal modification of Formula (II) are provided: in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; each R5-OR5 'in which R5' is selected, regardless of a vinyl-terminated group, a silyl-terminated group, an amine-terminated group, an epoxy-terminated group, a thiol-terminated group, and an isocyanate-terminated group ; and Z represents the core of a Z (OH) m-valent valent precursor.
[0013] In an eighth aspect of the present disclosure, compositions are provided comprising a terminally modified sulfur-containing polymer provided by the present disclosure and a curing agent that is reactive with the terminally-modified sulfur-containing polymer.
[0014] In a ninth aspect of the present disclosure, openings are provided which are sealed with a seal comprising a composition comprising a terminally modified sulfur-containing polymer provided by the present disclosure and a curing agent which is reactive with the terminally-modified sulfur-containing polymer .
[0015] The present disclosure also relates to methods for preparing sulfur-containing polymers and compositions thereof, such as sealing compositions, including aerospace sealing compositions, comprising sulfur-containing polymers provided by the present disclosure.
Detailed description Definitions [0016] A dash (“-“) that is not between two letters or symbols is used to indicate a point of attachment for a substituent or between two atoms. For example, -CONH2 attaches to another portion through a carbon atom.
[0017] "Ethylenically activated unsaturated monoisocyanate" refers to a compound comprising an ethylenically unsaturated group and a monoisocyanate group in which the double bond is electron deficient such that it is activated in relation to the addition of Michael, that is, the double link is a Michael receiver.
[0018] "Aldehyde" refers to a compound of the formula CH (O) R where R is hydrogen or a hydrocarbon group such as an alkyl group, as defined herein. In certain embodiments, the aldehyde is C1-10 aldehyde, C1-6 aldehyde, C1-4 aldehyde, C1-3 aldehyde, and in certain incorporations, C1-2 aldehyde. In certain embodiments, aldehyde is formaldehyde. In certain aldehyde incorporations, R is selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (cycloalkyl of Substituted C6-12, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl.
[0019] "Alcanodiyl" refers to a divalent radical of a normal or branched chain saturated acyclic hydrocarbon group having, for example, from 1 to 18 carbon atoms (C1-1s), from 1 to 14 carbon atoms ( C1-14), from 1 to 6 carbon atoms (C1-6), from 1 to 4 carbon atoms (C1-4), or from 1 to 3 carbon atoms (C1-3). In certain embodiments, the alkanediyl is C2-14 alkanediyl, C2-10 alkanediyl, C2-8 alkanediyl, C2-6 alkanediyl, C2-4 alkanediyl, and in certain C2-3 alkanediyl. Examples of alkanodiyl groups include methanodiyl (-CH2-), ethane-1,2-diyl (-CH2CH2-), propane-1,3-diyl (-CH2CH2CH2-), isopropanol-1,2-diyl (-CH (CH3 ) CH2-), butane-1,4-diyl (- CH2CH2CH2CH2-), pentane-1,5-diyl (-CH2CH2CH2CH2CH2-), hexane-1,6-diyl (-CH2CH2CH2CH2CH2CH2-), heptane-1,7- diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, dodecane-1,12-diyl, and the like.
[0020] "Alkane dithiol" refers to an alkane group in which two of the hydrogen atoms are replaced by thiol groups, -SH. In certain embodiments, the dithiol alkane is a C2-12 dithiol alkane, C2 dithiol alkane -10, C2-8 dithiol alkane, C2-6 dithiol alkane, and in certain embodiments, C2-3 alkane dithiol.
[0021] "Alkane arene" refers to a hydrocarbon group having one or more aryl and / or arenodiyl groups and one or more alkyl and / or alkanodiyl groups, where aryl, arenodiyl, alkyl, and alkanodiyl are defined herein. incorporations, each aryl and / or arenodiyl group is C6-12, C6-10, and in certain phenyl or benzenodiyl incorporations, in certain incorporations, each alkyl and / or alkanodiyl group is C1-6, C1-4, C1-3, and in certain embodiments, methyl, methanediyl, ethyl, or ethane-1,2-diyl. In certain embodiments, the arane alkane group is C4-18 arane alkane, C4-16 arane alkane, C4-12 arane alkane, C4-8 alkane arene, C6-12 arane alkane, C6-10 arane alkane, and in certain embodiments, C6-9 arane alkane Examples of alkane arene groups include diphenyl methane.
[0022] "Alkenyl alkyne" refers to a divalent radical of an arane alkane group. In certain embodiments, the arenoidyl alkane group is C4-18 aryl alkane, C4-16 aryl alkane, C4-12 aryl alkane, C4-8 sandstone alkane, C6-12 sandstone alkane, C6-10 sandstone alkane, and in certain embodiments, C6-9 sandstone alkane Examples of sandstone alkane groups include diphenyl methane-4,4'-diyl.
[0023] "Cycloalkane alkane" refers to a saturated hydrocarbon group having one or more cycloalkyl and / or cycloalkanodiyl groups and one or more alkyl and / or alkanodiyl groups, where cycloalkyl, cycloalkanodiyl, alkyl, and alkanodiyl are defined herein. certain incorporations, each cycloalkyl and / or cycloalkanodiyl group is C3-6, C5-6, and in certain incorporations, cyclohexyl or cyclohexanodiyl. In certain incorporations, each alkyl and / or alkanodiyl group is C1-6, C1-4, C1-3, and in certain embodiments, methyl, methanediyl, ethane, or ethane-1,2-diyl In certain embodiments, the cycloalkane alkane group is C4-18 cycloalkane alkane, C4-16 cycloalkane alkane , C4-12 cycloalkane alkane, C4-8 cycloalkane alkane, C6-12 cycloalkane alkane, C6-10 cycloalkane alkane, and in certain embodiments, C6-9 cycloalkane alkane Examples of cycloalkane alkane groups include 1.1 , 3,3-tetramethyl cyclohexane and cyclohexyl met year. [0024] "Cycloalkanediyl alkane" refers to a divalent radical of a cycloalkane alkane group. In certain groups the cycloalkanodiyl alkane group is C4-16 cycloalkanodiyl alkane, C4-12 cycloalkanodiyl alkane, C4-8 cycloalkanodiyl alkane, C6-12 cycloalkanodiyl alkane, C6-10 cycloalkanodiyl alkane, C6-10 cycloalkanodiyl alkane, and in certain embodiments, C6-9 cycloalkanodiyl alkane. Examples of alkane cycloalkanediyl groups include 1,1,3,3-tetramethyl cyclohexane-1,5-diyl and cyclohexyl methane-4,4'-diyl.
[0025] "Alkoxy" refers to an -OR group where R is alkyl as defined herein. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. In certain embodiments, the alkoxy group is C1-8 alkoxy, C1-6 alkoxy, C1-4 alkoxy, and in certain embodiments, C1-3 alkoxy.
[0026] "Alkyl" refers to a monovalent radical of an abnormal, branched or branched acyclic hydrocarbon group having, for example, from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, from 1 to 4 carbon atoms, or from 1 to 3 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, terciobutyl, n-hexyl, n-decyl, tetradecyl, and the like. In certain embodiments, the alkyl group is C2-6 alkyl, C2-4 alkyl, and in certain embodiments, C2-3 alkyl.
[0027] "Aminoalkyl" refers to an alkyl group, as defined herein, in which one of the hydrogen atoms of the alkyl group is replaced by an amino group, -NH2. In certain embodiments, the aminoalkyl group is C1-10 aminoalkyl, C1-6 aminoalkyl, C1-4 aminoalkyl, C1-3 aminoalkyl, and in certain embodiments, C1-2 aminoalkyl.
[0028] "Arenodiila" refers to a bivalent radical of a monocyclic or polycyclic aromatic group. Examples of arenodiila groups include benzenodiila and naphthalenediila. In certain incorporations, the group arenodiila is C6-12 arenodiila, C6-10 arenodiila, C6-9 arenodiila, and in certain incorporations, benzenodiila.
[0029] "Aryl" refers to a monovalent aromatic hydrocarbon radical derived by removing a hydrogen atom from a single carbon atom from a precursor ring system. Arila comprises aromatic carbocyclic rings of 5 and 6 components, for example, benzene; bicyclic ring systems in which at least one ring is carbocyclic and aromatic, for example, naphthalene, indane, and tetralin; and tricyclic ring systems in which at least one ring is carbocyclic and aromatic, for example, fluorene. Arila encompasses multiple ring systems having at least one carbocyclic aromatic ring fused to at least one carbocyclic aromatic ring, cycloalkyl ring, or heterocycloalkyl ring. For example, aryl includes aromatic carbocyclic rings of 5 and 6 components fused to a 5- to 7-component heterocycloalkyl ring containing one or more heteroatoms chosen from N, O, and S. For such fused bicyclic ring systems in which only one of the rings is a carbocyclic aromatic ring, the point of attachment can be on the carbocyclic aromatic ring or the heterocycloalkyl ring. Examples of aryl groups include, but are not limited to, aceanthylene, acenaphthene, acephenanthrene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene, hexafene, hexalene, as-indacene, s-indacene, indane, indene, naphthalene , octacene, octafen, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentafene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinafthalene, and the like. In certain embodiments, the aryl group may have 6 to 20 carbon atoms, and in certain incorporations, 6 to 12 carbon atoms. However, aryl does not in any way cover or overlap heteroaryl, defined here separately. Hence, a multiple ring system in which one or more carbocyclic aromatic rings fuse with a heterocycloalkyl aromatic ring is heteroaryl, not aryl, as defined herein. In certain embodiments, an aryl group is phenyl.
[0030] "Arylalkyl" refers to an alkyl group in which one of the hydrogen atoms is replaced by an aryl group. In certain embodiments of an arylalkyl group, a hydrogen atom of the terminal carbon atom of an alkyl group is replaced by an aryl group. In certain incorporations of arylalkyl, the aryl group is an aryl group of C6-12, in certain incorporations an aryl group of C6-10, and in certain incorporations, a phenyl or naphthyl group. In certain embodiments, the alkanediyl portion of an arylalkyl group can be, for example, C1-10 alkanediyl, C1-6 alkanediyl, C1-4 alkanediyl, C1-3 alkanediyl, propane-1,3-diyl, ethane -1,2-diyl or methanodiyl. In certain embodiments, the arylalkyl group is C7-18 arylalkyl, C7-16 arylalkyl, C7-12 arylalkyl, C7-10 arylalkyl, or C7-9 arylalkyl. For example, C7-9 arylalkyl may include a C1-3 alkyl group attached to a phenyl group.
[0031] "Cycloalkanediyl" refers to a bivalent radical of a saturated, monocyclic or polycyclic hydrocarbon group. In certain incorporations, the cycloalkanodiyl group is C3-12 cycloalkanodiyl, C3-8 cycloalkanodiyl, C3-6 cycloalkanodiyl, and in certain incorporations, C5-6 cycloalkanodiyl. Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl.
[0032] "Cycloalkyl" refers to a monovalent radical of saturated, monocyclic or polycyclic hydrocarbon group. In finished incorporations, the cycloalkyl group is C3-i2 cycloalkyl, C3-8 cycloalkyl, C3-6 cycloalkyl, and in certain incorporations, C5-6 cycloalkyl.
[0033] "Cycloalkyl alkyl" refers to an alkyl group in which one of the hydrogen atoms is replaced by a cycloalkyl group. In certain embodiments of the cycloalkyl alkyl group, a hydrogen atom of the terminal carbon of an alkyl group is replaced by a cycloalkyl group In certain incorporations of cycloalkyl alkyl, the cycloalkyl alkyl group is a C3-6 cycloalkyl alkyl group, in certain embodiments a C5-6 cycloalkyl alkyl group, and in certain embodiments, a cyclopropyl, cyclobutyl group, or In certain embodiments, the alkanediyl portion of the cycloalkyl alkyl group can be, for example, C1-10 alkanediyl, C1-6 alkanediyl, C1-4 alkanediyl, C1-3 alkanediyl, propane-1,3 -diyl, ethane-1,2-diyl or methanediyl In certain embodiments, the cycloalkyl alkyl group is C4-16 cycloalkyl, C4-12 cycloalkyl, C4-10 cycloalkyl, cycloalkyl a C6-12 alkyl, or C6-9 cycloalkyl alkyl. For example, C6-9 cycloalkyl alkyl includes a C1-3 alkyl group attached to a cyclopentyl or cyclohexyl group.
[0034] "Cycloalkyl alkanodiyl" refers to a bivalent radical of a cycloalkyl alkane group. In certain embodiments, the cycloalkyl alkanodiyl group is C4-16 alkanodiyl cycloalkyl, C4-12 alkanodiyl cycloalkyl, C4-10 alkanodiyl cycloalkyl C6-12 cycloalkylalkylalkyl, or C6-9 cycloalkylalkylalkyl For example, C6-9 cycloalkylalkylalkyl includes a C1-3 alkyl group attached to a cyclopentyl or cyclohexyl group.
[0035] "Cycloalkyl alkane" refers to a normal or branched chain saturated acyclic hydrocarbon group in which one of the hydrogen atoms is replaced by a cycloalkane group. In certain embodiments of the alkane cycloalkyl group, a hydrogen atom is replaced. of a terminal carbon atom of a linear alkane group by a cycloalkyl group. In certain embodiments, the cycloalkyl group is a C3-6 cycloalkyl group, in certain incorporations a C5-6 cycloalkyl group, and in certain incorporations a cyclopropyl group, cyclobutyl, cyclopentyl, or cyclohexyl The alkane portion of the cycloalkyl alkane group can be, for example, C1-10 alkane, C1-6 alkane, C1-4 alkane, C1-3 alkane, propane, ethane, or methane In certain embodiments, a cycloalkyl alkane group is C4-16 cycloalkyl alkane, C4-12 cycloalkyl alkane, C4-10 cycloalkyl alkane, C6-12 cycloalkyl alkane, or C6-9 cycloalkyl alkane. for example, C6-9 cycloalkyl alkane includes a C1-3 alkyl group attached to a cyclopentyl or cyclohexyl group.
[0036] "Diisocyanate-derived group" refers to a group in which one or both of the terminal isocyanate groups of a precursor diisocyanate form a urethane (-OC (O) -NR-), thiourethane (-SC (O ) -NR-), or urea (-NR-C (O) -NR-), where R is hydrogen or a hydrocarbon group.The group derived from a diisocyanate includes groups derived from aliphatic diisocyanates and groups derived from aromatic diisocyanates. certain incorporations, the group derived from a diisocyanate is a group derived from an aliphatic diisocyanate, and in certain embodiments a group derived from an diisocyanate is a group derived from aromatic diisocyanate. For example, a compound derived from 2,6-diisocyanate toluene has the structure: where each R is a bond to a group -O-. -S-, or -NR-.
[0037] Examples of aliphatic diisocyanates include 1,6-hexamethylene diisocyanate, 1,5-diisocyanate-2-methyl pentane, methyl 2,6-diisocyanate hexanoate, bis (methyl isocyanate) cyclohexane, 1,3-bis (methyl isocyanate) cyclohexane, 2,2,4-trimethyl hexane 1,6-diisocyanate, 2,4,4-trimethyl hexane 1,6-diisocyanate, 2,5 (6) -is (methyl isocyanate) cycle [ 2.2.1] heptane, 1,3,3-trimethyl-1- (methyl isocyanate) -5-isocyanate cyclohexane, 1,8-diisocyanate-2,4-dimethyl octane, octahydro-4,7-methane diisocyanate -1H-dimethyl indene, and 1,1'-methylene bis (4-isocyanate cyclohexane), and 4,4-methylene dicyclohexyl diisocyanate (Hi2MDI). Examples of aromatic diisocyanates include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2.6-toluene diisocyanate (2,6-TDI), 2,4-toluene diisocyanate (2,4-TDI), a mixture of 2,4-TDI and 2,6-TDI, 1,5-naphthalene diisocyanate, diphenyl oxide 4,4'-diisocyanate, 4,4'-methylene diphenyl diisocyanate (4,4-MDI), diisocyanate diphenyl 2,4'-methylene (2,4-MDI), diphenyl methane 2,2'-diisocyanate (2,2-MDI), diphenyl methane diisocyanate (MDI), 3,3'-dimethyl-4 isocyanate , 4'-biphenylene, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1 - [(2,4-phenyl) methyl] -3-isocyanate-2-methyl benzene, and 2, 4,6-triisopropyl-m-phenylene.
[0038] Examples of alicyclic diisocyanates from which diisocyanates can be selected include isophorone diisocyanate (IPDI), cyclohexane diisocyanate, methyl cyclohexane diisocyanate, bis (methyl isocyanate) cyclohexane, bis (cyclohexane isocyanate) -hexyl) methane, bis (cyclohexyl isocyanate) -2,2-propane, bis (cyclohexyl isocyanate) -1,2-ethane, methyl-3- (3-propyl isocyanate) -5-isocyanate methyl-bicyclo [2.2.1] -heptane, 2-isocyanate methyl-3- (3-isocyanate propyl) -6-isocyanate methyl-bicyclo [2.2.1] -heptane, 2-isocyanate methyl-2- (3-isocyanate propyl) -5-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanate methyl-2- (3-isocyanate propyl) -6-isocyanate methyl-bicyclo [2.2.1] -heptane, 2-isocyanate methyl-3 - (propyl 3-isocyanate) -6- (ethyl 2-isocyanate) -bicyclo [2.2.1] -heptane, methyl 2-isocyanate-2- (propyl 3-isocyanate) -5- (ethyl 2-isocyanate) -bicycle [2.2.1] -heptane, and methyl 2-isocyanate-2- (propyl 3-isocyanate) -6- (ethyl 2-isocyanate) -bicyclo [2.2.1] -heptane.
[0039] Examples of aromatic diisocyanates in which the isocyanate groups directly bind to the aromatic ring include, but are not limited to bis (methyl isocyanate) benzene, α, α, α ', α'-tetramethyl xylene diisocyanate, 1,3 -bis (1-isocyanate-1-methyl ethyl) benzene, bis (butyl isocyanate) benzene, bis (methyl isocyanate) naphthalene, bis (methyl isocyanate) diphenyl ether, bis (methyl isocyanate) phthalate, and 2,5-di ( methyl isocyanate) furan. Aromatic diisocyanates having isocyanate groups directly attached to the aromatic ring include phenylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate, phenylene dimethyl diisocyanate, diethylene phenyl diisocyanate, diisopropyl phenylene diisocyanate, dihydocyanate diisocyanate, diisocyanate na biphenyl, 4,4'-diphenyl methane diisocyanate, bis (3-methyl-4-phenyl isocyanate) methane, bis (phenyl isocyanate) ethylene, 3,3'-dimethoxy-biphenyl-4,4'-diisocyanate, diisocyanate diphenyl ether, bis (phenyl ether isocyanate) ethylene glycol, bis (phenyl ether isocyanate) -1,3-propylene glycol, benzophenone diisocyanate, carbazole diisocyanate, carbazole ethyl diisocyanate, dichloro carbazole diisocyanate, 4.4 diisocyanate '-diphenyl methane, p-phenylene diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. [0040] "Group derived from an ethylenically unsaturated monoisocyanate" refers to a group in which the isocyanate group of an ethylenically unsaturated monoisocyanate precursor forms an urethane, thiourethane or urea bond and the ethylenically unsaturated group bonds to another portion or not binds to another portion. In certain embodiments, a group derived from an ethylenically unsaturated isocyanate refers to a group in which an isocyanate group from an ethylenically unsaturated precursor monoisocyanate forms a urethane, thiourethane or urea bond and the ethylenically unsaturated group is not connects to another parcel.
For example, a group derived from ethylenically unsaturated monoisocyanate ethyl 2-isocyanate methacrylate may have the structure: where the carbonyl group binds to -O-, -S-, or -NR- to form a urethane, thiourethane group, respectively or urea. In certain embodiments, a group derived from an ethylenically unsaturated isocyanate refers to a group in which an isocyanate group from a precursor ethylenically unsaturated monoisocyanate forms an urethane, thiourethane or urea bond and the ethylenically unsaturated group bonds with another portion. In such incorporations, a group derived from ethylenically unsaturated monoisocyanate ethyl 2-isocyanate methacrylate has the structure: where the carbonyl group binds to -O-, -S-, or -NR- to form, respectively, a urethane, thiourethane group or urea, and the previous vinyl group is linked to another parcel. [0041] "Heteroalkane arene" refers to an alkane arene group in which one or more carbon atoms are replaced by heteroatoms, such as N, O, S, or P. In certain embodiments of heteroalkane arene, the heteroatom is selected of N and O.
[0042] "Heteroalkane arenodiila" refers to an alkene arenodiyl group in which one or more carbon atoms are replaced by heteroatoms, such as N, O, S, or P. In certain embodiments of arenodiyl heteroalkane, the heteroatom is selected of N and O.
[0043] "Heteroalkane cycloalkane" refers to a cycloalkane alkane group in which one or more carbon atoms are replaced by heteroatoms, such as N, O, S, or P. In certain embodiments of cycloalkane heteroalkane, the heteroatom is selected of N and O.
[0044] "Cycloalkanodiyl heteroalkane" refers to a cycloalkanodiyl alkane group in which one or more carbon atoms are replaced by heteroatoms, such as N, O, S, or P. In certain embodiments of cycloalkanodiyl heteroalkane, the heteroatom is selected of N and O.
[0045] "Heteroalkanediyl" refers to an alkanediyl group in which one or more carbon atoms are replaced by heteroatoms, such as N, O, S, or P. In certain embodiments of heteroalkanodiyl, the heteroatom is selected from N and THE.
[0046] "Heterocycloalkanodiyl" refers to a cycloalkanodiyl group in which one or more carbon atoms are replaced by heteroatoms, such as N, O, S, or P. In certain embodiments of heterocycloalkanodiyl, the heteroatom is selected from N and THE.
[0047] "Heteroalkyl" refers to an alkyl group in which one or more carbon atoms are replaced by heteroatoms, such as N, O, S, or P. In certain heteroalkyl embodiments, the heteroatom is selected from N and THE.
[0048] "Heteroarenodiila" refers to an arenodiyl group in which one or more carbon atoms are replaced by heteroatoms, such as N, O, S, or P. In certain embodiments of heteroarenodiila, the heteroatom is selected from N and THE.
[0049] "Heteroaryl" refers to a monovalent heteroaromatic radical derived by removing a single atom of hydrogen from a precursor heteroaromatic ring system. Heteroaryl encompasses multiple ring systems having at least one heteroaromatic ring fused to at least one other ring, which may or may not be aromatic. Heteroaryl comprises aromatic monocyclic rings of 5 to 7 components containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3 heteroatoms chosen from N, O, S, and P with the remaining ring atoms being carbon atoms; and bicyclic heterocycloalkyl rings containing one or more, for example, from 1 to 4, or in certain embodiments, from 1 to 3 heteroatoms chosen from N, O, S, and P with the remaining ring atoms being carbon atoms and being at least one heteroatom is present in an aromatic ring. For example, heteroaryl includes a 5 to 7 component heteroaromatic ring fused to a 5 to 7 membered cycloalkyl ring. For such fused bicyclic heteroaryl ring systems in which only one of the rings contains one or more heteroatoms, the point of attachment may be at the heteroaromatic ring or the cycloalkyl ring. In certain embodiments, where the total number of N, O, S, and P atoms in the heteroaryl group is greater than 1, the heteroatoms are not adjacent. In certain embodiments, the total number of N, O, S, and P atoms in the heteroaryl group is less than or equal to 2. In certain embodiments, the total number of N, O, S, and P atoms in the heteroaryl group is less than or equal to 1. Heteroaryl does not cover or overlap with aryl defined here. Examples of heteroaryl groups include, but are not limited to, groups derived from acridine, arsindol, carbazole, α-carboline, chroman, chromene, cinoline, furan, imidazole, indazole, indole, indoline, indolizine, isobenzofuran, isochromene, isoindole, isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine, phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazol, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, quinoline, quinoline, quinoline thiazole, thiophene, triazole, xanthene, and the like. In certain embodiments, a heteroaryl group is C5-20 heteroaryl, C5-12 heteroaryl, C5-10 heteroaryl, and in certain C5-6 heteroaryl incorporations. In certain embodiments, heteroaryl groups are derived from thiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine, quinoline, imidazole, oxazole, or pyrazine.
[0050] "Ketone" refers to a compound of the formula CO (R) 2 where each R is a hydrocarbon group. In certain embodiments of a ketone, each R is selected, regardless of C1-6 alkyl, C7-12 phenyl alkyl, substituted C7-12 alkyl, C6-12 cycloalkyl, and substituted C6-12 cycloalkyl . In certain ketone incorporations, each R is independently selected from methyl, ethyl, and propyl. In certain embodiments, the ketone is selected from propan-2-one, butan-2-one, pentan-2-one, and pentan-3-one. In certain ketone incorporations, each R is selected, regardless of hydrogen, C1-6 alkyl, C7-12 phenyl alkyl, substituted C7-12 alkyl, C6-12 cycloalkyl, substituted C6-12 cycloalkyl , C6-12 aryl, and substituted C6-12 aryl.
[0051] "Phenyl alkyl" refers to an alkyl group in which one of the hydrogen atoms is replaced by a phenyl group. In certain phenyl alkyl embodiments, one of the terminal carbon atoms of an alkyl group is replaced by a phenyl group In certain embodiments, the phenyl alkyl group is C7-12 phenyl alkyl, C7_9 phenyl alkyl, and in certain embodiments, benzyl.
[0052] "Substituted" refers to a group in which one or more hydrogen atoms are independently substituted by at least one substituent or by different substituents. In certain embodiments, the substituent is selected from halogen, -S (O) 2H, - S (O) 2, -SH, -SR where R is C1-6 alkyl, -COOH, -NO2, -NR2 where each R is independently selected from hydrogen and C1-3 alkyl, -CN, = O, alkyl C1-6 alkyl, C1-3 alkyl, -CF3, -OH, phenyl, C2-6 heteroalkyl, C5-6 heteroaryl, C1-6 alkoxy, and -COR where R is C1-6 alkyl. certain embodiments, the substituent is chosen from -OH, -NH2, and C1-3 alkyl.
[0053] For the purposes of the following description, it will be understood that incorporations provided by the present disclosure may assume various sequences of steps and alternative variations, except where expressly specified to the contrary. Furthermore, differently in the examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and in the claims will be understood to be modified in all cases by the term "about". Consequently, unless if indicated to the contrary, the numerical parameters presented in the following specification and in the appended claims are approximations that may vary depending on the desired properties to be obtained by the present invention, at least, and not as an attempt to limit the application of the doctrine of equivalents to scope of the claims, each numerical parameter must be constructed in the light of the reported number of significant figures and applying usual rounding techniques. [0054] Despite the fact that the numerical ranges and parameters presenting the wide scope of the invention are approximations, numerical values presented in the and Specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors that necessarily result from the standard variation found in their respective test measures.
[0055] Likewise, it should be understood that any numerical range mentioned here intends to include all the sub-ranges contained therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the minimum mentioned value of 1 and the maximum mentioned value of 10, that is, having a minimum value greater than or equal to 1 and a value maximum less than or equal to 10.
[0056] Certain incorporations of polymers, compositions, and methods are now mentioned. The disclosed mergers are not intended to limit claims. To the contrary, the claims are intended to cover all alternatives, modifications, and equivalents.
Multifunctional polymers containing sulfur [0057] As indicated, certain embodiments provided by the present disclosure refer to multifunctional polymers containing sulfur. Sulfur-containing polymers include polyethers, polydisulfides, and polymer containing both thioether groups and disulfide groups. In general, polythioether refers to a polymer containing at least two thioether groups, for example, two groups -C-S-C-. Polydisulfide refers to a polymer containing at least two disulfide groups, for example, two groups -C-S-S-C-. In addition to at least two thioether and / or disulfide groups, sulfur-containing polymers provided by the present disclosure comprise at least two formal, acetal and / or ketal groups, for example, at least two groups -O-CR2-O-, where each R is independently selected from hydrogen, C1_6 alkyl, substituted alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), substituted alkyl (C6-12 cycloalkyl), cycloalkyl C3-12, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl. When used herein, "polymer" refers to oligomers, homopolymers, and copolymers. Unless stated otherwise, molecular weights are numerical average molecular weights for polymeric materials indicated by "Mn" and determined, for example, by gel permeation chromatography using a polystyrene standard recognized in the art.
[0058] In certain embodiments, polymers containing sulfur provided by the present disclosure comprise the reaction products of reagents comprising: (a) a sulfur-containing diol; (b) a polyol containing at least three hydroxyl groups per polyol molecule; and (c) a reagent selected from an aldehyde, a ketone, and a combination thereof. The reagents may comprise one or more types of sulfur-containing diol, one or more types of polyol, and / or one or more types of aldehyde and / or ketone.
[0059] In certain embodiments of the reaction, the sulfur-containing diol comprises the structure: where p is selected from 1 and 2; and each R1 is independently selected from C2-6 alkadienyl. In certain embodiments of a sulfur-containing diol, p is 1 and in certain embodiments p is 2. In certain embodiments of a sulfur-containing diol the R1 groups are the same and in certain embodiments, the R1 groups are different. In certain embodiments, each R1 is selected from C2-5 alkadienyl, C2-4 alkadienyl, C2-3 alkadienyl, and in certain embodiments, each R1 is ethane-1,2-diyl. In certain embodiments of the reaction, the sulfur-containing diol comprises a sulfur-containing diol selected from 2,2'-thio-diethanol, 3,3'-thiobis (propan-1-ol), 4,4'-thiobis (butan-1 -ol), and a combination of any of the above. In certain embodiments of the reaction, the sulfur-containing diol comprises 2,2'-thio-diethanol.
[0060] In certain embodiments of the reaction, the sulfur-containing diol comprises a single type of sulfur-containing diol, and in certain embodiments, it comprises a mixture of sulfur-containing diols. A mixture of sulfur-containing diols may comprise from 5 mol% to 95 mol% of one or more thioethers (p is 1) and from 95 mol% to 5 mol% of one or more disulfides (p is 2). In certain embodiments, a mixture of sulfur-containing diols comprises 50 mol% of one or more thioethers and 50 mol% of one or more disulfides. In certain embodiments, a mixture of sulfur-containing diols comprises from 0 mol% to 30 mol% of one or more disulfides, and from 100 mol% to 70 mol% of one or more thioethers.
[0061] In certain embodiments, a polyol contains at least three hydroxyl groups per polyol molecule. For example, a polyol can contain three to ten hydroxyl groups per polyol molecule, three to eight hydroxyl groups per polyol molecule, three to six hydroxyl groups per polyol molecule, and in certain embodiments, three to four groups hydroxyl per polyol molecule. In certain embodiments, a polyol contains four hydroxyl groups per polyol molecule, and in certain embodiments, a polyol contains three hydroxyl groups per polyol molecule. The polyol can be a single type of polyol or it can be a mixture of different polyols having the same or different numbers of hydroxyl groups per molecule.
[0062] In certain embodiments, a polyol comprises a triol of Formula (1): 2 ✓ where each R is independently C1-6 alkanediyl; and in certain embodiments, a polyol comprises a triol of Formula (2): 2 where each R is independently C 1-6 alkanediyl. In certain embodiments of a Formula (i) and Formula (2) polyol, each R2 can be selected, independently, from C1-4 alkanediyl, and in certain embodiments of a C1-3 alkanediyl. In certain embodiments, the 2 R groups may be the same, and in certain embodiments, the 2 R groups may be different. In certain incorporations of a Formula (1) and Formula (2) polyol, each R2 is selected from methanediyl, ethane-1,2-diyl, propane-1,3-diyl, and in certain incorporations, butane-1,4 -diila. [0063] In certain embodiments of the reaction, the reagent (c) is an aldehyde. In certain embodiments in which reagent (c) is an aldehyde, the aldehyde comprises a C1-6 aldehyde, a C1-4 aldehyde, a C1-3 aldehyde, and in certain embodiments, a C1-2 aldehyde. In certain embodiments, the aldehyde comprises an alkyl group and is selected from acetaldehyde, propionic (propanal) aldehyde, isobutyric aldehyde, and butyric aldehyde. In certain embodiments, aldehyde is formaldehyde (formic aldehyde). [0064] In certain embodiments of the reaction, the reagent (c) is a ketone. In certain embodiments in which reagent (c) is a ketone, the ketone has the formula C (O) R2 where each R is independently selected from C1-6 alkyl, alkyl (C7-12 phenyl), alkyl ( Substituted C7-12, alkyl (C6-12 cycloalkyl), substituted alkyl (C6-12 cycloalkyl), C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and C6-12 aryl substituted. In certain ketone incorporations, each R is independently selected from methyl, ethyl, and propyl. In certain embodiments, a ketone is selected from propan-2-one, butan-2-one, pentan-2-one, and 3-methyl-butan-2-one.
[0065] In certain embodiments, a sulfur-containing polymer of Formula (I) is the reaction product of reagents comprising 2,2'-dithioethanol and formaldehyde, and is referred to here as thio-diglycol polythioether or poly-formal thio-diglycol.
[0066] In embodiments in which the one or more polyols used to form sulfur-containing polymers provided by the present disclosure have the same number of hydroxyl groups, the sulfur-containing polymer will have a hydroxyl functionality approximately equivalent to that of the polyols. For example, when using, to prepare a sulfur-containing polymer, a polyol having a hydroxyl functionality of three or a mixture of polyols in which each of the polyols in the mixture has a hydroxyl functionality of three, the sulfur-containing polymer will have a functionality equal to three. In certain embodiments, a sulfur-containing polymer may have an average hydroxyl functionality of three, four, five, and in certain embodiments, six.
[0067] When using polyols having different hydroxyl functionalities to prepare sulfur-containing multifunctional polymers, sulfur-containing multifunctional polymers can exhibit a range of functionalities. For example, sulfur-containing multifunctional polymers provided by the present disclosure may have an average hydroxyl functionality of 3 to 12, 3 to 9, 3 to 6, 3 to 4, and in certain embodiments, from 3.1 to 3.5 . In certain embodiments, a sulfur-containing polymer having an average hydroxyl functionality of three to four can be prepared by reacting a combination of one or more polyols having a hydroxyl functionality of three and one or more polyols having a hydroxyl functionality of four. [0068] In certain incorporations, polymers containing sulfur of Formula (I) have a number of hydroxyls from 10 to 100, from 20 to 80, from 20 to 20, from 20 to 50, and in certain incorporations, from 20 to 40. The number of hydroxyls is the hydroxyl content of the sulfur-containing polymer, and can be determined, for example, by acetylating the hydroxyl groups and titrating the resulting acid against potassium hydroxide. The hydroxyl number (or index) is the weight of potassium hydroxide in mg (milligram) that will neutralize the acid of one gram of the sulfur-containing polymer.
[0069] In certain embodiments, a sulfur-containing polymer provided by the present disclosure of a numerical average molecular weight of 200 to 6,000 Dalton, from 500 to 5,000 Dalton, from 1,000 to 4,000 Dalton, from 1,500 to 3,500 Dalton, and in certain embodiments, from 2,000 to 3,000 Dalton.
[0070] In certain embodiments, a sulfur-containing polymer provided by the present disclosure is the reaction product of reagents comprising 2,2'-thiodiethanol, formaldehyde, and a triol of Formula (1). In certain embodiments, a sulfur-containing polymer provided by the present disclosure is the reaction product of reagents comprising 2,2'-thiodiethanol, formaldehyde, and a triol of Formula (2).
[0071] The reaction used to prepare a sulfur-containing polymer of Formula (I) can take place in the presence of an acid catalyst, such as sulfuric acid, sulfonic acid, or a combination thereof. In certain embodiments, a sulfonic acid can be used. Examples of sulfonic acids include alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, terciobutanol sulfonic acid, 2-propane sulfonic acid, and cyclohexyl sulfonic acid; alkene sulfonic acids such as α-olefin sulfonic acid, dimerized α-olefin sulfonic acid, and 2-hexene sulfonic acid; aromatic sulfonic acids such as para-toluene sulfonic acid, benzenesulfonic acid, and naphthalene sulfonic acid; and polymer-supported sulfonic acids such as AMBERLYST ™ sulfonic acid catalysts obtainable from Dow Chemical.
[0072] In certain embodiments, a sulfur-containing multifunctional polymer has the structure of Formula (I): in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor. 12 Each R can be the same or can be different, and each R can be the same or can be different.
[0073] In certain incorporations of a sulfur-containing polymer of Formula (I), each R1 is independently selected from C2-6 alkanediyl, C2-4 alkanediyl, C2-3 alkanediyl, and in certain embodiments, ethane- 1,2-diyl. In certain embodiments of a compound of Formula (I), each R1 is ethane-1,2-diyl.
[0074] In certain incorporations of a sulfur-containing polymer of Formula (I), each R3 is independently selected from hydrogen, C1-6 alkyl, C1-4 alkyl, C1-3 alkyl, and C1- alkyl 2. In certain embodiments of a compound of Formula (I), each R3 is methyl, and in certain embodiments, ethyl. In certain incorporations of a sulfur-containing polymer of Formula (I), each R3 is hydrogen, and in certain 3 incorporations, each R is selected from hydrogen, methyl, and ethyl. In certain embodiments of a sulfur-containing polymer of Formula (I), each R1 is ethane-1,2-diyl and each R3 is hydrogen.
[0075] In certain incorporations of a sulfur-containing polymer of Formula (I), each R1 is the same and is selected from C2-3 alkanediyl such as ethane-1,2-diyl and 3 propane-1,3-diyl; and each R is the same and is selected from hydrogen and C1-3 alkyl such as methyl, ethyl and propyl. In certain embodiments of a polymer of Formula (I), each R3 is hydrogen, and in certain 3 incorporations, each R is methyl. In certain embodiments of a sulfur-containing polymer of Formula (I), 13 each R is ethane-1,2-diyl and each R is hydrogen. In certain incorporations of a sulfur-containing polymer of Formula (I), each R1 is the same and is selected from ethane-1,2-3 diyl and propane-1,3-diyl; and each R is independently selected from hydrogen, methyl and ethyl.
[0076] In certain incorporations of a sulfur-containing polymer of Formula (I), n is an integer selected from 1 to 50, an integer selected from 2 to 40, an integer selected from 4 to 30, and in certain embodiments , an integer selected from 7 to 30.
[0077] In certain incorporations of a sulfur-containing polymer of Formula (I), p is the same and is 1, and in certain incorporations, each p is the same and is 2.
[0078] In certain embodiments of a compound of Formula (I), m is 1, m is 2, m is 3, m is 4, m is 5, and in certain embodiments, m is 6.
[0079] In certain embodiments of a compound of Formula (I), m is 3 and the polyol Z (OH) m precursor is a triol of Formula (1): where each R is independently C1-6 alkanediyl; and in certain embodiments, a polyol comprises a triol of Formula (2): 2 where each R is independently C 1-6 alkanediyl. Consequently, Z has, respectively, the structure: respectively 2 where each R is, independently, a C1-4 alkanediyl, and each Δ represents a bond to the group within the outer parenthesis of Formula (I).
[0080] In certain embodiments, a sulfur-containing polymer of Formula (I) has a number of hydroxyls from 10 to 100, from 20 to 80, from 20 to 60, from 20 to 50, and in certain embodiments, from 20 to 40 .
[0081] In certain embodiments, a sulfur-containing polymer of Formula (I) has a numerical average molecular weight of a numerical average molecular weight of 200 to 6,000 Dalton, from 500 to 5,000 Dalton, from 1,000 to 4,000 Dalton, from 1,500 to 3,500 Dalton, and in certain incorporations, from 2,000 to 3,000 Dalton.
Sulfur-containing polymers with terminal modification [0082] Multifunctional sulfur-containing polymers terminated by hydroxyl of Formula (I) can be derived such that the hydroxyl end groups are replaced by a group selected from a group terminated by vinyl, a group terminated by epoxy, a amine-terminated group, silyl-terminated group, thiol-terminated group, and isocyanate-terminated group.
[0083] In certain embodiments, a terminally modified sulfur-containing polymer comprises reagent reaction products comprising: (a) a sulfur-containing polymer of Formula (I): in which: each n is an integer selected from 1 to 50 ; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (b) a compound comprising a terminal group selected from a vinyl group, a silyl group, an epoxy group and an isocyanate group; and a group that is reactive with the hydroxyl end groups of the polymer of Formula (I).
[0084] In certain embodiments, a terminally modified sulfur-containing polymer comprises the reaction products of reagents comprising: (a) a sulfur-containing polymer of Formula (I): in which: each n is an integer selected from 1 to 50 ; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (b) a compound comprising a terminal group selected from a vinyl group, a silyl group, an epoxy group and an isocyanate group; and a group that is reactive with the hydroxyl end groups of the polymer of Formula (I).
[0085] In certain embodiments, a terminally modified sulfur-containing polymer comprises the reaction products of reagents comprising: (a) a sulfur-containing polymer of Formula (I): in which: each n is an integer selected from 1 to 50 ; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (b) a compound comprising a terminal group selected from a vinyl group, a silyl group, an epoxy group and an isocyanate group; and a group which is reactive with the hydroxyl end groups of the polymer of Formula (I).
[0086] In certain embodiments of a sulfur-containing polymer with terminal modification, the terminal group is a vinyl group and the compound comprising a terminal vinyl group is selected from an ethylenically unsaturated monoisocyanate and an ethylenically unsaturated alcohol.
[0087] An ethylenically unsaturated monoisocyanate includes ethylenically unsaturated aromatic monoisocyanates and ethylenically unsaturated aliphatic monoisocyanates. Examples of ethylenically unsaturated monoisocyanates include vinyl isocyanate, allyl isocyanate, 3-isocyanate-2-methyl-2-propene, methacryl isocyanate, ethyl isocyanate methacrylate, benzyl vinyl isocyanate, 3-isocyanate-1-butene, 3- isocyanate-3-methyl-1-butene, 4-isocyanate-2-methyl-1-butene, 4-isocyanate-3,3-dimethyl-1-butene, 4-isocyanate-4-methyl-1-pentene, and 5 -isocyanate-1-pentene, ethyl 2-isocyanate methacrylate, and dimethyl-meta-isopropenyl-benzyl isocyanate (TMI). In certain embodiments, an ethylenically unsaturated monoisocyanate is selected from vinyl isocyanate, allyl isocyanate, and methacryl isocyanate. In certain embodiments, an ethylenically unsaturated monoisocyanate is selected from C2-10 alkenyl isocyanate, C2-8 alkenyl isocyanate, C2-6 alkenyl isocyanate, and in certain embodiments, C2-3 alkenyl isocyanate.
[0088] Examples of ethylenically unsaturated alcohols include, for example, allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, ethylene glycol monovinyl ether, ethylene glycol monoalyl ether, glycerin monoalyl ether, trimethylol ethane monoalyl ether , trimethylolpropane monoalyl ether, poly (ethylene glycol) monoalyl ether, poly (propylene glycol) monoalyl ether, 1-vinyl-cyclobutanol, 2-vinyl-cyclobutanol, 3-vinyl-cyclobutanol, vinyl phenol, 2-allyl phenol, 4-allyl phenol, 4-allyl-2-methoxy phenol, 4-ally-2,6-dimethoxy phenol, 4- (2-propenyl) 1,2-benzenediol, and 4- (2,4-dihydroxy phenyl) -3-buten -2-one. In certain embodiments, an ethylenically unsaturated alcohol is selected from allyl alcohol, poly (ethylene glycol) monoalyl ether, 2-allyl phenol, and 4-allyl phenol.
[0089] In certain embodiments, the compound comprising a vinyl group is an ethylenically unsaturated monoisocyanate is selected from 3-isopropenyl-α isocyanate, α-dimethyl benzyl (CAS 2094-99-7) and ethyl 2-isocyanate methacrylate.
[0090] In certain embodiments of a reaction to form a terminally modified sulfur-containing polymer, the terminal group is a silyl group and the compound comprising a terminal silyl group is an alkyl alkoxysilane isocyanate. Examples of alkyl alkoxysilanes isocyanate include, for example, propyl methoxysilane isocyanate, propyl methyl dimethoxysilane isocyanate, propyl methyl diethoxysilane isocyanate, propyl trioxysilane isocyanate, propyl triisopropoxy silane, isocyanate propyl methoxylsilyl, methylshoxy, methoxy silane, diisoxypropane , neo-hexyl diethoxysilane isocyanate, neo-hexyl triethoxysilane isocyanate, neo-hexyl triisopropoxy silane isocyanate, neo-hexyl diisopropoxy silane isocyanate, isoamyl trimethoxysilane, isocyanate isoamyl dimethoxy silane, isocyanate isoamyl, isocyanate isoamyl, isocyanate isoamyl isocyanate isoamyl methyl diisopropoxy silane. In certain embodiments, the alkyl alkoxysilane isocyanate is propyl trimethoxysilane 3-isocyanate.
[0091] In certain embodiments of a sulfur-containing polymer with terminal modification, the terminal group is an epoxy group and the compound comprising a terminal epoxy group is selected from C1-6 epoxy alkanol, C1-6 epoxy halo alkane, and a combination of them. Examples of C1-6 alkanol epoxides include oxiran-2-ol, oxiran-2-yl methanol, and 2- (pxiran-2-yl) ethanol. Examples of halo C1-6 epoxy alkanes include, for example, 2- (chloro methyl) oxirane and 2- (2-chloro ethyl) oxirane.
[0092] In certain embodiments, a terminally modified sulfur-containing polymer comprises the reaction products of reagents comprising (a) and (b), where (a) comprises the reaction products of reagents comprising (i) and (ii), where (i) comprises a sulfur-containing polymer of Formula (I), where each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (ii) comprises a first compound selected from a diisocyanate, an ethylenically unsaturated activated monoisocyanate, and a tosylate; and (b) comprises a second compound comprising a terminal group selected from a vinyl group, a silyl group, and an epoxy group; and a group selected from a group that is reactive with an isocyanate group, a group that is reactive with an ethylenically unsaturated group, and a group that is reactive with a tosylate. [0093] In certain embodiments, an amine-terminated sulfur-containing polymer comprises reagent products comprising (a) and (b), where (a) comprises reagent reaction products comprising (i) and (ii), where ( i) comprises a sulfur-containing polymer of Formula (I): where each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (ii) comprises a first compound selected from a diisocyanate, an ethylenically unsaturated monoisocyanate, and a tosylate; and (b) comprises a second compound comprising an amine group and a group selected from a group that is reactive with a group that is reactive with an isocyanate group, an ethylenically unsaturated group, and a tosylate.
[0094] In certain embodiments, the first compound is a diisocyanate and is selected, for example, from 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,6-toluene diisocyanate (2,6-TDI ), 2,4-toluene diisocyanate (2,4-TDI), a mixture of 2,4-TDI and 2,6-TDI, 1,5-naphthalene diisocyanate, 4'-diphenyl oxide diisocyanate, diphenyl 4,4'-methylene diisocyanate (4,4-MDI), diphenyl 2,4'-methylene diisocyanate (2,4-MDI), diphenyl methane 2,2'-diisocyanate (2,2-MDI), diphenyl methane diisocyanate (MDI), 3,3'-dimethyl-4,4'-biphenylene isocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1 - [(2,4-phenyl diisocyanate ) methyl] -3-isocyanate-2-methyl benzene, 2,4,6-triisopropyl-m-phenylene diisocyanate, 4,4-methylene dicyclohexyl diisocyanate (H12MDI), and a combination of any of the above.
[0095] In certain embodiments of the reaction to form a terminally modified sulfur-containing polymer, the first compound is an ethylenically unsaturated monoisocyanate such as ethyl 2-isocyanate methacrylate. Examples of other ethylenically unsaturated monoisocyanates are disclosed herein.
[0096] In certain embodiments, the first compound is a tosylate such as a sulfonyl chloride, for example, p-toluene sulfonyl chloride.
[0097] In certain embodiments of a reaction to form a terminally modified sulfur-containing polymer, the second compound comprising a terminal amino group is selected from aniline, an aminoalkyl-substituted aniline, an aminoalkyl, and a sulfur-containing diamine. In certain embodiments, an aniline substituted with aminoalkyl of 4- (amino methyl) aniline and 4- (amino ethyl) aniline is selected. In certain embodiments, an aminoalkyl of ethanamine, propan-1-amine, and butan-1 amine is selected. Suitable sulfur-containing diamines include, for example, ETHACURE® 300.
[0098] In certain embodiments of a reaction to form a terminally modified sulfur-containing polymer, the second compound is an alkyl amino benzoate. Examples of suitable alkyl amino benzoates include, for example, methyl 4-amino benzoate, ethyl 4-amino benzoate, methyl 3-amino benzoate, ethyl 3-amino benzoate, ethyl 2-amino benzoate methyl, and ethyl 2-amino-benzoate. In certain embodiments, an alkyl amino benzoate is ethyl 4-amino benzoate.
[0099] In certain embodiments, a thiol-terminated sulfur-containing polymer comprises the reaction products of reagents comprising (a) and (b), where (a) comprises the reaction products of reagents comprising (i) and (ii), where (i) comprises a sulfur-containing polymer of Formula (I): where n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, 3 C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a Z (OH) m-valent valent precursor; and (ii) comprises a first compound selected from a diisocyanate, thio-urea, an activated ethylenically unsaturated monoisocyanate, and a tosylate; and (b) comprises an alkanol mercapto when (ii) comprises a diisocyanate; a hydrogen metal sulfide when (ii) comprises thio-urea; and a hydrogen metal sulfide when (ii) comprises a tosylate.
[0100] In certain embodiments, the first compound and a diisocyanate including any of those described here.
[0101] In certain embodiments, the first compound is an ethylenically unsaturated monoisocyanate including any of those described herein.
[0102] In certain embodiments, the first compound is a tosylate including any of those described herein such as p-toluene sulfonyl chloride.
[0103] In certain embodiments, the second compound is an alkanol mercapto such as, for example, C2-6 alkanol mercapto such as 2-mercapto ethane-1-ol, 3-mercapto propan-1-ol, 4-mercapto butan -1-ol, 5-mercapto pentan-1-ol, and 6-mercapto hexan-1-ol. Examples of suitable dithiols include, for example, alkane dithiols such as ethane-1,2-dithiol, propane-1,3-dithiol, butane-1,4-dithiol, combing-1,5-dithiol, and hexane-1, 6-dithiol.
[0104] In certain embodiments, the second compound is a metal hydrogen sulfide such as sodium hydrogen sulfide.
[0105] In certain embodiments of a reaction to form a terminally modified sulfur-containing polymer, the compound comprising a terminal thiol group is selected from a dithiol and an alkyl (bis) oxy dialcanothiol. In certain embodiments, the second compound is a dithiol including, for example, 1,2-ethane-dithiol, 1,2-propane-dithiol, 1.3-propane-dithiol, 1,3-butane-dithiol, 1,4-butane -ditiol, 2.3- butane-dithiol, 1,3-pentane-dithiol, 1,5-pentane-dithiol, 1,6-hexane-dithiol, 1,3-dimercapto-3-methyl-butane, dipentene dimercaptan, ethyl cycle -hexyl dithiol, diethyl dimercapto sulfide, dimethyl-substituted diethyl dimercapto sulfide, dimercapto di oxa octane, and 1,5-dimercapto-3-oxa-pentane. A dithiol may have one or more pendant groups selected from C1-4 alkyl, C1-4 alkoxy, and hydroxyl. [0106] In certain embodiments, a dithiol is an alkyl (bis) oxy dialcano thiol. Alkyl (bis) oxy dialcanol thiols may have the general formula HS-ROROR-HS, where each R is an alkanodiyl group such as, for example, C2-6 alkanediyl, C2-4 alkanediyl, or ethane-1,2 -diila. Suitable dithiols include alkyl (bis) oxy alkane dithiols such as 1,8-dimercapto-3, 6-dioxa octane (DMDO) or diethyl dimercapto sulfide (DMDS). In certain embodiments, a diethyl dimercapto sulfide dithiol (DMDS), dimercapto-dioxa octane (DMDO), and 1,5-dimercapto-3-oxa-pentane are selected.
[0107] Other examples of suitable dithiols include compounds of the formula HS-R-HS where R is C2-6 alkanediyl, having one or more pendant groups, which can be, for example, hydroxyl groups, C1-6 alkyl groups such as methyl or ethyl groups; C1-6 alkoxy groups, C6-8 cycloalkanodiyl groups, C6-10 cycloalkanodiyl alkane, - [- (CH2) sX-] q- (CH2) r-, or - [- (CH2) sX-] q- ( CH2) r- in which at least one -CH2- unit is replaced by a methyl group and in which each s is independently selected from an integer from 2 to 6, each q is independently selected from an integer from 1 to 5, and each r is independently selected from an integer from 2 to 10. Dithols may include one or more substituent hetero atoms in the main carbon chain, for example, dithols in which X is a hetero atom such as O, S or another bivalent heteroatom radical, a secondary or tertiary amine group such as, -NR-, where R is hydrogen or methyl, or another substituted trivalent heteroatom. In certain embodiments, X is O or S, and in certain embodiments, p and r are the same, and in certain embodiments both p and r are 2. In certain embodiments, X is a bond. Other examples of suitable dithiols are disclosed, for example, in U.S. Patent No. 6,172,179, which is incorporated herein entirely by reference.
[0108] In certain incorporations of the sulfur-containing polymers with terminal modification above, the sulfur-containing polymer with terminal modification has a numerical average molecular weight of 200 to 6,000 Dalton, from 500 to 5,000 Dalton, from 1,000 to 5,000 Dalton, from 1,500 to 4,000 Dalton, and in certain incorporations, from 2,000 to 3,600 Dalton.
[0109] Certain terminally modified sulfur-containing polymers provided by the present disclosure have the structure of Formula (II): where each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; each R5 is -OR5 'in which R5' is selected, regardless of a vinyl-terminated group, a silyl-terminated group, an amine-terminated group, an epoxy-terminated group, a thiol-terminated group, and a group terminated by isocyanate; and Z represents the core of a Z (OH) m-valent valent precursor.
[0110] Certain terminally modified sulfur-containing polymers provided by the present disclosure have the structure of Formula (II): where each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkadienyl; each R is independently selected from hydrogen, C1-6 alkyl, alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), alkyl (C6-12 cycloalkyl), alkyl (C6- cycloalkyl) 12) substituted, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; each R5 is -OR5 'in which R5' is selected, regardless of a vinyl-terminated group, a silyl-terminated group, an amine-terminated group, an epoxy-terminated group, and a thiol-terminated group; and Z represents the core of a Z (OH) m-valent valent precursor. [0111] In certain incorporations of a sulfur-containing polymer of Formula (II), each R1 is independently selected from C2-6 alkanediyl, C2-4 alkanediyl, C2-3 alkanediyl, and in certain incorporations, ethane- 1,2-diyl. In certain embodiments of a sulfur-containing polymer of Formula (II), each R1 is ethane-1,2-diyl. [0112] In certain incorporations of a sulfur-containing polymer of Formula (II), each R3 is independently selected from C1-6 alkyl, C1-4 alkyl, C1-3 alkyl, and in certain embodiments, alkyl of C1-2. In certain incorporations of a sulfur-containing polymer of Formula (II), each R3 is hydrogen, and in certain incorporations, methyl, and in certain ethyl incorporations. [0113] In certain incorporations of a sulfur-containing polymer of Formula (II), each R1 is the same and is selected from C2-3 alkanediyl, such as ethane-1,2-diyl 3 and propane-1,3-diyl ; and each R is the same and is selected from hydrogen and C1-3 alkyl such as methyl, ethyl, and propyl. In certain embodiments of a sulfur-containing polymer of Formula (II), each R1 is ethane-1,2-diyl. In certain incorporations of a sulfur-containing polymer of Formula (II), each R3 is hydrogen. In certain embodiments of a sulfur-containing polymer of Formula 13 (II), each R is ethane-1,2-diyl and each R is hydrogen.
[0114] In certain embodiments of a compound of Formula (II), m is 1, m is 2, m is 3, m is 4, m is 5, and in certain embodiments, m is 6.
[0115] In certain embodiments of a sulfur-containing polymer of Formula (II) where m is 3, the precursor polyol Z (OH) m is a triol of Formula (1): where each R is independently C1-6 alkanediyl; and in certain embodiments, a triol of Formula (2): 2 where each R is independently C1-6 alkanediyl. Consequently, in these incorporations Z has the structure: 2 χ Respectively, where each R is independently C1-6 alkanediyl.
[0116] In certain embodiments of a sulfur-containing polymer of Formula (II), each n is an integer selected from 1 to 50, an integer selected from 2 to 40, an integer selected from 4 to 30, and in certain incorporations, a whole number selected from 7 to 30.
[0117] In certain embodiments of a sulfur-containing polymer of Formula (II), each p is the same and is 1, and in certain embodiments, each p is the same and is 2.
[0118] In certain embodiments, a sulfur-containing polymer of Formula (II) has a numerical average molecular weight of 200 to 6,000 Dalton, 500 to 5,000 Dalton, 1,000 to 5,000 Dalton, 1,500 to 4,000 Dalton, and in certain embodiments , from 2,000 to 3,600 Dalton.
[0119] In certain embodiments of a sulfur-containing polymer of Formula (II), each R5 is the same.
[0120] In certain incorporations of a sulfur-containing polymer of Formula (II), each R5 is selected from a vinyl-terminated group of Formula (a), Formula (b), Formula (c), Formula (d), and Formula (e): where each R6 is a portion derived from an ethylenically unsaturated monoisocyanate; each R is selected from C2-6 alkanediyl, C2-6 heteroalkanediyl; C6-12 arenodiyl, substituted C6-12 arenodiyl, C6-12 heteroarenodiyl, substituted C6-12 heteroarenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, C3-12 heterocycloalkanodiyl, C3-12 heterocycloalkanodiyl substituted, C7-18 arenodiyl alkane, substituted C7-18 arenodiyl heteroalkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane.
[0121] In certain embodiments, each R6 is derived from an ethylenically unsaturated aliphatic monoisocyanate, an ethylenically unsaturated alicyclic monoisocyanate, and in certain embodiments, from an ethylenically unsaturated aromatic monoisocyanate.
[0122] In certain incorporations of Formula (b) and Formula (d), each R7 is selected from C2-4 alkanediyl, C2-3 alkanediyl, and in certain embodiments it is selected from ethane-1,2-diyl, propane -1,3-diyl, propane-1,2-diyl, and propane-1,1-diyl. In certain incorporations of Formula (b) and Formula (d), each R7 is selected from ethane-1,2-diyl and propane-1,3-diyl.
[0123] In certain incorporations of Formula (b), Formula (c), Formula (d), and Formula (e), each R8 is selected from hydrogen, methyl, ethyl, isopropyl, and n-propyl.
[0124] In certain embodiments of formula (e) each R9 is selected from C2-6 alkanodiyl, C6-12 arenodiyl, substituted C6-12 arenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, arenodiyl alkane C7-18 alkane, substituted C7-18 alkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane. In finished incorporations of Formula (e), each R9 is the same and is selected from methanediyl, ethane-1,2-diyl, and propane-1,2-diyl. In certain embodiments of Formula (e), each R9 is C2-5 alkanediyl, C2-4 alkanediyl, C2-3 alkanediyl, and in certain incorporations, ethane-1.2-diyl.
[0125] In certain sulfur-containing polymers containing Formula (II), each R5 is selected from a group terminated by the silyl of Formula (f) and Formula (g): where each R6 is derived from an ethylenically unsaturated monoisocyanate; each R10 is independently selected from C1-6 alkyl, C1-6 alkoxy, C5-6 cycloalkyl, alkyl (C6-12 cycloalkyl), phenyl, and alkyl (C7-12 phenyl), and at least at least one R10 is C1-6 alkoxy; and each R11 is C1-6 alkanediyl.
[0126] In certain embodiments of Formula (g), each R11 is selected from methanediyl, ethane-1,2-diyl, and propane-1,2-diyl. In certain incorporations of Formula (f) and Formula (g), each R10 is the same and is selected from methoxy, ethoxy, and propoxy. In certain incorporations of Formula (f) and Formula (g), the terminal silyl group is a trialkoxysilane, in certain embodiments, a dialkoxysilane, and in certain incorporations, a monoalkoxysilane.
[0127] In certain sulfur-containing polymers containing Formula (II), each R5 is selected from the group terminated by the amine of Formula (h), Formula (i), Formula (j), Formula (k), Formula (l ), and Formula (m): where each R6 is selected from a group derived from a diisocyanate and a group derived from an ethylenically unsaturated monoisocyanate; each R is selected from a bond and C2-6 alkanediyl; each R9 is selected from C2-6 alkanediyl, C2-6 heteroalkanediyl; C6-12 arenodiyl, substituted C6-12 arenodiyl, C6-12 heteroarenodiyl, substituted C6-12 heteroarenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, C3-12 heterocycloalkanodiyl, C3-12 heterocycloalkanodiyl substituted, C7-18 arenodiyl alkane, substituted C7-18 arenodiyl heteroalkane, C4-12 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane; and each R is selected from hydrogen, C1-6 alkyl, C6-12 aryl, substituted C6-12 aryl, C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C7-18 alkyl aryl, alkyl aryl Substituted C7-18, C4-18 cycloalkyl, and substituted C4-18 cycloalkyl.
[0128] In certain embodiments of Formula (h), each R6 is a group derived from a diisocyanate, and in certain embodiments the group is derived from TDI, ISONATE ™ 143L (diphenyl methane diisocyanate modified with polycarbodiimide), DESMODUR® N3400 (1 , 3-diazetidine-2,4-dione, 1,3-bis (6-isocyanate hexyl) -), DESMODUR® (I) (isophorone diisocyanate, IPDI), and DESMODUR® W (H12MDI). [0129] In certain embodiments of Formula (h), each R6 is a group derived from an ethylenically unsaturated monoisocyanate, and in certain embodiments it is selected from ethyl 2-isocyanate methacrylate.
[0130] In certain incorporations of Formula (h), Formula (i), Formula (j), Formula (k), Formula (l), and Formula 7 (m), each R is selected from C2-4 alkanediyl, alkanodiyl of C2-3, and in certain embodiments it is selected from ethane-1,2-diyl, propane-1,3-diyl, and propane-1,1-diyl. In certain incorporations of Formula (h), Formula (i), Formula (j), Formula (k), Formula (l), and Formula (m), each R7 is selected from ethane-1,2-diyl and propane- 1,3-diyl.
[0131] In certain incorporations of Formula (k) and Formula (l), each R9 is selected from C2-6 alkanodiyl, C6-12 arenodiyl, substituted C6-12 arenodiyl, C3-12 cycloalkanediyl, C3 cycloalkanediyl -12 substituted, C7-18 arenodiyl alkane, substituted C7-18 arenodiyl alkane, C4-18 cycloalkanodiyl alkane and substituted C4-18 cycloalkanodiyl alkane.
[0132] In certain embodiments of Formula (h), Formula (i), Formula (j), Formula (k), Formula (l), and Formula (m), each R12 is selected from C1-6 alkyl, phenyl , and phenyl substituted by amino. of Formula (h), Formula (i), Formula (j), Formula (k), Formula (l), and Formula (m), each 12 z R is selected from phenyl, methyl, ethyl, propyl, methyl-phenyl , ethyl-phenyl, propyl-phenyl, benzyl, phenethyl, - (CH2) -aniline, and amino-phenyl.
[0133] In certain incorporations of a Formula (II) polymer, each R5 is selected from an epoxy-terminated group of Formula (n): where each R11 is, independently, C1-6 alkanediyl.
[0134] In certain embodiments of Formula (n), each R11 is selected from methanediyl, ethane-1,2-diyl, and propane-1,3-diyl. In certain embodiments, each R11 is the same and is selected from ethane-1,2-diyl, and propane-1,3-diyl. where each R6 is selected from a portion derived from a diisocyanate and a portion derived from an ethylenically unsaturated monoisocyanate; each R7 is selected from C2-i4 alkanodiyl and C2-i4 heteroalkanediyl; and each R9 is selected from C2-6 alkanediyl, C2-6 heteroalkanediyl; C6-i2 arenodiyl, substituted C6-i2 arenodiyl, Ce-12 heteroarenodiyl, substituted Ce-12 heteroarenodiyl, C3_i2 cycloalkanodiyl, C3_i2 substituted heterocycloalkane, C3_i2 heterocycloalkane, heterocycloalkane, heterocycloalkane 18, substituted C7-18 arenodiyl heteroalkane, C4_8 cycloalkanodiyl alkane, and substituted C4_8 cycloalkanodiyl alkane. is a group derived from a diisocyanate, and in certain embodiments the group is derived from TDI, ISONATE ™ 143L (diphenyl methane diisocyanate modified with polycarbodiimide), DESMODUR® N3400 (1,3-diazetidine-2,4-dione, 1,3 -bis (6-hexyl isocyanate) -), DESMODUR® I (isophorone diisocyanate, IPDI), and DESMODUR® W (Hi2MDI). [0137] In certain embodiments of Formula (o), each R6 is a group derived from an ethylenically unsaturated monoisocyanate, and in certain embodiments it is selected from ethyl 2-isocyanate methacrylate.
[0138] In certain incorporations of Formula (o), Formula (p), Formula (q), Formula (r), Formula (s), Formula (t), Formula (u), and Formula (v), each R7 is selected from -CH2-S- (CH2) 2-O- (CH2) 2-O- (CH2) 2-, - (CH2) 2-O- (CH2) 2-O- (CH2) 2-, and - (CH2) 2-S- (CH2) 2-0- (CH2) 2-0- (CH2) 2-.
[0139] In certain incorporations of Formula (t) and Formula (u), each R9 is selected from C2_6 alkanodiyl, C6-i2 arenodiyl, substituted C6-i2 arenodiyl, C3_i2 cycloalkanodiyl, substituted C3_i2 alkanodiyl, arenodiyl alkane C7-18, alkaline substituted C7-18 alkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane.
[0140] In certain incorporations of a sulfur-containing polymer of Formula (II), each R5 is selected from a group terminated by isocyanate of Formula (w) and Formula (x): in which: each R9 is selected from C2- alkanediyl 6, C2-6 heteroalkanediyl; C6-12 arenodiyl, substituted C6-12 arenodiyl, C6-12 heteroarenodiyl, substituted C6-12 heteroarenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, C3-12 heterocycloalkanodiyl, C3-12 heterocycloalkanodiyl substituted, C7-18 arenodiyl alkane, substituted C7-18 arenodiyl heteroalkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane; and each R is a group derived from a diisocyanate.
[0141] In certain embodiments of Formula (w), each R9 is selected from C2-6 alkanodiyl, C6-12 arenodiyl, substituted C6-12 arenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, alkane C7-18 arenodiyl, substituted C7-18 arenodiyl alkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane.
[0142] In certain embodiments of Formula (x), each 12 R is a group derived from a diisocyanate, and in certain embodiments the group is derived from TDI, ISONATE ™ 143L (diphenyl methane diisocyanate modified with polycarbodiimide), DESMODUR® N3400 ( 1,3-diazetidine-2,4-dione, 1,3-bis (6-isocyanate hexyl) -), DESMODUR® I (isophorone diisocyanate, IPDI), and DESMODUR® W (H12MDI). Synthesis of sulfur-containing polymers [0143] Multifunctional sulfur-containing polymers provided by the present disclosure and precursors thereof can be prepared by a number of methods known to those skilled in the art, including those described herein in the examples. For example, to obtain multifunctional polymers containing sulfur of Formula (I), a sulfur-containing diol, a polyol containing at least three hydroxyl groups per polyol molecule, and an aldehyde can react in an organic solvent in the presence of a sulfonic acid such as AMBERLYST ™ 15 to provide the resulting sulfur-containing multifunctional polymer of Formula (I). Synthesis of sulfur-containing multifunctional polymers with terminal modification [0144] Multifunctional sulfur-containing polymers with terminal modification provided by the present disclosure and precursors thereof can be prepared by a number of methods known to those skilled in the art, including those described in the examples. For example, to obtain multifunctional polymers containing sulfur with terminal modification of Formula (II), a multifunctional polymer containing sulfur of Formula (I) can react with a compound having appropriate terminal groups and a group that is reactive with the terminal hydroxyl group of the polymer of Formula (I).
[0145] For example, to obtain a vinyl-terminated sulfur-containing polymer of Formula (II), a sulfur-containing polymer of Formula (I) can react with a compound containing a vinyl terminal group and an isocyanate group, for example, a monoisocyanate ethylenically unsaturated, such as TMI, ethyl 2-isocyanate, or allyl isocyanate in the presence of dibutyl tin dilaurate and benzyl chloride at 76 ° C. As a further example, a sulfur-containing polymer of Formula (I) can be reacted with an alkanol such as 3-butene-1-ol and an aldehyde such as formaldehyde in the presence of a sulfonic acid (eg 4.7 meq / g of H +) such as AMBERLYST ™ 15 in an organic solvent such as toluene to provide a vinyl-terminated sulfur-containing polymer of Formula (II).
[0146] Sulfur-containing polymers terminated by silyl of Formula (II) can be prepared, for example, by reacting a sulfur-containing polymer of Formula (I) with an alkyl trialoxy silane isocyanate such as propyl trimethoxysilane 3-isocyanate or propyl ethoxy 3-isocyanate silane in the presence of dibutyl tin dilaurate at a temperature of 76 ° C to provide the sulfur-containing polymer terminated by the corresponding Formula (II) silyl.
[0147] Formula (II) epoxy-terminated sulfur-containing polymers can be prepared, for example, by reacting a sulfur-containing polymer of Formula (I) in the presence of a monopoxide such as epichlorohydrin to provide the sulfur-containing polymer terminated by Formula-silyl. (II) corresponding.
[0148] Amine-terminated sulfur-containing polymers of Formula (III) can be prepared, for example, by reacting a vinyl-terminated sulfur-containing polymer of Formula (II) with aniline, an amino substituted aniline such as 4- (amino methyl) aniline, or alkylamine such as n-butylamine, optionally in the presence of a catalyst such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), in an organic solvent to provide the amine-terminated sulfur-containing polymer of Corresponding formula (III). Alternatively, the amine-terminated sulfur-containing polymers of Formula (III) can be obtained by reacting an isocyanate-terminated sulfur-containing polymer of Formula (II) with a diamine such as 4- (amino ethyl) aniline to provide the sulfur-containing polymer terminated by corresponding amine of Formula (III). Amine-terminated sulfur polymers of Formula (III) can also be obtained by reacting a sulfur-containing polymer of Formula (I) with an amino substituted benzoate such as ethyl 4-amino-benzoate in the presence of Bu2SnO or NaOMe at elevated temperature to provide the corresponding amine-terminated sulfur-containing polymer of Formula (III). Amine-terminated sulfur polymers of Formula (III) can also be prepared by reacting a tosyl ester of a sulfur-containing polymer of Formula (III) with an amine-containing compound such as aniline in an organic solvent at elevated temperature to provide the terminated sulfur-containing polymer corresponding amine of Formula (III).
[0149] Sulfur-containing polymers terminated by thiol of Formula (IV) can be prepared by reacting a vinyl-terminated sulfur-containing polymer of Formula (IV) such as ethyl 2-isocyanate methacrylate adduct or allyl isocyanate adduct disclosed herein with a dithiol such as DMDO. Thiol-terminated polymers terminated by Formula (IV) thiol can also be prepared by reacting a tosyl ester of a sulfur-containing polymer of Formula (I) with NaSH in the presence of MeN (Bu) 3 + Cl- in water to provide the sulfur-containing polymer terminated by corresponding Formula (IV) thiol. Alternatively, a tosyl ester of a sulfur-containing polymer of Formula (I) can react with thio-urea in the presence of MeN (Bu) 3 + Cl- in water to provide a tosylate salt of the thio-urea adduct, which can then react in the presence of a base at elevated temperature to provide the corresponding sulfur-terminated polymer of Formula (IV). Alternatively, to obtain thiol-terminated polymers containing sulfur of Formula (IV), a sulfur-containing polymer of Formula (I) can first react with a diisocyanate such as TDI in the presence of dibutyl tin dilaurate at a temperature of 75 ° C to 80 ° C to provide the corresponding thiol-terminated sulfur-containing polymer of Formula (IV). The isocyanate-terminated sulfur-containing polymer of Formula (IV) can then be reacted with an alkanol mercapto such as 2-mercapto-ethanol or 3-mercapto-propanol to provide the corresponding Formula (IV) thiol-terminated sulfur-containing polymer.
[0150] Formula (II) isocyanate-terminated sulfur-containing polymers can be prepared, for example, by reacting a sulfur-containing polymer of Formula (II) with a diisocyanate such as TDI, ISONATE ™ 143L (polycarbodiimide-modified diphenyl methane diisocyanate) , DESMODUR® N3400 (1,3-bis (6-isocyanate-hexyl-1,3-diazetidine-2,4-dione), DESMODUR® I (isophorone diisocyanate, IPDI), or DESMODUR® W (H12MDI), optionally in the presence of a catalyst such as dibutyl tin dilaurate, at a temperature of 70 ° C to 80 ° C. Isocyanate-terminated sulfur-containing polymers can be used as intermediates in the synthesis of other terminally modified sulfur-containing polymers such as certain sulfur-containing polymers amine-terminated and thiol-terminated provided by the present disclosure Properties of multifunctional polymers containing sulfur with terminal modification [0151] In certain embodiments, multifunctional polymers Sulfur containing terminal modifications provided by the present disclosure are liquids at room temperature. In addition, in certain embodiments, polymers containing sulfur have a viscosity, in 100% solids, less than or equal to 500 Poise, such as 10 to 300 Poise or, in some cases, 100 to 200 Poise, at a temperature of 25 ° C and a pressure of 760 mm Hg according to ASTM D-2849 § 79-90 using a Brookfield CAP 2000 viscometer. In certain embodiments, the glass transition temperature (Tg) of sulfur-containing polymer provided by this disclosure is less than or equal to -50 ° C.
[0152] Multifunctional sulfur-containing polymers provided by the present disclosure can be used in compositions, such as sealants, coatings, and / or electrical fill compositions that include one or more sulfur-containing polymers provided by the present disclosure. A sealing composition refers to a composition capable of producing a film that has the ability to withstand operating conditions, such as humidity and temperature, and at least partially block the transmission of materials, such as water, fuel, and other liquids and gases. In certain embodiments, sealing compositions provided by the present disclosure are useful, for example, as aerospace seals and as coatings for fuel tanks.
[0153] In certain embodiments, a composition comprises a hydroxyl-terminated sulfur-containing polymer of Formula (I) or a sulfur-containing polymer produced by the reaction of (a) a sulfur-containing diol; (b) a polyol containing at least three hydroxyl groups per polyol molecule; and (c) a reagent selected from an aldehyde, a ketone, and a combination thereof; a compound having a group that is reactive with hydroxyl groups; and a healing agent. In certain embodiments, a group that is reactive with hydroxyl groups is selected from an isocyanate, an alcohol, and a thiol.
[0154] In certain embodiments, a composition comprises a terminally modified sulfur-containing polymer of Formula (II) or a terminally-modified sulfur-containing polymer, which is the reaction product of any of the reactions disclosed herein, and at least one agent curing agent that is reactive with terminally modified sulfur-containing polymer.
[0155] In certain embodiments, the compositions provided by the present disclosure comprise, in addition to the sulfur-containing polymer of Formula (II), or the reaction products of a reaction disclosed herein, one or more additional sulfur-containing polymers. A sulfur-containing polymer can be any polymer having at least one sulfur atom in the repeating unit, including polymeric thiols, polythiols, thioethers, sulfur-containing polymers, poliforms, and polysulfides. When used herein, a "thiol" refers to a compound comprising a thiol or mercaptan group, that is, a -SH group, which as the only functional group or in combination with other functional groups, such as hydroxyl groups, as is the case, for example, with thioglycerols. A polythiol refers to a compound having more than one -SH group, such as a higher functionality dithiol or polythiol. Such thiol groups are typically terminal and / or pendant groups such that they have an active hydrogen that is reactive with other functional groups. When used herein, the term "polysulfide" refers to any compound that comprises a sulfur-sulfur (-S-S-) bond. A polythiol may comprise either a terminal and / or pendent sulfur (-SH) or a non-reactive sulfur atom (-S- or -S-S-). Thus, the term polythiol generally encompasses polymers containing sulfur and polysulfides. Examples of additional sulfur-containing polymers useful in compositions provided by the present disclosure include, for example, those disclosed in U.S. Patent Nos. 6,172,179, 6,509,418, and 7,009,032.
[0156] In certain embodiments, compositions provided by the present disclosure comprise a polyetherether having the structure: in which: R1 is selected from C2-6 alkanodiyl, C6-8 cycloalkanodiyl, C6-10 cycloalkylalkyl, - [(-CH2 -) sX-] q - (- CH2) -) r-, and - [(- CH2-) s "X-] q - (- CH2) -) r- in which at least one -CH2- unit is replaced with a methyl group; R is selected from C2-6 alkanediyl, C6-8 cycloalkanediyl, C6-10 cycloalkylalkylalkyl, - [(-CH2-) sX-] q - (- CH2) -) r-; X is selected from O, S, and -NR- where R is selected from hydrogen or methyl; t is an integer selected from 0 to 10; u is an integer selected from 1 to 60; r is an integer selected from 2 to 10. Such polythioethers are described in US Patent No. 6,172,179, which is incorporated herein entirely by reference. The one or more additional sulfur-containing polymers may be difunctional or multifunctional, for example, having 3 to 6 terminal groups, or a mis their structure.
[0157] In certain embodiments, the compositions provided by the present disclosure comprise from 10% by weight to 90% by weight of a sulfur-containing polymer provided by the present disclosure, from 20% by weight to 80% by weight, 30% by weight at 70% by weight, and in certain embodiments, from 40% by weight to 60% by weight, where the weight percentages are based on the total weight of all non-volatile components of the composition (i.e., dry weight). In certain embodiments, the compositions provided by the present disclosure comprise 10% by weight to 90% by weight of a sulfur-containing polymer provided by the present disclosure, from 20% by weight to 90% by weight, from 30% by weight to 90% by weight. weight, from 40% by weight to 90% by weight, from 50% by weight to 90% by weight, from 60% by weight to 90% by weight, from 70% by weight to 90% by weight, and in certain embodiments, from 80% by weight to 90% by weight, where weight percentages are based on the total weight of all non-volatile components of the composition (i.e., dry weight).
[0158] Suitable curing agents in compositions provided by the present disclosure include compounds that are reactive with the sulfur-containing polymer terminal groups of Formula (II) or provided by the reactions disclosed herein, such as compounds that are reactive with hydroxyl groups, vinyl groups , epoxy groups, thiol groups, amine groups, or isocyanate groups.
[0159] Examples of suitable curing agents that are reactive with hydroxyl groups include diisocyanates and polyisocyanates, examples of which are disclosed herein. [0160] Examples of suitable curing agents that are reactive with vinyl groups include dithols and polythioles, examples of which are disclosed herein.
[0161] Sulfur-containing polymers terminated by silyl provided by the present disclosure hydrolyze in the presence of water inducing self-polymerization via condensation. It can be understood that as the curing agent for silyl-terminated sulfur-containing polymers can be atmospheric moisture, it is not necessary to include a curing agent in a curable composition containing silyl-terminated sulfur-containing polymers. Therefore, compositions comprising sulfur-containing polymers terminated by silyl and a curing agent for the silyl group refer to atmospheric humidity. Compositions comprising sulfur-containing polymers terminated by silyl may further comprise a catalyst. Catalysts for use with silyl-terminated sulfur-containing polymers include organic titanium compounds such as titanium tetraisopropoxy, titanium tetra-tert-butoxy, titanium di (isopropoxy) bis (acetyl acetate); organic tin compounds such as dibutyl tin dilaurate, dibutyl tin bis acetyl aceto, and tin octylate; metallic dicarboxylates such as lead dioctylate; organic zirconium compounds such as zirconium tetra acetyl acetonate, and organic aluminum compounds such as aluminum triacetyl acetonate. Specific examples include titanium di (isopropoxy) bis (ethyl acetate), titanium di (isopropoxy) bis (acetyl acetate), and titanium dibutoxy bis (methyl acetate).
[0162] Examples of suitable curing agents that are reactive with epoxy groups include amines such as diethylene triamine (DTA), triethylene tetramine (TTA), tetraethylene pentamine (TEPA), dipropene-diamine (DPDA), diethylamino propylamine (DEAPA), N-aminoethyl piperazine (N-AEP), isophorone diamine (IPDA), m-xylene diamine, diamine diphenyl methane (DDM), and diamine diphenyl sulfone (DDS); aromatic amines; satinin; polyamines; polyamides; phenolic resins; anhydrides such as phthalic anhydride, trimellitic anhydride, pyromelitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimethylate, glycerol tris trimellate, maleic anhydride, tetrahydrophthalic anhydride, tetrahydrophthalic methyl anhydride; polimercaptanas; polysulfides; ultraviolet curing agents such as diphenyl iodine hexafluorine phosphate, triphenyl sulfonium hexafluror phosphate; and other curing agents known to those skilled in the art.
[0163] Examples of suitable curing agents that are reactive with thiol groups include diepoxides.
[0164] Examples of suitable curing agents that are reactive with amine groups include isocyanates, diisocyanates, and polymeric polyisocyanates, non-limiting examples of which include polyisocyanates having selected urethane (-NH-C (O) -O) backbone bonds -), thiourethane (-NH-C (O) -S-) bonds, thiocarbamate (- NH-C (S) -O-) bonds, dithiourethane (-NH-C (S) -S-) bonds, and combinations any of the above.
[0165] Examples of suitable curing agents that are reactive with isocyanate groups include diamines, polyamines, polythioles, and polyols, including those disclosed herein.
[0166] Compositions provided by the present disclosure may contain from 90% to 150%, from 95% to 125%, and in certain embodiments, from 95% to 105% of the stoichiometric quantity, where the stoichiometric quantity is the proportion of the number of groups reactive isocyanates for the number of groups reactive with isocyanate groups. For example, a composition containing the same number of isocyanate groups and amine groups before the reaction will have a stoichiometric amount of isocyanate groups and amine groups.
[0167] Compositions provided by the present disclosure may contain one or more different types of cargo. Suitable fillers include those commonly known in the art, including inorganic fillers, such as carbon black and calcium carbonate (CaCO3), and light weight fillers. Appropriate light weight loads include, for example, those described in U.S. Patent No. 6,525,168. In certain embodiments, a composition includes from 5% by weight to 60% by weight of the cargo or cargo combination, from 10% by weight to 50% by weight, and in certain embodiments from 20% by weight to 40% by weight , based on the total dry weight of the composition.
[0168] As can be understood, the sulfur-containing polymers, curing agents, and fillers employed in a composition, as well as any additives, can be selected so as to be compatible with each other.
[0169] Compositions provided by the present disclosure may include one or more colorants, thixotropic agents, accelerators, retardants, adhesion promoters, solvents, masking agents or a combination of any of the foregoing.
[0170] When used here, the term "colorant" means any substance that imparts color and / or other opacity and / or other visual effect to the composition. The dye can be in any suitable form, such as discrete particles, dispersions, solutions and / or flakes. In a composition, a single colorant or a mixture of two or more colorants can be used.
[0171] Examples of colorants include pigments, dyes and dyes, such as those used in the paint industry or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include, for example, a finely divided solid powder that is insoluble, but capable of moistening under conditions of use. A colorant can be organic or inorganic and can be agglomerated or non-agglomerated. The dyes can be incorporated into a composition using a grinding vehicle, such as an acrylic grinding vehicle.
[0172] Exemplary pigments and / or pigment compositions include crude carbazole dioxazin, azo, mono-azo, diazo, naphthol AS, salt-type (flakes), benzimidazolone, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, dicetopyrrole pyrrole, thio-indigo, anthraquinone, indantrone, anthrapyrimidine, flavantrone, pyrantrone, antantrone, dioxazine, triaryl carbonium, quinophthalone pigments, pyrrole pyrrole red (“DPPBO red”), titanium dioxide, carbon black and mixtures of the same.
[0173] Exemplary dyes include, but are not limited to, those that are solvent based and / or aqueous such as phthalus green or blue, iron oxide, bismuth vanadate, anthraquinone, quinacridone and perylene.
[0174] Exemplary dyes include, but are not limited to, pigments dispersed in water-based or water-miscible vehicles such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions division of Eastman Chemical, Inc.
[0175] As noted above, the dye can be in the form of a dispersion including, but not limited to, a dispersion of nanoparticles. Nanoparticle dispersions can include one or more highly dispersed nanoparticle dyes and / or dye particles that produce a desired effect of visible color and / or opacity and / or visual effect. Dispersions of nanoparticles can include dyes such as pigments or dyes having a particle size less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by grinding stock organic or inorganic pigments with grinding media having a particle size less than 0.5 nm. Dispersions of nanoparticles and methods for preparing them are identified in U.S. Patent No. 6,875,800. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and / or chemical friction (i.e., partial dissolution). In order to minimize the re-agglomeration of nanoparticles within the coating, a dispersion of resin coated nanoparticles can be used. When used herein, a "dispersion of resin coated nanoparticles" refers to a continuous phase in which discrete "composite nanoparticles" are dispersed that comprise a nanoparticle and a resin coating on the nanoparticle. Exemplary dispersions of nanoparticles coated with resin and methods for preparing them are identified in U.S. patent 7,438,972.
[0176] Exemplary special effect compositions that can be used in the compositions of the present invention include pigments and / or compositions that produce one or more appearance effects such as reflectance, perolescence, metallic luster, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and / or color change. Additional special effect compositions can provide other noticeable properties, such as opacity or texture. In a non-limiting embodiment, special effect compositions can produce a color change such that the color of the coating changes when the coating is viewed at different angles. Exemplary special effect compositions are identified in U.S. Patent No. 6,894,086. Exemplary color effect compositions are identified. Additional may include clear coated mica and / or synthetic mica, coated silica, coated alumina. transparent liquid crystal pigment, liquid crystal coating, and / or any composition in which the interference results from a refractive index differential within the material and not because of the refractive index differential between the material surface and the air.
[0177] In general, a colorant can comprise from 1 to 65 weight percent of a composition, such as from 3 to 40 weight percent or from 5 to 35 weight percent, based on the total dry weight of the composition .
[0178] Thixotropes, for example, silica, are often used in an amount of 0.1 to 5 weight percent, based on the total dry weight of the composition.
[0179] Curing catalysts known in the art, such as amines, can be present in an amount of 0.15 weight percent, based on the total weight of the composition. Examples of suitable catalysts include 1,4-diaza-bicyclo [2.2.2] octane (DABCO®, commercially available from Air Products, Chemical Additives Division) and DMP-30® (an accelerant composition including 2,4,6-tris ( dimethylamino methyl) phenol).
[0180] Retardants, such as stearic acid, are also often used in an amount of 0.1 to 5 weight percent, based on the total dry weight of the composition. Adhesion promoters can be present in an amount of 0.1 to 15 weight percent of a composition, based on the total dry weight of the composition. Examples of adhesion promoters include phenolics, such as METHYLON phenolic resin obtainable from Occidental Chemicals, and organosilanes, such as epoxy, mercapto or amino silanes, such as SILQUEST A-187 and SILQUEST A-1100 obtainable from Momentive Performance Materials. Masking agents, such as pine fragrance or other fragrances, which can be useful in covering any low odor level of the composition, can be present in an amount of 0.1 to 1 weight percent, based on the total dry weight of the composition. composition.
[0181] In certain embodiments, the compositions provided by the present disclosure may comprise a plasticizer that can facilitate the use of sulfur-containing polymers having a glass transition temperature, Tg, which is more than commonly useful in an aerospace seal. For example, the use of a plasticizer can effectively reduce the Tg of a composition, and therefore, increase the low temperature flexibility of the cured polymerizable composition beyond what would be expected based on the Tg of the sulfur-containing polymers alone. Suitable plasticizers in certain embodiments of the compositions include, for example, phthalate esters, chlorinated paraffins, and hydrogenated terphenyls. A plasticizer or combination of plasticizers can make up 1 to 40 weight percent of a composition. In certain embodiments, a composition can comprise one or more organic solvents, such as isopropyl alcohol, in an amount ranging, for example, from 0 to 15 weight percent based on the total weight of the composition, from 0 weight% to 10% by weight, or from 0% by weight to 5% by weight, based on the non-dry weight of the composition.
[0182] In certain embodiments, the compositions provided by the present disclosure are substantially free or, in some cases, completely free of any solvent, such as an organic solvent or an aqueous solvent, i.e., water. In certain embodiments, differently stated, the compositions provided by the present disclosure are substantially 100% solids. [0183] In certain embodiments, compositions, such as sealing compositions, may be provided as multi-component compositions, such as two-component compositions, in which one component comprises one or more sulfur-containing polymers provided by the present disclosure and a second component comprises a or more curing agents for the one or more sulfur-containing polymers. When desired or necessary, additives and / or other materials can be added to any of the components. The two components can be combined and mixed before use. In certain incorporations, the use time of the polymer mixture containing sulfur and curing agent is at least 30 minutes, at least 1 hour, at least 2 hours, and in certain incorporations, more than 2 hours, where the Usage refers to the time interval over which the composition remains suitable for use as a sealant after mixing. [0184] Compositions provided by the present disclosure can be applied to any one of a variety of substrates. Examples of substrates, on which a composition can be applied, include titanium, stainless steel, and aluminum, which can be anodized, coated with primer or coated with chromate or with organic compound; epoxy; urethane; graphite; fiberglass composite; KEVLAR®; acrylics; and polycarbonates.
[0185] The compositions provided by the present disclosure can be applied on the surface of a substrate or on an underlying layer by any suitable coating process known to those skilled in the art.
[0186] In certain embodiments, the compositions provided by this disclosure are resistant to fuels. When used here, the term “fuel resistant” means that a composition, when applied to a substrate and cured, can provide a cured product, such as a sealant, that has a percentage of volumetric swelling less than or equal to 40%, in some cases less than or equal to 25%, in some cases less than or equal to 20%, in other cases even less than or equal to 10%, after immersion for one week at 60 ° C (140 ° F) and ambient pressure in reference fluid JRF Type I jet (JRF) according to methods similar to those described in ASTM D792 or AMS 3269, incorporated herein by reference. JRF Type I jet reference fluid, when used here to determine fluid resistance, has the following composition ( see AMS 2629, published on July 1, 1989), § 3.1.1 etc., obtainable from SAE (Society of Automotive Engineers): toluene: 28 ± 1% by volume; cyclohexane (technical): 34 ± 1% by volume; isoctane: 38 ± 1% by volume; ditherciobutyl disulfide: 1 ± 0.005% by volume. [0187] In certain embodiments, the compositions provide a cured product, such as a sealant, exhibiting a tensile strength of at least 400 psi and an elongation of at least 100% when measured according to the procedure described in AMS 3279, § 3.3.17.1, test procedure AS127 / 1, § 7.7.
[0188] In certain embodiments, the compositions provide a cured product, such as a sealant, exhibiting an overlapping shear strength greater than 200 psi and in some cases at least 400 psi when measured according to the procedure described in SAE AS5127 / 1 paragraph 7.8. [0189] In certain embodiments, a cured seal comprising a sulfur-containing polymer provided by the present disclosure meets or exceeds the requirements for aerospace sealants set out in MAS 3277.
[0190] In addition, methods are provided to seal an opening using a composition provided by the present disclosure. These methods comprise, for example, applying a composition provided by the present disclosure to a surface to seal an opening; and cure the composition. In certain embodiments, a composition can be cured under ambient conditions, where ambient conditions refer to a temperature of 20 ° C to 25 ° C, and atmospheric humidity. In certain embodiments, a composition can be cured under ambient conditions covering a temperature of 0 ° C to 100 ° C and a relative humidity of 0% to 100%. In certain embodiments, a composition can be cured at a higher temperature such as at least 30 ° C, at least 40 ° C, and in certain embodiments, at least 50 ° C. In certain embodiments, a composition can be cured by exposure to actinic radiation such as ultraviolet radiation. As will also be considered, the methods can be used to seal openings in aerospace vehicles. Examples [0191] The following examples further illustrate embodiments provided by the present disclosure, which describe the synthesis, properties, and uses of certain sulfur-containing polymers. It will become obvious to those skilled in the art that many modifications of both materials and methods can be practiced without departing from the scope of the disclosure.
Example 1 Synthesis of sulfur-containing trifunctional polymer [0192] A 3 L round bottom flask with 4 necks with thio-diglycol (1,215.81 g), paraformaldehyde (95% purity) (300.63 g), was loaded, AMBERLYST ™ 15 (212.80 g, Dow Chemical Company), 1,3,5-tris (2-hydroxy ethyl) isocyanurate (13.14 g, Aldrich), and toluene (500 ml). The flask was equipped with a thermal blanket, thermocouple, temperature controller, and a Dean-Stark adapter equipped with a reflux condenser, a dropper funnel and an inlet for positive nitrogen pressure. During this period, the collected water was removed periodically from the Dean-Stark adapter. Nitrogen stirring was started and the batch was heated to 120 ° C and maintained at 120 ° C for about 10 hours. Then, the reaction mixture was cooled to room temperature and it was suction filtered through a coarse fried Büchner funnel (600 mL volume) with a 9.0 cm diameter Whatman GF / A filter paper over the fries. The flask and filter cake were washed with 500 ml of toluene. A filtrate was obtained. Then, the filtrate was vacuum extracted using a 2 L round-bottom flask (rotary evaporator, 5 Torr final vacuum, 90 ° C water bath). A yellow viscous polymer (993.53 g) was obtained. The resulting poliform polymer had a hydroxyl number of 25.3 and a viscosity of 214 Poise.
Example 2 Synthesis of sulfur-containing trifunctional polymer [0193] A 3 L round-bottom flask with 4 necks with thio-diglycol (1,209.67 g), paraformaldehyde (95% purity) (300.48 g), was loaded, AMBERLYST ™ 15 (26.18 g, Dow Chemical Company), 1,3,5-tris (2-hydroxy ethyl) isocyanurate (20.9 g, Aldrich), and toluene (500 ml). The flask was equipped with a thermal blanket, thermocouple, temperature controller, and a Dean-Stark adapter equipped with a reflux condenser, a dropper funnel and an inlet for positive nitrogen pressure. During this period, the collected water was removed periodically from the Dean-Stark adapter. Nitrogen stirring was started and the batch was heated to 120 ° C and maintained at 120 ° C for about 10 hours. Then, the reaction mixture was cooled to room temperature and it was suction filtered through a coarse fried Büchner funnel (600 mL volume) with a 9.0 cm diameter Whatman GF / A filter paper over the fries. The flask and filter cake were washed with 500 ml of toluene. A filtrate was obtained. Then, the filtrate was vacuum extracted using a 2 L round-bottom flask (rotary evaporator, 5 Torr final vacuum, 90 ° C water bath). A yellow viscous polymer (953.33 g) was obtained. The resulting poliform polymer had a hydroxyl number of 22.8 and a viscosity of 377 Poise.
Example 3 Synthesis of sulfur-containing trifunctional polymer [0194] A 3 L round-bottom flask with 4 necks with thio-diglycol (1,197.45 g), paraformaldehyde (95% purity) (300.83 g), was loaded, AMBERLYST ™ 15 (213.06 g, Dow Chemical Company), 1,3,5-tris (2-hydroxy ethyl) isocyanurate (52.58 g, Aldrich), and toluene (500 ml). The flask was equipped with a thermal blanket, thermocouple, temperature controller, and a Dean-Stark adapter equipped with a reflux condenser, a dropper funnel and an inlet for positive nitrogen pressure. During this period, the collected water was removed periodically from the Dean-Stark adapter. Nitrogen stirring was started and the batch was heated to 120 ° C and maintained at 120 ° C for about 10 hours.
Then, the reaction mixture was cooled to room temperature and it was suction filtered through a coarse fried Büchner funnel (600 mL volume) with a 9.0 cm diameter Whatman GF / A filter paper over the fries. The flask and filter cake were washed with 500 ml of toluene. A filtrate was obtained. Then, the filtrate was vacuum extracted using a 2 L round-bottom flask (rotary evaporator, 5 Torr final vacuum, 90 ° C water bath). A yellow viscous polymer (1,039.64 g) was obtained. The resulting poliform polymer had a hydroxyl number of 23.2 and a viscosity of 942 Poise.
Example 4 Acrylate-terminated sulfur-containing polymer [0195] The sulfur-containing polymer from Example 1 (222.40 g) was loaded into a 500-ml round-bottomed flask with 4 necks. The flask was equipped with a thermal blanket, thermocouple, temperature controller, an inlet for positive nitrogen pressure, and a mechanical stirrer (PTFE support and mixer). The polymer was stirred at ca. 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of ethyl isocyanate methacrylate (15.68 g) and a 0.05% solution of dibutyl tin dilaurate dissolved in methyl ethyl ketone (2 , 51 g). The reaction mixture was kept at 76.6 ° C for 5 h and then cooled to room temperature. The resulting acrylate-terminated polymer (222.08 g) had a viscosity of 299 Poise.
Example 5 Acrylate-terminated sulfur-containing polymer [0196] The sulfur-containing polymer of Example 2 (247.26 g) was loaded into a 500 ml round-bottomed flask with 4 necks. The flask was equipped with a thermal blanket, thermocouple, temperature controller, an inlet for positive nitrogen pressure, and a mechanical stirrer (PTFE support and mixer). The polymer was stirred at ca. 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of ethyl isocyanate methacrylate (15.61 g) and a 0.05% solution of dibutyl tin dilaurate dissolved in methyl ethyl ketone (2 , 66 g). The reaction mixture was kept at 76.6 ° C for 5 h and then cooled to room temperature. The resulting acrylate-terminated polymer (242.14 g) had a viscosity of 439 Poise.
Example 6 Acrylate-terminated sulfur-containing polymer [0197] The sulfur-containing polymer of Example 3 (243.71 g) was loaded into a 500 ml round-bottomed flask with 4 necks. The flask was equipped with a thermal blanket, thermocouple, temperature controller, an inlet for positive nitrogen pressure, and a mechanical stirrer (PTFE support and mixer). The polymer was stirred at ca. 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of ethyl isocyanate methacrylate (15.58 g) and a 0.05% solution of dibutyl tin dilaurate dissolved in methyl ethyl ketone (2 , 74 g). The reaction mixture was kept at 76.6 ° C for 5 h and then cooled to room temperature. The resulting acrylate-terminated polymer (226.09 g) had a viscosity of 1,026 Poise.
Example 7 TMI-terminated sulfur-containing polymer
[0198] The sulfur-containing polymer of Example 1 (226.6 g) was loaded into a 500 ml round-bottomed flask with 4 necks. The flask was equipped with a thermal blanket, thermocouple, temperature controller, an inlet for positive nitrogen pressure, and a mechanical stirrer (PTFE support and mixer). The polymer was stirred at ca. 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of 3-isopropenyl-a isocyanate, α-dimethyl benzyl (TMI) (20.25 g, Cytec Industries) and a 0 05% dibutyl tin dilaurate dissolved in methyl ethyl ketone (2.47 g). The reaction mixture was kept at 76.6 ° C for 6 hours and then cooled to room temperature. The resulting TMI-terminated polymer (217.32 g) had a viscosity of 378 Poise. Example 8 TMI-terminated sulfur-containing polymer
[0199] The sulfur-containing polymer of Example 3 (243.70 g) was loaded into a 500 ml round-bottomed flask with 4 necks. The flask was equipped with a thermal blanket, thermocouple, temperature controller, an inlet for positive nitrogen pressure, and a mechanical stirrer (PTFE support and mixer). The polymer was stirred at ca. 200 rpm and heated to 76.6 ° C (170 ° F), followed by the addition of 3-isopropenyl-a, α-dimethyl benzyl (TMI) isocyanate (20.18 g, Cytec Industries) and a 0 ° solution, 05% dibutyl tin dilaurate dissolved in methyl ethyl ketone (2.62 g). The reaction mixture was kept at 76.6 ° C for 6 hours and then cooled to room temperature. The resulting TMI-terminated polymer (230.42 g) had a viscosity of 1.261 Poise.
Example 9 Cure of polymer containing sulfur terminated by acrylate [0200] The curing reaction was carried out in a 100 g plastic container equipped with a lid. The acrylate-terminated sulfur polymer of Example 4 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) were manually mixed in the container. Then, the container was placed in a speed mixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer was poured into a metallic lid (5 inches in diameter) (treated with Valspar 225 release agent), and placed under ultraviolet radiation for 30 seconds, after which the polymer was completely cured. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300 W H bulb, which produced UV wavelengths ranging from 200 nm to 450 nm. A total UV energy dosage of 3.103 J / cm2 was measured using a UV feed unit (EIT, INC., Sterling, VA) was applied to the polymeric composition. A ½ inch thick disc of cured polymer was obtained. The polymer hardness was measured with a durometer and 53 Shore A was obtained. The hardness was determined according to ASTM D 2240.
Example 10 Curing of acrylate-terminated sulfur-containing polymer [0201] The curing reaction was carried out in a 100 g plastic container equipped with a lid. The acrylate-terminated sulfur-containing polymer of Example 5 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) were manually mixed in the container. Then, the container was placed in a speed mixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer was poured into a metallic lid (5 inches in diameter) (treated with Valspar 225 release agent), and placed under ultraviolet radiation for 30 seconds, after which the polymer was completely cured. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300 W H bulb, which produced UV wavelengths ranging from 200 nm to 450 nm. A total UV energy dosage of 3.103 J / cm2 was measured using a UV feed unit (EIT, INC., Sterling, VA) was applied to the polymeric composition. A ½ inch thick disc of cured polymer was obtained. The polymer hardness was measured with a durometer and 51 Shore A was obtained. The hardness was determined according to ASTM D 2240.
Example 11 Curing of acrylate-terminated sulfur-containing polymer [0202] The curing reaction was carried out in a 100 g plastic container equipped with a lid. The acrylate-terminated sulfur polymer of Example 6 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) were manually mixed in the container. Then, the container was placed in a speed mixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer was poured into a metallic lid (5 inches in diameter) (treated with Valspar 225 release agent), and placed under ultraviolet radiation for 30 seconds, after which the polymer was completely cured. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300 W H bulb, which produced UV wavelengths ranging from 200 nm to 450 nm. A total UV energy dosage of 3.103 J / cm2 was measured using a UV feed unit (EIT, INC., Sterling, VA) was applied to the polymeric composition. A ½ inch thick disc of cured polymer was obtained. The polymer hardness was measured with a durometer and 54 Shore A was obtained. The hardness was determined according to ASTM D 2240.
Example 12 TMI-terminated sulfur-containing polymer cure
[0203] The curing reaction was carried out in a 100 g plastic container equipped with a lid. The TMI-terminated sulfur-containing polymer described in Example 7 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) were manually mixed in the container. Then, the container was placed in a speed mixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer was poured into a metallic lid (5 inches in diameter) (treated with Valspar 225 release agent), and placed under ultraviolet radiation for 30 seconds, after which the polymer was completely cured. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300 W H bulb, which produced UV wavelengths ranging from 200 nm to 450 nm. A total UV energy dosage of 3.103 J / cm2 was measured using a UV feed unit (EIT, INC., Sterling, VA) was applied to the polymeric composition. A 1 mm thick disc of cured polymer was obtained.
Example 13 TMI-terminated sulfur-containing polymer cure
[0204] The curing reaction was carried out in a 100 g plastic container equipped with a lid. The TMI-terminated sulfur-containing polymer described in Example 8 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) were manually mixed in the container. Then, the container was placed in a speed mixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer was poured into a metallic lid (5 inches in diameter) (treated with Valspar 225 release agent), and placed under ultraviolet radiation for 30 seconds, after which the polymer was completely cured. A Super Six curing unit (Fusion Systems Inc.) was used to provide UV radiation. The curing unit was equipped with a 300 W H bulb, which produced UV wavelengths ranging from 200 nm to 450 nm. A total UV energy dosage of 3.103 J / cm2 was measured using a UV feed unit (EIT, INC., Sterling, VA) was applied to the polymeric composition. A 1 mm thick disc of cured polymer was obtained.
[0205] Finally, it should be noted that there are alternative ways to implement the incorporations disclosed here. Consequently, the mergers present are considered illustrative and not restrictive. In addition, the claims are not limited to the details given here, and enable its full scope and equivalents thereof.

权利要求:
Claims (14)
[1]
1. Sulfur-containing polymer, characterized by the fact that it comprises the reaction products of reagents comprising: (a) a sulfur-containing diol; (b) a polyol containing at least three hydroxyl groups per polyol molecule; and (c) a reagent selected from an aldehyde, a ketone, and a combination thereof.
[2]
2. Sulfur-containing polymer according to claim 1, characterized in that the sulfur-containing diol comprises the structure: in which: p is selected from 1 and 2; and each R1 is, independently, C2-6 alkanediyl; or the polyol comprises from 3 to 6 hydroxyl groups per molecule.
[3]
3. Sulfur-containing polymer according to claim 1, characterized by the fact that it has the structure of Formula (I): in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkanediyl; each R is independently selected from hydrogen, C1-6 alkyl, substituted alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), substituted alkyl (C6-12 cycloalkyl), substituted alkyl (C6-12 cycloalkyl), cycloalkyl C3-12, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a m-valent relative Z (OH) polyol.
[4]
4. Sulfur-containing polymer with terminal modification, characterized by the fact that it comprises the reaction products of reagents comprising: (a) a sulfur-containing polymer of Formula (I): in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkanediyl; 3 each R is independently selected from hydrogen, C1-6 alkyl, substituted alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), substituted alkyl (C6-12 cycloalkyl), substituted alkyl (C6-12 cycloalkyl), C3-12 cycloalkyl, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; and Z represents the core of a m-valent relative Z (OH) polyol; and (b) a compound selected from: - a compound comprising a vinyl group and a group that is reactive with the hydroxyl groups of the polymer of Formula (I); - a compound comprising a silyl group and a group that is reactive with the hydroxyl groups of the polymer of Formula (I); - a compound comprising an epoxy group and a group that is reactive with the hydroxyl groups of the polymer of Formula (I); - a compound comprising an isocyanate group and a group that is reactive with the hydroxyl groups of the polymer of Formula (I); - a compound comprising an amine group and a group selected from a group that is reactive with an isocyanate group, a group that is reactive with an ethylenically unsaturated group, and a group that is reactive with a tosylate; and - a compound selected from an alkanol mercapto, a metal hydrogen sulfide, and a dithiol.
[5]
5. Terminally modified sulfur-containing polymer according to claim 4, characterized in that (I): (b) is a compound comprising an amine group and a group selected from a group that is reactive with an isocyanate group, a group that is reactive with an ethylenically unsaturated group, and a group that is reactive with a tosylate; and the reagents further comprising: (c) a compound selected from a diisocyanate, an ethylenically activated unsaturated monoisocyanate, and a tosylate; or where (II) (b) is selected from an alkanol mercapto, a metal hydrogen sulfide, and a dithiol; and the reagents further comprise: (c) a compound selected from a diisocyanate, an ethylenically unsaturated monoisocyanate, and a tosylate; or (III): (b) comprising a second compound comprising a terminal group selected from a vinyl group, a silyl group, an epoxy group, and an isocyanate group; and a terminal group selected from a group that is reactive with an isocyanate group, an ethylenically unsaturated group, and a tosylate; and the reagents further comprise: (c) a compound selected from a diisocyanate, an ethylenically unsaturated monoisocyanate, and a tosylate.
[6]
6. Sulfur-containing polymer with terminal modification, according to claim 4, characterized by the fact of having Formula (II): in which: each n is an integer selected from 1 to 50; m is an integer selected from 3 to 6; each p is independently selected from 1 and 2; each R1 is, independently, C2-6 alkanediyl; each R is independently selected from hydrogen, C1-6 alkyl, substituted alkyl (C7-12 phenyl), substituted alkyl (C7-12 phenyl), substituted alkyl (C6-12 cycloalkyl), substituted alkyl (C6-12 cycloalkyl), cycloalkyl C3-12, substituted C3-12 cycloalkyl, C6-12 aryl, and substituted C6-12 aryl; each R5 is -OR5 'in which R5' is selected, regardless of a vinyl-terminated group, a silyl-terminated group, an amine-terminated group, an epoxy-terminated group, a thiol-terminated group, and a group terminated by isocyanate; and Z represents the core of a m-valent relative Z (OH) polyol.
[7]
7. Terminally modified sulfur-containing polymer according to claim 6, characterized in that each R5 is selected from a vinyl-terminated group of Formula (a), Formula (b), Formula (c), Formula (d) , and Formula (e): in which: each R6 is a portion derived from an ethylenically unsaturated monoisocyanate; each R is selected from C2-6 alkanediyl, C2_6 heteroalkanediyl; C6-12 arenodiyl, substituted C6-12 arenodiyl, C6-12 heteroarenodiyl, substituted C6-12 heteroarenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, C3-12 heterocycloalkanodiyl, substituted C3-12 heterocycloalkyniyl, C-18-12 alkane substituted C7-18 arenodiyl heteroalkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane.
[8]
8. Terminally modified sulfur-containing polymer according to claim 6, characterized in that each R5 is selected from a group terminated by silyl of Formula (f) and Formula (g): in which: each R6 is derived from a monoisocyanate ethylenically unsaturated; each R10 is independently selected from C1-6 alkyl, C1-6 alkoxy, C5-6 cycloalkyl, alkyl (C6-i2 cycloalkyl), phenyl, and alkyl (C7-12 phenyl), with at least one R10 being alkoxy C1-6; and each R11 is C1-6 alkanediyl.
[9]
9. Terminally modified sulfur-containing polymer according to claim 6, characterized in that each R5 is selected from an amine-terminated group of Formula (h), Formula (i), Formula (j), Formula (k) , Formula (l), and Formula (m): in which: each R6 is selected from a group derived from a diisocyanate and a group derived from an ethylenically unsaturated monoisocyanate; each R is selected from a bond and C2-6 alkanediyl; each R9 is selected from C2-6 alkanediyl, C2-6 heteroalkanediyl; C6-12 arenodiyl, substituted C6-12 arenodiyl, C6-12 heteroarenodiyl, substituted C6-12 heteroarenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, C3-12 heterocycloalkanodiyl, substituted C3-12 heterocycloalkyniyl, C-18-12 alkane substituted C7-18 arenodiyl heteroalkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane; and 12 each R is selected from hydrogen, C1-6 alkanodiyl, C6-12 arenodiyl, substituted C6-12 arenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, C7-18 arenodiyl alkane, substituted C7-18 alkanodiyl alkane cycloalkanodiyl C4-18, and substituted cycloalkanodiyl alkane C4-18.
[10]
10. Terminally modified sulfur-containing polymer according to claim 6, characterized in that each R5 is selected from an epoxy-terminated group of Formula (n): in which: each R11 and, independently, C1-6 alkanediyl .
[11]
11. Terminally modified sulfur-containing polymer according to claim 6, characterized in that each R5 is selected from a group terminated by the thiol of Formula (o), Formula (p), Formula (q), Formula (r) , Formula (s), Formula (t), Formula (u), and Formula (v): in which: each R6 is selected from a portion derived from a diisocyanate and a portion derived from an ethylenically unsaturated monoisocyanate; each R is selected from C2-14 alkanediyl and C2-14 heteroalkanediyl; and each R9 is selected from C2-6 alkanediyl, C2-6 heteroalkanediyl; C6-12 arenodiyl, substituted C6-12 arenodiyl, C6-12 heteroarenodiyl, substituted C6-12 heteroarenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, C3-12 heterocycloalkanodiyl, substituted C3-12 heterocycloalkyniyl, C-18-12 alkane substituted C7-18 arenodiyl heteroalkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane.
[12]
12. Sulfur-containing polymer with terminal modification, according to claim 6, characterized in that each R5 is selected from a group terminated by the isocyanate of Formula (w) and Formula (x): in which: each R9 is selected from alkanodiyl C2-6, C2-6 heteroalkanediyl; C6-12 arenodiyl, substituted C6-12 arenodiyl, C6-12 heteroarenodiyl, substituted C6-12 heteroarenodiyl, C3-12 cycloalkanodiyl, substituted C3-12 cycloalkanodiyl, C3-12 heterocycloalkanodiyl, substituted C3-12 heterocycloalkyniyl, C-18-12 alkane substituted C7-18 arenodiyl heteroalkane, C4-18 cycloalkanodiyl alkane, and substituted C4-18 cycloalkanodiyl alkane; and each R12 is a group derived from a diisocyanate.
[13]
13. Composition, characterized by the fact that it comprises the terminally modified sulfur-containing polymer, as defined in claims 4 or 6, and a curing agent that is reactive with the terminally-modified sulfur-containing polymer, as defined in claims 4 and 6, respectively.
[14]
14. Opening sealed with a seal, characterized by the fact that the seal comprises the composition, as defined by claim 13.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112013023900B1|2020-03-10|POLYMER CONTAINING SULFUR, POLYMER CONTAINING SULFUR WITH TERMINAL MODIFICATION, COMPOSITION AND OPENING SEALED WITH A SEALER

---

BR112013023772B1|2020-03-10|POLYMER CONTAINING SULFUR WITH TERMINAL MODIFICATION, COMPOSITION AND OPENING SEALED WITH A SEALER

---

ES2768080T3|2020-06-19|Polyurea compositions and methods of use

---

JP6635953B2|2020-01-29|Polyurea compositions and methods of use

同族专利:

---

公开号 | 公开日

---

EP2686369A1|2014-01-22|

---

US9382447B2|2016-07-05|

---

US20150344631A1|2015-12-03|

---

CN103502316A|2014-01-08|

---

US9012592B2|2015-04-21|

---

EP2686369B1|2018-12-19|

---

KR20150027309A|2015-03-11|

---

CN103502316B|2015-09-02|

---

MX2013010652A|2013-10-30|

---

US20150183806A1|2015-07-02|

---

MX349576B|2017-07-27|

---

RU2553658C1|2015-06-20|

---

HK1192269A1|2014-08-15|

---

US9109089B2|2015-08-18|

---

US9260567B2|2016-02-16|

---

AU2012231279B2|2014-05-08|

---

US20120234205A1|2012-09-20|

---

WO2012129088A1|2012-09-27|

---

US20150018550A1|2015-01-15|

---

US20160115350A1|2016-04-28|

---

US8877887B2|2014-11-04|

---

KR20130132652A|2013-12-04|

---

RU2013146510A|2015-05-27|

---

CA2830506C|2015-06-09|

---

JP5921044B2|2016-05-24|

---

CA2830506A1|2012-09-27|

---

KR101797328B1|2017-11-13|

---

ES2713554T3|2019-05-22|

---

AU2012231279A1|2013-10-10|

---

BR112013023900A2|2016-12-13|

---

JP2016053186A|2016-04-14|

---

KR101546174B1|2015-08-20|

---

US8729216B2|2014-05-20|

---

JP2014514377A|2014-06-19|

---

US20140206866A1|2014-07-24|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2466963A|1945-06-16|1949-04-12|Thiokol Corp|Polysulfide polymer|

---

GB850178A|1956-03-23|1960-09-28|Hudson Foam Plastics Corp|Improvements in the manufacture of polyformal materials|

---

DE1262500B|1960-04-09|1968-03-07|Bayer Ag|Process for the production of highly elastic threads or fibers|

---

US3290382A|1963-12-13|1966-12-06|Olin Mathieson|High viscosity sulfur containing polyformals and method|

---

GB1286394A|1969-05-26|1972-08-23|Thiokol Chemical Corp|Polyethers containing gem-dithioether and monosulfide linkages and polyurethanes therefrom|

---

US3647766A|1970-04-23|1972-03-07|Thiokol Chemical Corp|Method of making hydroxyl-terminated polysulfide polymers|

---

US3959277A|1972-07-14|1976-05-25|E. I. Du Pont De Nemours And Company|Diimidazopyrazines and tetracarboxamidopyrazines|

---

US3997613A|1972-10-25|1976-12-14|Reichhold Chemicals, Inc.|Polyacetal and polyketal compositions|

---

US3997612A|1972-10-25|1976-12-14|Reichhold Chemicals, Inc.|Polythiaformal compositions|

---

US3997614A|1972-10-25|1976-12-14|Reichhold Chemicals, Inc.|Polythiaformals|

---

CA1035899A|1973-02-20|1978-08-01|Eugene R. Bertozzi|Process for producing halogen-terminated polysulfide polymers|

---

US3959227A|1973-05-02|1976-05-25|American Cyanamid Company|Polyformals having low methylol end-group content and polyurethanes produced therefrom|

---

US4209426A|1979-05-29|1980-06-24|American Home Products Corporation|Polypeptides related to somatostatin|

---

US4366307A|1980-12-04|1982-12-28|Products Research & Chemical Corp.|Liquid polythioethers|

---

US4320221A|1980-12-12|1982-03-16|The Dow Chemical Company|Addition polymerizable isocyanate-polyol anaerobic adhesives|

---

US4609762A|1984-01-30|1986-09-02|Products Research & Chemical Corp.|Thioethers having a high sulfur content and method therefor|

---

US5225472A|1992-05-19|1993-07-06|Courtaulds Aerospace, Inc.|Low viscosity polythiol and method therefor|

---

JPH08259859A|1995-03-24|1996-10-08|Dainippon Ink & Chem Inc|Magnetic coating composition and its production|

---

US5912319A|1997-02-19|1999-06-15|Courtaulds Aerospace, Inc.|Compositions and method for producing fuel resistant liquid polythioether polymers with good low temperature flexibility|

---

US6372849B2|1997-02-19|2002-04-16|Prc-Desoto International, Inc.|Sealants and potting formulations including polymers produced by the reaction of a polythiol and polyvinyl ether monomer|

---

EP1297095A2|2000-06-30|2003-04-02|PRC-DE Soto International, Inc.|Sealants and potting formulations including mercapto-terminated polymers produced by the reaction of a polythiol and polyvinyl ether monomer|

---

US6509418B1|1997-02-19|2003-01-21|Prc-Desoto International, Inc.|Sealants and potting formulations including mercapto-terminated polymers produced by the reaction of a polythiol and polyvinyl ether monomer|

---

US5959071A|1998-03-31|1999-09-28|Courtaulds Aerospace, Inc.|Composition and method for producing polythioethers having pendent methyl chains|

---

US6383324B1|1999-11-24|2002-05-07|Morton International, Inc.|Polysulfide-based polyurethane sealant for insulating glass|

---

CA2402113A1|2000-03-09|2001-09-13|Jonathan D. Zook|Chemically resistant polythioethers and formation thereof|

---

US6875800B2|2001-06-18|2005-04-05|Ppg Industries Ohio, Inc.|Use of nanoparticulate organic pigments in paints and coatings|

---

US6894086B2|2001-12-27|2005-05-17|Ppg Industries Ohio, Inc.|Color effect compositions|

---

US7009032B2|2002-12-20|2006-03-07|Ppg Industries Ohio, Inc.|Sulfide-containing polythiols|

---

US7067612B2|2003-01-30|2006-06-27|Prc-Desoto International, Inc.|Preformed compositions in shaped form|

---

US20050245695A1|2004-04-30|2005-11-03|Cosman Michael A|Polymer blend and compositions and methods for using the same|

---

US20040220327A1|2003-04-30|2004-11-04|Prc-Desoto International, Inc.|Preformed EMI/RFI shielding compositions in shaped form|

---

US7097883B2|2003-06-05|2006-08-29|Ppg Industries Ohio, Inc.|Low temperature liquid polythioether polymers|

---

US7465778B2|2003-12-19|2008-12-16|Bayer Materialscience Llc|Silante terminated polyurethane|

---

US7438972B2|2004-06-24|2008-10-21|Ppg Industries Ohio, Inc.|Nanoparticle coatings for flexible and/or drawable substrates|

---

DE102004047791B4|2004-10-01|2006-12-14|Thioplast Chemicals Gmbh & Co.Kg|Process for the preparation of polymeric hydroxyalkyl-terminated polysulfides|

---

US20070096396A1|2005-10-27|2007-05-03|Sawant Suresh G|Dimercaptan terminated polythioether polymers and methods for making and using the same|

---

EP2079795A1|2006-10-06|2009-07-22|Teijin Aramid B.V.|Particle-matrix composition coated with mixture comprising polysulfide polymer|

---

DE102006054237A1|2006-11-17|2008-05-21|Bayer Materialscience Ag|Polyurethane-modified alkyd resin dispersions|

---

EP1925628A1|2006-11-23|2008-05-28|Ciba Holding Inc.|Process for polyolefin silane crosslinking|

---

US7879955B2|2007-05-01|2011-02-01|Rao Chandra B|Compositions including a polythioether|

---

US8063140B2|2007-06-13|2011-11-22|Momentive Performance Materials Inc.|Moisture-curable, graft-modified resin composition, process for its manufacture and process for bonding substrates employing the resin composition|

---

US8466220B2|2008-04-24|2013-06-18|PRC DeSoto International, Inc|Thioethers, methods for their preparation, and compositions including such thioethers|

---

CN102498157A|2009-04-29|2012-06-13|汉高公司|Moisture curable polydisulfides|

---

US8541513B2|2011-03-18|2013-09-24|Prc-Desoto International, Inc.|Terminal-modified difunctional sulfur-containing polymers, compositions thereof and methods of use|

---

US8729216B2|2011-03-18|2014-05-20|Prc Desoto International, Inc.|Multifunctional sulfur-containing polymers, compositions thereof and methods of use|WO2014066039A1|2012-10-24|2014-05-01|Prc-Desoto International, Inc.|Uses of uv-curable polythioether sealants for sealing fasteners and for smoothing surfaces|

---

US8729216B2|2011-03-18|2014-05-20|Prc Desoto International, Inc.|Multifunctional sulfur-containing polymers, compositions thereof and methods of use|

---

US8541513B2|2011-03-18|2013-09-24|Prc-Desoto International, Inc.|Terminal-modified difunctional sulfur-containing polymers, compositions thereof and methods of use|

---

US8816044B2|2011-09-21|2014-08-26|PRC DeSoto International, Inc|Flexible polyamines, flexible amine-terminated adducts, compositions thereof and methods of use|

---

US9303149B2|2012-06-21|2016-04-05|Prc-Desoto International, Inc.|Adhesion promoting adducts containing metal ligands, compositions thereof, and uses thereof|

---

EP3063206A2|2013-10-29|2016-09-07|PRC-Desoto International, Inc.|Metal ligand-containing prepolymers, methods of synthesis, and compositions thereof|

---

US9062162B2|2013-03-15|2015-06-23|Prc-Desoto International, Inc.|Metal ligand-containing prepolymers, methods of synthesis, and compositions thereof|

---

US9062139B2|2013-03-15|2015-06-23|Prc-Desoto International, Inc.|Sulfone-containing polythioethers, compositions thereof, and methods of synthesis|

---

US9650552B2|2013-03-15|2017-05-16|Prc-Desoto International, Inc.|Energy curable sealants|

---

KR20160003851A|2013-05-02|2016-01-11|바스프 에스이|Water-emulsifiable isocyanates for coatings having an improved gloss|

---

US8952124B2|2013-06-21|2015-02-10|Prc-Desoto International, Inc.|Bisalkanol-containing polythioethers, methods of synthesis, and compositions thereof|

---

US9611359B2|2013-10-29|2017-04-04|Prc-Desoto International, Inc.|Maleimide-terminated sulfur-containing polymers, compositions thereof, and uses thereof|

---

CN105684074B|2014-01-20|2020-01-07|索尼公司|Image display device, image display method, image output device, image output method, and image display system|

---

US9328275B2|2014-03-07|2016-05-03|Prc Desoto International, Inc.|Phosphine-catalyzed, michael addition-curable sulfur-containing polymer compositions|

---

US9334403B2|2014-03-07|2016-05-10|Prc-Desoto International, Inc.|Moisture-curable urethane-containing fuel resistant prepolymers and compositions thereof|

---

US9518197B2|2014-03-07|2016-12-13|Prc-Desoto International, Inc.|Cure-on-demand moisture-curable urethane-containing fuel resistant prepolymers and compositions thereof|

---

CN103865472B|2014-03-12|2015-12-30|浙江兴宇汽车零部件有限公司|A kind of flame-proof environmental protection polysulfide sealant and production method thereof|

---

US10982105B2|2014-11-24|2021-04-20|Ppg Industries Ohio, Inc.|Methods for reactive three-dimensional printing by extrusion|

---

US9422451B2|2015-01-09|2016-08-23|Prc-Desoto International, Inc.|Low density fuel resistant sulfur-containing polymer compositions and uses thereof|

---

BR112018009837A8|2015-11-19|2019-02-26|Ppg Ind Ohio Inc|catalytic composition and curable composition|

---

US10444626B2|2015-04-27|2019-10-15|Sony Corporation|Hologram recording composition, hologram recording medium, and method of producing hologram recording medium|

---

US9951252B2|2015-08-10|2018-04-24|Prc-Desoto International, Inc.|Moisture-curable fuel-resistant sealant systems|

---

US9777139B2|2015-10-26|2017-10-03|Prc-Desoto International, Inc.|Reactive antioxidants, antioxidant-containing prepolymers, and compositions thereof|

---

US9902799B2|2015-11-11|2018-02-27|Prc-Desoto International, Inc.|Urethane-modified prepolymers containing pendent alkyl groups, compositions and uses thereof|

---

US10035926B2|2016-04-22|2018-07-31|PRC—DeSoto International, Inc.|Ionic liquid catalysts in sulfur-containing polymer compositions|

---

US10370561B2|2016-06-28|2019-08-06|Prc-Desoto International, Inc.|Urethane/urea-containing bis ethers, prepolymers prepared using urethane/urea-containing bis ethers, and uses thereof|

---

US9920006B2|2016-06-28|2018-03-20|Prc-Desoto International, Inc.|Prepolymers exhibiting rapid development of physical properties|

---

RU2728557C1|2016-11-04|2020-07-30|Прк-Десото Интернэшнл, Инк.|Sulphur-containing polyethers, prepolymers containing sulphur-containing polyethers, and use thereof|

---

US10273391B2|2017-01-11|2019-04-30|Prc-Desoto International, Inc.|Delayed curing catalysts for thiol/epoxy reactions|

---

AU2018279855B2|2017-06-09|2020-06-18|Prc-Desoto International, Inc.|Dual cure sealants|

---

US10597565B2|2017-07-07|2020-03-24|Prc-Desoto International, Inc.|Hydraulic fluid and fuel resistant sealants|

---

US10434704B2|2017-08-18|2019-10-08|Ppg Industries Ohio, Inc.|Additive manufacturing using polyurea materials|

---

US10351674B2|2017-10-17|2019-07-16|Prc-Desoto International, Inc.|Sulfur-containing polymeric particles and compositions|

---

US11098222B2|2018-07-03|2021-08-24|Prc-Desoto International, Inc.|Sprayable polythioether coatings and sealants|

---

US10843180B2|2018-10-02|2020-11-24|Prc-Desoto International, Inc.|Delayed cure micro-encapsulated catalysts|

---

US10981158B2|2018-12-20|2021-04-20|Ppg Industries Ohio, Inc.|Catalytic compositions and thiolene-based compositions with extended pot life|

---

EP3924167A1|2019-02-11|2021-12-22|PPG Industries Ohio Inc.|3d printing of seal caps|

---

WO2020167626A1|2019-02-11|2020-08-20|Ppg Industries Ohio, Inc.|Multilayer systems and methods of making multilayer systems|

---

AU2020221466A1|2019-02-11|2021-09-30|Ppg Industries Ohio, Inc.|Methods of making chemically resistant sealing components|

---

US11015097B2|2019-03-06|2021-05-25|Prc-Desoto International, Inc.|Chemically resistant sealant compositions and uses thereof|

---

US11015057B2|2019-04-03|2021-05-25|Prc-Desoto International, Inc.|Dual-cure compositions|

---

US11173692B2|2019-12-19|2021-11-16|Prc-Desoto International, Inc.|Free radical polymerizable adhesion-promoting interlayer compositions and methods of use|

---

US20210189206A1|2019-12-19|2021-06-24|Prc-Desoto International, Inc.|Adhesion-promoting interlayer compositions containing organic titanates/zirconates and methods of use|

---

US20210189069A1|2019-12-19|2021-06-24|Prc-Desoto International, Inc.|Low nucleation temperature polythioether prepolymers and uses thereof|

---

US20210230457A1|2020-01-29|2021-07-29|Prc-Desoto International, Inc.|Photocurable adhesion-promoting compositions and methods of use|

---

US11214666B2|2020-04-15|2022-01-04|Prc-Desoto International, Inc.|Controlling cure rate with wetted filler|

法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-01-21| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-03-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/03/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201161453978P| true| 2011-03-18|2011-03-18|

---

US61/453,978|2011-03-18|

---

US13/413,143|2012-03-06|

---

US13/413,143|US8729216B2|2011-03-18|2012-03-06|Multifunctional sulfur-containing polymers, compositions thereof and methods of use|

---

PCT/US2012/029428|WO2012129088A1|2011-03-18|2012-03-16|Multifunctional sulfur-containing polymers, compositions thereof and methods of use|

---