• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A hydrocarbon polymer comprising two exo-vinylene cyclocarbonate end groups of the following formula (1), process for the preparation and use for the preparation of coating compositions, putties or adhesives: in which F1 is: and F2 is
    公开号:FR3034770A1
    申请号:FR1553103
    申请日:2015-04-10
    公开日:2016-10-14
    发明作者:Guillaume Michaud；Frederic Simon；Stephane Fouquay
    申请人:Bostik SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to hydrocarbon polymers comprising two exo-vinylene cyclocarbonate end groups (also referred to as exo-vinylene cyclocarbonate-terminated hydrocarbon polymers in the present application). The invention also relates to the use of these hydrocarbon polymers for the preparation of polyurethanes, without isocyanate, by reaction with at least one compound comprising at least one amine group. These polyurethanes, once formulated, are intended for use in coating, sealant or adhesive compositions. The synthesis of polyurethanes is usually done by reaction between a diol and a diisocyanate. Diisocyanates are toxic compounds as such, and are generally obtained from phosgene, itself highly toxic by inhalation or contact. The manufacturing process used in the industry generally involves the reaction of an amine with an excess of phosgene to form an isocyanate. The search for alternatives to the synthesis of polyurethanes without the use of isocyanate (or NIPU for "non-Isocyanate Polyurethane" in English, ie "polyurethane without isocyanate"), therefore represents a major challenge. This research has been the subject of numerous studies. The most studied approaches concern the use of polymers capable of reacting with amines or oligomers of amines to form polyurethanes. The patent application WO 2014/091173 in the name of Bostik and the CNRS describes hydrocarbon polymers comprising two terminal groups (2-0x0-1,3-dioxolan-4-yl) which can be obtained by opening polymerization. metathesis ring cycle from at least one cyclic cycloolefin, at least one noncyclic unsaturated chain transfer agent comprising a terminal group (2-0x0-1,3-dioxolan-4-yl), and at least one metathesis catalyst.
    [0002] These polymers can then be reacted with a (poly) amine to form polyurethanes without isocyanate which can be advantageously used to formulate coating compositions, mastics or adhesives. However, this reaction is relatively long and remains to be improved. Example 4 of the patent application WO 2014/091173 discloses in particular the reaction of an unsaturated polyolefin comprising two terminal groups (2-oxo-1,3-dioxolan-4-yl) methyl oxycarbonyl with a primary diamine of polyether type. diamine, used in stoichiometric proportions, to form a polyurethane that can be formulated as a two-component adhesive composition. The duration of this reaction is 12 hours at 80 ° C. In order to overcome the drawbacks disclosed in the patent application WO 2014/091173, it is proposed to use novel intermediates for the synthesis of polyurethanes without the use of isocyanate, intended in particular for the manufacture of coating compositions, mastics or plastics. adhesives. Thus, the present invention relates to a hydrocarbon polymer comprising two end groups exo-vinylene cyclocarbonate, said hydrocarbon polymer having the following formula (I): R 1 R 5 R 6 R 3 R 1 R 7 R 8 R 17 F 2 n -1 R 4 R 1 R 2 R 5 R 13 R 13 R16 R14 R15 (1) wherein: - each bond denoted -I is a carbon-carbon single bond oriented geometrically to one side or the other with respect to the double bond (cis or trans) to which it is connected; the groups R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8, which may be identical or different, are chosen from a hydrogen atom, a 3034 atom, a hydrogen atom and a hydrogen atom; halogen, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one, and preferably one, of the groups R1 to R8 being part of the same hydrocarbon or heterocycle ring, saturated or unsaturated, with at least one other, and preferably with another, groups R1 to R8, according to the valence rules of organic chemistry; at least one of the pairs (R1, R2), (R3, R4), (R5, R6) and (R7, R8) may be an oxo group; x and y, which are identical or different, are integers in a range from 0 to 5, preferably from 0 to 2, even more preferably x is equal to 1 and y is equal to 1, the sum x + y being preferably in a range from 0 to 4 and even more preferably from 0 to 2; the groups R 13, R 14, R 15 and R 16 which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the R 13 groups; R16 may be part of the same hydrocarbon ring or heterocycle, saturated or unsaturated, with at least one other of the groups R13 to R16, according to the valence rules of organic chemistry; the group R17 is CH2, O, S, C (= O) or NR0, Ro being an alkyl group, preferably linear, comprising from 1 to 22, preferably from 1 to 14, carbon atoms; and n is an integer greater than or equal to 2 and m is an integer greater than or equal to 0, the molar ratio m / n being in a range from 0/100 to 90/10, and preferably ranging from / 100 to 75/50; n and m being further such that the number average molar mass Mn of the hydrocarbon polymer of formula (1) is in a range of from 400 to 50,000 g / mol, preferably from 600 to 20,000 g / mol, and the polymolecularity (PDI) of the hydrocarbon polymer of formula (1) is in a range of from 1.0 to 3.0, preferably from 1.0 to 2.0, more preferably from 1.45 to 1.85; F 1 is represented by the following formula: R 9 R 10 R 5 - and F 2 is represented by the following formula: R 9 R 10 R 10 in which: p 1 and p 2, which are identical or different, each represent an integer equal to 0, 1, 2 or 3, with preferably pl = 0 or p2 = 0, and more preferably pl = p2 = 0; X is an oxygen atom or a nitrogen group NR12 where R12 is a C1-C6 alkyl group; A is a C1-C6 alkylene group; R9 is a hydrogen atom, a C1-C6 alkyl group, a C5-C6 cycloalkyl group, a phenyl group or an alkylphenyl group with a C1-C4 alkyl chain; R10 and R11, which may be identical or different, each represents a hydrogen atom, a C1-C6 alkyl group, a C5-C6 cycloalkyl group, a phenyl group or an alkylphenyl group with a C1-C4 alkyl chain. Preferably, the C 1 -C 6 alkyl group oxyalkylenated by one or more C 1 -C 6 oxyalkylene groups as envisaged in the definition of R 9, R 10 and R 11 above is a C 1 -C 4 alkyl group oxyalkylenated by one or more oxyalkylene groups C 1 -C 4 (such as oxymethylene, oxyethylene, oxypropylene or oxybutylene).
    [0003] Of course, all formulas are given here in accordance with the valence rules of organic chemistry. The main chain of the polymer of formula (1) therefore comprises one or two types of repeating units, a first type of repeat unit repeated 5 times and a second type of repetition unit, optional, repeated m times. As it appears above, the terminal groups Fi and F2 are generally symmetrical with respect to the main chain, that is to say that they correspond substantially, with the exception of the indices p1 and p2. In the present application, in the absence of any indication to the contrary: "End group" means a group located at the end of the chain (or end of the main chain) of the polymer. The polymer according to the invention comprises a main chain, that is to say a longer chain, the two ends of which are the terminal groups of the polymer according to the invention. "Exo-vinylene cyclocarbonate group" means a group Fi or F2 as described above. "Alkyl group" means a linear or branched hydrocarbon compound, cyclic (including polycyclic) or acyclic, and comprising, unless otherwise indicated generally from 1 to 22 carbon atoms. Such an alkyl group most often comprises from 1 to 14, preferably from 1 to 8, carbon atoms. "Heteroalkyl" means according to the invention an alkyl group in which at least one of the carbon atoms is substituted by a heteroatom selected from the group formed by O and S. "Alkoxycarbonyl group" is understood to mean a linear or branched, saturated or partially unsaturated (monovalent) alkyl group comprising from 1 to 22, preferably from 1 to 14, carbon atoms, as well as a divalent - C00- group. "Heteroalkoxycarbonyl" means, according to the invention, an alkoxycarbonyl group in which at least one of the carbon atoms is substituted by a heteroatom chosen from the group formed by O and S. - By "halogen atom", an iodo, chloro, bromo or fluoro group, preferably chloro, is meant. "Hydrocarbon ring" means a cyclic (including polycyclic) hydrocarbon compound, saturated or unsaturated, which may contain from 3 to 22 carbon atoms and optionally at least one C = O group. "Heterocycle" means a hydrocarbon ring which may comprise an atom other than carbon in the ring chain, such as, for example, oxygen, sulfur or the NRO group as defined above, namely an alkyl group. , preferably linear, comprising from 1 to 22, preferably from 1 to 14, carbon atoms. - "at least one of the groups R1 to R8 may be part of the same hydrocarbon ring or heterocycle, saturated or unsaturated, with at least one other group R1 to R8, according to the valence rules of organic chemistry", according to the invention is meant that these groups, whether or not they are borne by the same carbon, are bonded together by a hydrocarbon chain (which may include the carbon atoms of the main chain of the polymer of formula (1)) comprising optionally at least one group C = O group and / or at least one heteroatom such as S or O, so as to form a hydrocarbon ring or a heterocycle, as defined above. In some cases, these groups may designate chemical bonds. For example, when one of the groups R 3 or R 4 with one of the groups R 5 or R 6 together with the carbon atoms of the main chain of the polymer of formula (1) supporting them, an epoxide ring, these denote a bond connecting the carbon atom supporting them to the oxygen atom of the epoxy group. These definitions are also applicable to groups R13 to R16. By "(R 1, R 2) may be an oxo" group, it is understood according to R 1 R 2) C the invention that the pair (R 1, R 2) is such that is where C is the carbon atom which supports the two groups forming the pair (R 1, R 2). This is also applicable to pairs (R3, R4), (R5, R6) and (R7, R8). PDI polymolecularity (or Dm dispersity) is defined as the Mw / Mn ratio, i.e. the ratio of the weight average molecular weight of the polymer to the number average molecular weight of said polymer.
    [0004] The two average molar masses Mn and Mw are measured according to the invention by Size Exclusion Chromatography (SEC), usually with PEG (PolyEthyleneGlycol) or PS (PolyStyrene) calibration, preferably PS.
    [0005] Preferably, the groups R5 to R8 are each a hydrogen atom. If p1 = 0 or p2 = 0 then there is no divalent group (CH2) 0 or (CH2) p2 in the formula Fi or F2 and - (CH2) 0- becomes a single bond - or - (CH2) ) p2- becomes a simple connection -.
    [0006] 10 When the index m, n or n-1, x or y, which applies to a set of two brackets equals zero, this means that there is no group between the brackets at which this index apply. Thus, each of the double bonds of the polymer of formula (1) is oriented geometrically cis or trans, and is preferably of cis orientation. The geometric isomers of the polymer of formula (1) are generally present in variable proportions, with most often a majority of cis (Z) and preferably all the double bonds are oriented cis (Z). It is also possible according to the invention to obtain only one of the geometric isomers, depending on the reaction conditions and in particular on the nature of the catalyst used. The polymers of formula (1) according to the invention may be solid polymers or liquid polymers, at room temperature (about 23 ° C.).
    [0007] Preferably, they are liquid polymers at 23 ° C, i.e., having a viscosity of from 1 to 500,000 mPa.s at 23 ° C. In general, the viscosity can be measured in a manner well known to those skilled in the art. In particular, the viscosity can be measured with a Brookfield viscometer, by selecting the needle and the speed of the module 30 appropriately, depending on the viscosity range to be measured.
    [0008] According to a variant of the invention, when m is equal to 0, the polymer of formula (1) can be represented by the following formula (2): ## STR2 ## in which: x, y, n, F1, F2, R1, R2, R3, R4, R5, R6, R7 and R8 have the meanings given above. Formula (2) illustrates the case where the main chain of the polymer of formula (1) comprises a single type of repeating unit, repeated n times. In a particularly preferred manner, x is equal to 1 and y is 1.
    [0009] When according to a preferred variant, m is equal to 0 and R1 to R8 denote hydrogen atoms, with at least one of the pairs (R1, R2), (R3, R4), (R5, R6) and / or R7, R8) may designate an oxo group, the polymer of formula (2) is solid at room temperature. According to another variant of the invention, preferably: m is different from zero and / or at least one of the groups R 1 to R 8 and / or R 13 to R 16 comprises an alkyl group (and therefore denotes a different group of a hydrogen atom and a halogen atom) or - at least one of the groups R1 to R8 is part of the same hydrocarbon or heterocycle ring, saturated or unsaturated, with at least one other group R1 to R8, according to the valence rules of organic chemistry, with - at least one of the pairs (R1, R2), (R3, R4), (R5, R6) and / or (R7, R8) being able to designate a group oxo.
    [0010] In this case, the polymer of formula (1) is liquid at ambient temperature. According to a particular embodiment of the invention F1 and F2 are identical.
    [0011] According to a preferred embodiment of the invention, F1 and F2 are different. According to a particular embodiment, X is an oxygen atom. According to another particular embodiment, X is a group NR12 where R12 is as defined above.
    [0012] Preferably: - p1 or p2 = 0, and more preferably p1 = p2 = 0, - X is an oxygen atom or a group NR12 where R12 is a methyl group, - A is a C1-C6 alkylene group, R 9 is a hydrogen atom; R 10 and R 11 are methyl groups. The hydrocarbon polymers with exo-vinylene cyclocarbonate terminations according to the invention can form, after reaction at temperatures below 100 ° C. with amines or oligomers of amines, an adhesive joint which has high, in particular higher, cohesion values. at 1.5 MPa (megapascal). Such cohesive values allow use as an adhesive, for example in the field of construction, transport or industry in general. The ability of the exvinylene-cyclocyanate-terminated hydrocarbon polymers of the invention to react more rapidly than those of the prior art with amine amines or oligomers at temperatures below 100 ° C or At room temperature (i.e., about 23 ° C) for the liquid polymers of the invention is therefore particularly advantageous.
    [0013] The hydrocarbon polymers with exo-vinylene cyclocarbonate terminations according to the invention thus make it possible to obtain an adhesive seal with satisfactory mechanical properties, more rapidly compared with the hydrocarbon polymers of the prior art mentioned above. The mechanical properties of the adhesive joint, and in particular its cohesion values, can be measured in accordance with the standard ISO 527-1 or ASTM D 638-03, and in particular under the operating conditions described in example 9 of the patent application. FR No. 15/50500. In this example, the measurement of tensile strength and elongation by tensile test has been carried out, for each of the adhesive compositions, according to the protocol described hereinafter.
    [0014] The principle of measuring the tensile strength and tensile elongation of adhesive compositions is to stretch in a tensile machine, the moving jaw of which travels at a constant speed of 100 mm / min, a standard test specimen consisting of the crosslinked adhesive composition and to record, at the moment when the test piece breaks, the applied tensile stress (in MPa) and the elongation of the specimen (in%). The standard test piece is dumbbell-shaped, as shown in International Standard ISO 37. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 μm.
    [0015] To prepare the dumbbell, the adhesive composition was heated to 100 ° C and then extruded onto an A4 sheet of silicone paper in an amount sufficient to form a film having a thickness of 300 μm thereto. The film is left for 7 days at 23 ° C. and 50% relative humidity for crosslinking, then the dumbbell is obtained by simple cutting in the crosslinked film.
    [0016] The invention also relates to a process for the preparation of at least one hydrocarbon polymer comprising two terminal exovinylene cyclocarbonate groups according to the invention, said process comprising at least one metathesis ring opening polymerization step (or "RingOpening Metathesis Polymerization"). in the presence of: at least one metathesis catalyst, preferably a catalyst comprising ruthenium, even more preferably a Grubbs catalyst, at least one chain transfer agent ( CTA for "Chain Transfer Agent" in English) mono or di-exo vinylene cyclocarbonate respectively of formula (Cl) or (C2) below: (Cl) (C2) 5 in which: F1 and F2 are as defined above, and the bond is a single carbon-carbon bond oriented geometrically on one side or the other with respect to the double bond (cis or trans) in the formula (C2); Of at least one compound of formula (A) below: R 1 R 8 (A) in which: the groups R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, at least one of the groups R1 to R8 being part of the same saturated hydrocarbon or heterocycle ring; or unsaturated, with at least one other of the groups R1 to R8, according to the valence rules of organic chemistry, and - at least one of the pairs (R1, R2), (R3, R4), (R5, R6) and (R7, R8) may be an oxo group; x and y are integers independently in a range from 0 to 5, preferably from 0 to 2, even more preferably x is 1 and y is 1, the sum x + preferably being in a range of from 0 to 4 and even more preferably from 0 to 2; and 5 - optionally at least one compound of formula (B): R 17 R 13 (B) in which - the groups R 13, R 14, R 15 and R 16, which are identical or different, are chosen from a hydrogen atom, a halogen atom, a heteroalkyl group, an alkoxycarbonyl group and a heteroalkoxycarbonyl group, at least one, and preferably one, of the groups R13 to R16 being part of the same ring or saturated or unsaturated heterocycle with at least one other, and preferably with another, R13 to R16 groups, according to the valence rules of organic chemistry; and - the group R17 is CH2, O, S, C (= O) or NR0, Ro being an alkyl group, preferably linear, comprising from 1 to 22, preferably from 1 to 14, carbon atoms; during a reaction time of 2 to 24 hours and at a temperature in the range of 20 to 60 ° C. The duration and the temperature for this polymerization reaction generally depend on the reaction conditions and in particular the catalytic loading rate. The skilled person is able to adapt them depending on the circumstances.
    [0017] CTA is a compound that includes one or two exylenevinylcyclocarbonate functions.
    [0018] The CTA of formula (Cl) is said to be monofunctional when it comprises an exo-vinylene cyclocarbonate group. The CTA of formula (C2) is said to be difunctional when it comprises two exo-vinylene cyclocarbonate groups, which may be identical or different. The molar ratio of the CTA of formula (Cl) to the compound of formula (A), or to the sum of the compounds of formulas (A) and (B) if the compound of formula (B) is present, is included in a range ranging from 1.10-3 to 1.0 and preferably from 1.10-2 to 0.250.
    [0019] The molar ratio of CTA of formula (C2) to the compound of formula (A), or to the sum of compounds of formulas (A) and (B) if the compound of formula (B) is present, is included in a range from 0.5 × 10 -3 to 0.5 and preferably from 0.5 × 10 -2 to 0.125. Compounds of formula (A) generally comprise from 6 to 30, preferably from 6 to 22, carbon atoms. The compounds of formula (B) generally comprise from 6 to 30, preferably from 6 to 22, carbon atoms. In a preferred embodiment of the invention, x = y = 1. Metathesis ring opening polymerization (or ROMP 20 for "Ring-Opening Methathesis Polymerization") is a well known reaction of the human job. In the present application, this reaction is carried out in the presence of a mono-functional CTA of formula (Cl) or a difunctional CTA of formula (C2). The cyclic compounds of formula (A) are preferably, according to the invention, selected from the group consisting of cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, 1,5-cyclooctadiene, cyclononadiene, 1,5,9-cyclodecatriene, 5-epoxycyclooctene, 5-oxocyclooctene, 5-alkyl-cyclooctene including C1-C22-alkyl, and preferably C1-C14-alkyl, and mixtures thereof.
    [0020] The cyclooctene (C0E) O, the 5-epoxy-cyclooctene, the 5-oxocyclooctene and the 5-alkyl-cyclooctene where R is an alkyl group comprising from 1 to 22, preferably 1 to 14, carbon atoms, are preferred according to the invention; cyclooctene being very particularly preferred. For example, R is n-hexyl. The cyclic compounds of formula (B) are preferably according to the invention selected from the group consisting of norbornene (NBN), dicyclopentadiene and 7-oxanorbornene which are respectively of the following formulas: The cyclic compounds of formula (B) may also are selected from the group consisting of compounds of the following formulas: wherein R is an alkyl group comprising from 1 to 22, preferably 1 to 14, carbon atoms. For example, R is n-hexyl. Cyclic compounds of formula (B) may also be selected from the group consisting of adducts (or adducts in English) from the Diels-Alder reaction using cyclopentadiene or furan as starting material, as well as compounds derived from norbornene as described in WO 2001/04173 (such as: isobornyl norbornene carboxylate, phenyl norbornene carboxylate, norbornene ethylhexyl carboxylate, phenoxyethyl norbornene carboxylate and norbornene alkyl dicarboxymide, the alkyl having the most often from 3 to 8 carbon atoms) and those described in WO 2011/038057 (norbornene dicarboxylic anhydrides and optionally 7-oxanorbornene dicarboxylic anhydrides). According to a first embodiment of the preparation process according to the invention (called "monofunctional CTA"), the CTA used is of formula (C1) defined above and can also be represented as follows, with pi, X, A, R9, R10 and R11 having the meanings given above: R11 R10 R9 (C1) In this case, preferably, - pl = 0, - X is an oxygen atom or an NR12 group where R12 is a methyl group, - A is a C1-C6 alkylene group, - R9 is a hydrogen atom, - R10 and R11 are methyl groups. The compound of formula (C1) can be obtained according to scheme (1) below, following the procedures described in patent applications DE1098953 and DE3433403, pl, X, A, R9, R10 and R11 having the meanings data previously: (CH X R11 R10 OH R1 R10 (CH A (C1) Scheme (1) According to a second embodiment of the preparation process according to the invention (called "CTA difunctional route"), the CTA2 is of formula (C2) defined above and can also be represented as follows, with p1, p2, Z, X, A, R9, R10, R11 and J having the meanings given above: R9 Ri 1 0 (CH; 1 R10 o R10 C Rul In this case, preferably, p1 or p2 = 0, and more preferably p1 = p2 = 0, X is an oxygen atom or an NR12 group where R12 is a methyl group, A is C 1 -C 6 alkylene, R 9 is hydrogen, R 10 and R 11 are methyl, and the compound of formula (C 2) can be obtained according to scheme (2) below, corresponding to an original variant of the scheme (1), pi, p2, X, A, R9, R10 and R11 having the meanings given above: RIO CH e, CH R11 R11 R 0 ( ## STR2 ## (2) The step of ring-opening polymerization by metathesis is carried out most often in the presence of at least one solvent, generally chosen from the group formed by the aqueous or organic solvents typically used in the polymerization reactions and which are inert under the conditions of polymerization described above. As an example of a solvent that can be used, mention may be made, for example, of aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water or their mixtures.
    [0021] Preferably, the solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, and the like. , hexane, heptane, methanol, ethanol, water or mixtures thereof. More preferably, the solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, and the like. hexane, heptane, methanol, ethanol, and mixtures thereof. More preferably, the solvent is toluene, heptane, or a mixture of toluene and methylene chloride. The solubility of the polymer formed during the polymerization reaction is generally and mainly dependent on the choice of solvent and the molecular weight of the polymer obtained. It is also possible that the reaction is carried out without solvent. The metathesis catalyst, such as for example a Grubbs catalyst, is generally a commercial product.
    [0022] The metathesis catalyst is most often a catalyst comprising at least one transition metal, such as ruthenium, most often in the form of complex. Preferably, the metathesis catalyst is chosen from ruthenium complexes such as a ruthenium-carbene complex.
    [0023] More preferably, the metathesis catalyst is selected from Grubbs catalysts. The term "Grubbs catalyst" generally means, according to the invention, a Grubbs 1st or 2nd generation catalyst, but also any other Grubbs type catalyst (ruthenium-carbene type) accessible to the person skilled in the art, such as for example, the substituted Grubbs catalysts described in US Patent 5,849,851 A Grubbs 1st generation catalyst is generally of formula (G1): ## STR3 ## wherein: Ph is the phenyl group; is cyclohexyl, and 5 - P (Cy) 3 is a tricyclohexylphosphine group The IUPAC name of the catalyst (G1) is: benzylidenebis (tricyclohexylphosphine) dichlororuthenium (CAS number 172222-30-9) A Grubbs 2nd generation catalyst is generally of formula (G2): ## STR2 ## wherein: Ph is phenyl, Cy is cyclohexyl, and P is ) 3 is a tricyclohexylphosphine group.
    [0024] The IUPAC name of the catalyst (G2) is: benzylidene [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (tricyclohexylphosphine) ruthenium (CAS number 246047-72-3). Preferably, the catalyst is a 2nd generation Grubbs catalyst, as defined for example by the formula (G2).
    [0025] The invention also relates to a process for the preparation of polyurethane comprising the reaction of at least one hydrocarbon polymer with exo-vinylene cyclocarbonate terminations according to the invention, capable in particular of being obtained by the preparation process according to the invention, with At least one compound comprising at least one, preferably at least two, amine groups, for example selected from monoamines, diamines, triamines and other polyamines; as well as the polyurethanes obtainable by this preparation process.
    [0026] The above-described amino compounds are preferably such that at least one amine group, preferably all amine groups, are primary amine groups. These amino compounds can be oligomers. These oligomers generally have a number average molecular weight of less than 2000.
    [0027] Preferably, the exvinylene cyclocarbonate terminated hydrocarbon polymer (s) and amine compound (s) are used in such amounts that all of the exo-vinylene cyclocarbonate groups of the polymer (s) have reacted. with an amino group of an amino compound to form a urethane group.
    [0028] More preferably, the exo-vinylene cyclocarbonate terminated hydrocarbon polymer (s) are reacted with one or more primary (poly) amine (s) in stoichiometric amounts, i.e. the molar ratio of the number of cyclocarbonate groups to the number of primary amine groups is approximately equal to 1.
    [0029] The polyurethanes thus obtained, which are new, have been advantageously prepared without isocyanate. These polyurethanes, once formulated (i.e., formulated with other optional additives), are intended to be used as such as coating, sealant or adhesive compositions, or in coating compositions, mastics or adhesives, for example as fillers and / or as resins. It is also possible to formulate independently the polymer terminated exo-vinylene cyclocarbonate according to the invention and the compound comprising at least one amine group before their mixing, especially in the form of a two-component composition.
    [0030] The invention will be better understood from the following examples. EXAMPLES The examples which follow illustrate the invention without limiting its scope.
    [0031] Examples 1 to 9: Synthesis of an Exo-Vinylene Cyclocarbonate Termination Polymer According to the Invention Exo-vinylene cyclocarbonate-terminated hydrocarbon polymers of Examples 1 to 9 were obtained by means of the following steps: 1- a step of synthesis of (s) cycloolefin (s) of formulas (A) and / or (B), 2- a step of synthesis of the transfer agent (CTA) of formula (Cl) or (C2) 3- a step of ring-opening metathesis polymerization of cycloolefin of formula (A) and optionally of compound of formula (B) in the presence of a Grubbs catalyst and the transfer agent, step 1 preferably being optional when the cycloolefin (s) of formulas (A) and (B) are commercially available. The ring-opening polymerization reactions by metathesis carried out in Examples 1 to 9 are represented by general schemes (3) and (4), respectively using a monofunctional CTA (Cl) and a difunctional CTA (C2), and will be explained case by case in the examples. (A) R 3 G 2 I R 14 Fi Scheme (3) R 4 R 7 R 8 k). (4) In these schemes (3) and (4): (1) In this scheme (3) and (4): - 1 equiv. means an equivalent and corresponds to the amount of metathesis catalyst used; DCM stands for dichloromethane; (A) and (B) are the cycloolefins corresponding to the formulas (A) and (B) respectively defined above; - (Cl) and (C2) are the transfer agents respectively corresponding to the formulas (Cl) and (C2) defined above; the link JJ is a single carbon-carbon bond oriented geometrically on one side or the other with respect to the double bond (cis or trans) for (C2); - G2 is the metathesis catalyst of formula (G2) as defined above; F1 and F2 are identical and both correspond to either the ester type group below: ## STR2 ## R 9 is the amide group: R 11 R 10 (CH 2) p R 12 R 9 in which: p = p1 or p2, and A, R9, R10 and R11 being as previously defined; n is the number of moles of cycloolefin (s) of formula (A); m is the number of moles of cycloolefin (s) of formula (B); q is the number of moles of CTA of formula (C1) or (C2). The number of monomer units in the polymer obtained after the polymerization reaction is equal to n + m. In each of Examples 1 to 9 described below, the reaction lasts 24 hours (h) at a temperature of 40 ° C. All polymerizations were performed in a similar manner. The only differences are in the nature and initial concentration of the chain transfer agent (s) (CTA) of type (C1) or (C2) used. The CTAs used in Examples 1 to 9 are the following: - [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] acrylate (denoted CTA1) 0 H H3C H3C (CTA1 ) (which corresponds to a CTA of formula (C1) in which: pl = 0, X is an oxygen atom, A is an ethylene -CH2-CH2- group, R9 is a hydrogen atom, R10 and R11 are methyl groups); [N-methyl, (5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] acrylamide (denoted CTA2) CH3 H3C H3C (CTA2) (which corresponds to a CTA of (C1) wherein p1 = 0, X is N-CH3 with R12 being methyl, A is ethylene -CH2-CH2-, R9 is hydrogen, R10 is methyl, R11 and R12 are methyl groups); bis [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] fumarate (denoted CTA3) H3C H3C H3C CH3 CH3 (CTA3) (which corresponds to a CTA of formula ( C2) where: p1 = p2 = 0, X is an oxygen atom, A is an ethylene group -CH2-CH2-, R9 is a hydrogen atom, R10 and R11 are methyl groups); and bis [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] fumaramide (denoted CTA) 1-13C CH 3 H 3 C H CH 3 CH 3 CH (CTA 4) (which corresponds to a CTA of formula (C2) wherein: p1 = p2 = 0, X is NCH3 where R12 is methyl, A is ethylene -CH2-CH2-, R9 is hydrogen, R10 and R11 are methyl groups).
    [0032] Two reaction possibilities (i and ii) exist, depending on whether the cycloolefin of formula (A) alone is used (examples 1 to 7) or whether the cycloolefins of formulas (A) and (B) are used. ) as a mixture (Examples 8 and 9). I) Examples 1 to 7: Polymerization of the cycloolefins of formula (A) The cycloolefins of formula (A) used in Examples 1 to 7 are the following: O (COE) - Epoxy-COE) Q 10 0 (5-6) = COE) c6H13 (5-Hexyl-COE). Cyclooctene (COE) and 5,6 epoxycyclooctene (5-EpoxyCOE) are commercial products of Sigma Aldrich. 5-Oocyclooctene (5-0 = COE) and 5-n-hexyl-cyclooctene (5-hexyl-COE) can be synthesized from 5,6-epoxycyclooctene (5-epoxy-COE) according to the indicated route. in the following reaction scheme (5): Concentrated HCI, Anc 12 Scheme (5) The 5-oxocyclooctene (5-0 = COE, referenced 2 in Scheme (5) above) was synthesized according to the procedure indicated in the publication of A. Diallo et al., Polymer Chemistry, Vol. 5, Issue 7, April 7, 2014, pages 25832591 (which referred to Hillmyer et al, Macromolecules, 1995, 28, pages 6311-5616). 5-Hexyl-cyclooctene (5-hexyl-COE referenced in Scheme (5) above) was synthesized according to the procedure outlined in A. Diallo et al., Polymer Chemistry, supra (which referred to Kobayashi et al., J. Am Chem Soc 2011, 133, pp. 5794-5797).
    [0033] The raw materials, reagents and solvents used for the synthesis of these cycloolefins of formula (A) are commercially available from Sigma Aldrich. In the following examples: The NMR spectra were recorded under AM-500 Bruker and AM-400 Brüker spectrometers, at 298 K in CDCl3. The chemical shifts were referenced to tetramethylsilane (TMS) using resonance (1H) or (13C) deuterated solvents. The number and weight average molar masses (M, and Mw) and PDI polydispersity (Mw / Mn) of the polymers were determined by size exclusion chromatography (SEC), with PS calibration using a Polymer Laboratories instrument. PL-GPC 50. Example 1 Synthesis of a polymer comprising two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] ester end groups from cyclooctene (COE) and [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] acrylate (CTA1). The reaction was carried out according to the following scheme (6), in a molar ratio m 0/100 and according to the procedure described below: ## STR2 ## Procedure (6) Procedure: The cycloolefin of formula (I) was mixed in a 1000 ml flask. (A) (108.00 mmol), hydroquinone (0.54 mmol) and dry CH2Cl2 (50 mL). The flask and its contents were then put under argon. The CTA (10.80 mmol) of type (Cl) was introduced into the flask by syringe. The flask was then immersed in an oil bath at 40 ° C. and immediately followed by the addition of a catalyst G2 (54.00 μmol) in solution in CH 2 Cl 2 (20 ml). . 24 hours after the addition of the catalyst, the product is removed from the flask after evaporation of the solvent in vacuo. The product is then recovered after precipitation in methanol, filtration and drying at 20 ° C under vacuum. Results: The polymer obtained is solid at room temperature. The degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in%), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of said polymer, determined by SEC gave the following results: Table 1: [Ru] (overnight) 1H NMR (CDCI 3, 500 MHz, 298 K) and 1H NMR (1H NMR (CDCl 3, 500 MHz, 298 K)) were 13C (CDCl3, 100 MHz, 298 K) of the polymer obtained for this test confirmed the structure of the expected polymer as shown in scheme (6) Example 2: Synthesis of a polymer comprising two terminal groups [N-methyl] (5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] amide from cyclooctene (COE) and [N-methyl, (5,5-dimethyl-2-oxo) 1,3-dioxolan-4-ylidene) propyl] acrylamide (CTA2) The reaction was carried out according to the following scheme (7), in a molar ratio m / n equal to 0/100 and according to the procedure that Example 1: (Cl ## STR5 ## The results obtained are solid at room temperature. The degree of conversion of the cycloolefin of formula (A) determined by NMR (expressed in%), the number-average molecular weight of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of said polymer, determined by SEC, gave the following results: Table 2: Ru) r.niot uno c-usion P 11) 1 mo 1: J: DOC! 1.49 The 1 H NMR (CDCl3, 500 MHz, 298 K) and 13 C (CDCl3, 100 MHz, 298 K) analyzes of the polymer obtained for this test confirmed the structure of the expected polymer as shown in scheme (7). Example 3 Synthesis of a polymer comprising two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] ester end groups from cyclooctene (COE) and bis [( 5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] fumarate (CTA3) The reaction was carried out according to the following scheme (8), in a molar ratio m / n equal to 0/100 and according to the procedure described below: F1 C 0 0 1 C CH '; EXAMPLE 8 Operating Procedure: The cycloolefin of formula (A) (108.00 mmol), hydroquinone (0.54 mmol), is mixed in a 1000 ml flask. ) and dry CH2Cl2 (50 mL). The flask and its contents were then put under argon. CTA (5.40 mmol) of type (C2) was introduced into the flask by syringe. The flask was then immersed in an oil bath at 40 ° C., then G2 catalyst (54.00 μmol) dissolved in CH 2 Cl 2 (20 ml) was immediately added by means of a cannula. ). 24 hours after the addition of the catalyst, the product is removed from the flask after evaporation of the solvent in vacuo. The product is then recovered after precipitation in methanol, filtration and drying at 20 ° C. under vacuum. Results: The polymer obtained is solid at room temperature. The results of the conversion rate of the cycloolefin of formula (A) determined by NMR (expressed in%), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of said polymer. , determined by SEC, have been reported in Table 3 below. 1 H NMR (CDCl 3, 500 MHz, 298 K) and 13 C (CDCl 3, 100 MHz, 298 K) analyzes of the polymer obtained for this test confirmed the structure of the expected polymer as shown in scheme (8). Example 4 Synthesis of a polymer comprising two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] amide end groups from cyclooctene (COE) and bis [( 5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] fumaramide (CTA4) The reaction was carried out according to the following scheme (9), in a molar ratio m / n equal to 0/100 and according to the procedure that Example 3: 3034770 31 0 o 0 CH; CH; H CH; C () o Scheme (9) Results: The polymer obtained is solid at room temperature.
    [0034] The results of the conversion rate of the cycloolefin of formula (A) determined by NMR (expressed in%), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of said polymer, determined by SEC, are shown in Table 3 below.
    [0035] 1 H NMR (CDCl 3, 500 MHz, 298 K) and 13 C (CDCl 3, 100 MHz, 298 K) analyzes of the polymer obtained for this test confirmed the structure of the expected polymer as shown in scheme (9). Example 5 Synthesis of a polymer comprising two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] ester end groups from cyclooctene monoepoxide (5-Epoxy-COE) and bis [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] fumarate (CTA3). The reaction was carried out according to the following scheme (10), in a molar ratio. m / n equal to 0/100 and according to the procedure as in Example 3 3: 3034 770 32 H - C o 11 - EpoxyCCF (CTA3) H I-13C Scheme (10) Results: The polymer obtained is liquid at temperature room.
    [0036] The results of the conversion rate of the cycloolefin of formula (A) determined by NMR (expressed in%), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of said polymer, determined by SEC, are shown in Table 3 below.
    [0037] 1 H NMR (CDCl 3, 500 MHz, 298 K) and 13 C (CDCl 3, 100 MHz, 298 K) analyzes of the polymer obtained for this test confirmed the structure of the expected polymer as shown in Scheme (10). Example 6 Synthesis of a polymer comprising two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] ester end groups from 5-oxocyclooctene (5 - O = COE ) and bis [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] fumarate (CTA3). The reaction was carried out according to the following scheme (11) in one report. m / n molar equal to 0/100 and according to the procedure as in Example 3: (11) Results: The polymer obtained is solid at ambient temperature.
    [0038] The results of the conversion rate of the cycloolefin of formula (A) determined by NMR (expressed in%), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of said polymer, determined by SEC, are shown in Table 3 below.
    [0039] 1 H NMR (CDCl 3, 500 MHz, 298 K) and 13 C (CDCl 3, 100 MHz, 298 K) analyzes of the polymer obtained for this test confirmed the structure of the expected polymer as shown in Scheme (11). Example 7 Synthesis of a polymer comprising two [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] ester end groups from 5-hexyl-cyclooctene (5-hexyl) -COE) and bis [(5,5-dimethyl-2-oxo-1,3-dioxolan-4-ylidene) propyl] fumarate (CTA3). The reaction was carried out according to the following scheme (12) in one report. m / n molar equal to 0/100 and according to the procedure that Example 3 3: 3034770 34 Ci3H13 HH HO 0 CH. ## STR2 ## Scheme (12) Results: The polymer obtained is liquid at room temperature.
    [0040] The results of the conversion rate of the cycloolefin of formula (A) determined by NMR (expressed in%), the number-average molar mass of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of said of the polymer, determined by SEC, were recorded in the following Table 3: Table 3: IM, Ft n, WE 1 1 4 800 1 _1 u 1.1 3Li 1.2 3034770 1H NMR (CDCl3, 500 MHz) , 298 K) and 13C (CDCl3, 100 MHz, 298 K) of the polymer obtained for this test confirmed the structure of the expected polymer as shown in scheme (12). Ii) Examples 8 to 9: Polymerization of a mixture of cycloolefins of formulas (A) and (B) The cycloolefins of formula (A) and (B) used in Examples 8 and 9 are respectively the following: (COE) (NBN) Cyclooctene (COE) of greater than 95% purity and norbornene (NBN) of greater than 99% purity are commercially available from Sigma Aldrich. These products were previously distilled on CaH2, before being used in Examples 8 and 9.
    [0041] EXAMPLE 8 Synthesis of a Polymer Comprising Two Endo-Vinylene Cyclocarbonate Terminal Groups from Cyclooctene (COE), Norbornene (NBN) and Bis ((5,5-dimethyl-2-oxo-1,3-dioxolan) The reaction was carried out according to the following scheme (13) in a molar ratio m / n equal to 50/50 and according to the procedure described below: ## STR2 ## - Scheme (13) 3034 770 36 Procedure: In a 1000 ml flask was mixed the cycloolefins of formulas (A) and (B), corresponding to COE (54.00 mmol) and NBN (54.00 mmol) hydroquinone (0.54 mmol) and dry CH2Cl2 (50 ml), respectively. The flask and its contents were then put under argon. CTA (5.40 mmol) of type (C2) was then introduced into the flask by syringe. The flask was then immersed in an oil bath at 40 ° C and then G2 catalyst (54 μmol) dissolved in CH2Cl2 (20 mL) was immediately added via a cannula. 24 hours after the addition of the catalyst, the product was removed from the flask after evaporation of the solvent in vacuo. The product was then recovered after precipitation in methanol, filtration and drying at 20 ° C. under vacuum. Results: The polymer obtained is liquid at room temperature.
    [0042] The conversion rates of the cycloolefins of formula (A) and (B) determined by NMR (expressed in%), the number-average molecular weight of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of the polymer. determined by SEC. The results are shown in the following Table 4: Table 4: Esa u TiA]. [B] (FDI inol'in conversion Mn, Ec me) 8 1 H NMR (CDCl 3, 500 MHz, 298 K) and 13C (CDCl3, 100 MHz, 298 K) of the obtained polymer confirmed the structure of the expected polymer as shown in scheme (13).
    [0043] EXAMPLE 9 Synthesis of a Polymer Comprising Two Exo-Vinylene Cyclocarbonate Terminal Groups from Cyclooctene (COE), Norbornene (NBN) and Bis ((5,5-dimethyl-2-oxo-1,3-dioxolan) The reaction was carried out according to the following scheme (14), in a molar ratio m / n equal to 50/50 and according to the same procedure as the example. 8: TLC 24 h 5 Scheme (14) Results: The polymer obtained is liquid at room temperature. The conversion rates of the cycloolefins of formula (A) and (B) determined by NMR (expressed in%), the number-average molecular weight of the polymer obtained (expressed in grams per mol) and the polymolecularity (PDI) of the polymer. determined by SEC. The results are shown in Table 5 below: Table 5: Test n: [A] 1.13] [CIA3] TRu flua mol) PDI I version) (e MOU, g 1 H NMR (CDCl 3, 500 MHz , 298 K) and 13C (CDCl3, 100 MHz, 298 K) of the obtained polymer confirmed the structure of the expected polymer as shown in Scheme (14).
    [0044] II-Comparative Example 10 Synthesis of a Polymer Comprising Two Methylene Cyclocarbonate Terminal Groups from Cyclooctene (COE) and Bis [(2-oxo-1,3-dioxolan-4-yl) methyl] fumarate (CTA5) The reaction was carried out according to the following scheme (15), in a molar ratio m / n equal to 0/100 and according to the same procedure as Example 3: Scheme (15) Results: The resulting polymer is solid at room temperature. The results of the conversion rate of the cycloolefin of formula (A) determined by NMR (expressed in%), the number-average molar mass of the polymer obtained (expressed in grams per mol) as well as the polymolecularity (PDI) of said polymer , determined by SEC, were reported in the following Table 6: Table 6: Test No. IA] .. [B] .. [CT Al] .. [Ru] (mol 'mol) Com-si o Idn The 1 H NMR (CDCl 3, 500 MHz, 298 K) and 13 C (CDCl 3, 125 MHz, 298 K) analyzes of the polymer obtained for this test confirmed the structure of the expected polymer as shown in the diagram (15).
    [0045] Example 11 to 13: Syntheses of polyurethanes from the unsaturated polyolefins of Examples 10, 3 and 8 respectively: Comparative Example 11: Synthesis of a polyurethane from the solid unsaturated polyolefin of Comparative Example 10 The polyolefin of comparative example 10 was reacted at 80 ° C., separately and in a stoichiometric ratio, with a primary diamine of the polyether diamine type (JEFFAMINE EDR 148, Huntsman) until complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups (at 1800 cm -1) and appearance of the characteristic bands of the carbamate bond (band at 1700 cm -1). The reaction time recorded during the complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups was approximately 12 hours at 80 ° C.
    [0046] Example 12: Synthesis of a polyurethane from the solid unsaturated polyolefin of Example 3 according to the invention Example 11 was reproduced by replacing the polyolefin of Example 10 with the polyolefin of Example 3.
    [0047] The reaction time during the complete disappearance of the infrared band characteristic of 1,3-dioxolan-2-one groups was less than 3 hours at 80 ° C. Example 13: Synthesis of a polyurethane from the liquid unsaturated polyolefin of Example 8 according to the invention Example 11 was reproduced by replacing the polyolefin of Example 3 with the polyolefin of Example 8 and performing the reaction at room temperature (23 ° C). The reaction time recorded during the complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups was less than 3 hours at 23 ° C. In each case, the products of Examples 12 and 13 could be formulated as a two-component mixture having satisfactory adhesive properties.
    权利要求:
    Claims (12)
    [0001]
    REVENDICATIONS1. A hydrocarbon polymer comprising two exo-vinylene cyclocarbonate end groups, said hydrocarbon polymer having the following formula (I): ## STR1 ## wherein R 1 is R 1 wherein: - - - - - - each bond denoted by -I is a single carbon-carbon bond oriented geometrically on one side or the other with respect to the double bond (cis or trans) to which it is bonded; R1, R2, R3, R4, R5, R6, R7 and R8 groups, which may be identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a group heteroalkoxycarbonyl, at least one of the groups R1 to R8 being part of the same hydrocarbon or heterocycle ring, saturated or unsaturated, with at least one of the groups R1 to R8, at least one of the pairs (R1, R2), (R3 , R4), (R5, R6) and (R7, R8) being an oxo group; x and y, which are identical or different, are integers in a range of 0 to 5; the groups R13, R14, R15 and R16, which may be identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl group, a heteroalkyl group, an alkoxycarbonyl group or a heteroalkoxycarbonyl group, 3034770 42 - at least one groups R13 to R16 which may form part of the same hydrocarbon or heterocycle ring, saturated or unsaturated, with at least one other of the groups R13 to R16; the group R17 is CH2, O, S, C (= O) or NR0, Ro being an alkyl group having from 1 to 22; and n is an integer greater than or equal to 2 and m is an integer greater than or equal to 0, the molar ratio m / n being in a range from 0/100 to 90/10; n and m being further such that the number average molar mass M n of the hydrocarbon polymer of formula (1) is in the range of 400 to 50,000 g / mol; F1 is represented by the following formula: R9 RO R1 - and F2 is represented by the following formula: ## STR1 ## in which: p1 and p2, which are identical or different, each represent an integer equal to 0, 1, 2 or 3; X is an oxygen atom or a nitrogen group NR12 where R12 is a C1-C6 alkyl group; A is a C1-C6 alkylene group; R9 is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkyl group oxyalkylenated with one or more C1-C6 oxyalkylene groups, a C5-C6 cycloalkyl group, a phenyl group or a phenyl group; alkylphenyl group with a C1-C4 alkyl chain; R10 and R11, which are identical or different, each represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkyl group oxyalkylenated with one or more C1-C6 oxyalkylene groups, a C5-C5 cycloalkyl group; C6, a phenyl group or an alkylphenyl group with a C1-C4 alkyl chain.
    [0002]
    2. A hydrocarbon polymer comprising two endo-vinylene cyclocarbonate end groups according to claim 1, in which m is equal to 10 0, the polymer having the following formula (2): (2) in which: x, y, n, Fi, F 2, R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 being as defined in claim 1.
    [0003]
    3. Hydrocarbon polymer comprising two exo-vinylene cyclocarbonate end groups according to claim 1 or 2, characterized in that X is an oxygen atom.
    [0004]
    4. A hydrocarbon polymer comprising two exo-vinylene cyclocarbonate end groups according to claim 1 or 2, characterized in that X is a NR12 group in which R12 is as defined in claim 1 or 2
    [0005]
    5. A hydrocarbon polymer comprising two end-vinylene cyclocarbonate end groups according to any one of claims 1, 2 and 4, characterized in that R12 is a methyl group. 25
    [0006]
    6. A hydrocarbon polymer comprising two exo-vinylene cyclocarbonate end groups according to any one of claims 1 to 5, characterized in that R 9 is a hydrogen atom, R 10 and R 11 are methyl groups, and with p 1 = 0 or p 2 = O. 3034770 44
    [0007]
    7. A hydrocarbon polymer comprising two exo-vinylene cyclocarbonate end groups according to any one of claims 1 to 5, characterized in that pl = p2 = O.
    [0008]
    8. Process for the preparation of at least one hydrocarbon polymer comprising two exo-vinylene cyclocarbonate end groups according to one of claims 1 to 7, said process comprising at least one metathesis ring opening polymerization step, in the presence: at least one metathesis catalyst; at least one mono or di-exovinylene cyclocarbonate chain transfer agent of the following formula (C1) or (C2): F1 (C1) (C2) in which: F1 and F2 are as defined in any one of claims 1 to 7, and the bond is a carbon-to-carbon single bond oriented geometrically to one side or the other with respect to the double bond (cis). or trans) in formula (C2); at least one compound of the following formula (A): ## STR5 ## in which: the groups R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8, x and y are as defined in any one of claims 1 to 7; and 3034 770 45 - optionally at least one compound of formula (B): Ri Wherein R13, R14, R15 and R16 are as defined in any one of claims 1 to 7; during a reaction time of 2 to 24 hours and at a temperature in the range of 20 to 60 ° C.
    [0009]
    9. Preparation process according to claim 8, said process being such that the molar ratio of the CTA of formula (Cl) on the compound of formula (A), or on the sum of the compounds of formulas (A) and (B) if the compound of formula (B) is present, is in a range of from 1.10-3 to 1.0 or the molar ratio of CTA of formula (C2) to the compound of formula (A), or the sum of compounds of formulas (A) and (B) if the compound of formula (B) is present, is in a range of 0.5-10-3 to 0.5.
    [0010]
    10. A process for the preparation of polyurethane comprising reacting the reaction of at least one hydrocarbon polymer of formula (1) according to any one of claims 1 to 7, with at least one compound comprising at least one amine group. 20
    [0011]
    11. Polyurethanes obtainable by the preparation process according to claim 10.
    [0012]
    A compound of formula (C2) as defined in claim 8.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP2931760B1|2016-09-28|Hydrocarbon-based polymers comprising two end groups with 2-oxo-1,3-dioxolan-4-yl endings, preparation thereof and use thereof
    EP3298062B1|2019-05-22|Hydrocarbon polymers comprising two |alkyloxycarbonyl end groups
    EP3280706B1|2019-05-22|Hydrocarbon polymers comprising twoexo-vinylene cyclic carbonate terminal groups
    WO2016116680A1|2016-07-28|Hydrocarbonated polymers with two alcoxysilane end groups
    EP3024854B1|2018-07-11|Hydrocarbon polymers with two alkoxysilane end groups
    WO2016110653A1|2016-07-14|Hydrocarbon polymers with two alcoxysilane end groups
    EP3284766A1|2018-02-21|Novel hydrocarbon polymers with dithiocyclocarbonate end groups
    WO2018002473A1|2018-01-04|New hydrocarbon polymers comprising two alkoxysilane end groups, and methods for preparing same
    FR3051471A1|2017-11-24|HYDROCARBON POLYMERS WITH TWO ALCOXYSILANE TERMINAL GROUPS
    FR3066762B1|2019-06-28|LIQUID HYDROCARBON COPOLYMERS WITH TWO ALCOXYSILANE TERMINAL GROUPS AND PROCESS FOR PREPARING THE SAME
    EP3523286B1|2021-02-24|Novel hydrocarbon polymers having exo-vinylene cyclic carbonate terminal groups
    WO2015107289A1|2015-07-23|Hydrocarbon-based polymers comprising an end group with a 2-oxo-1,3-dioxolane-4-yl ending, preparation thereof and use thereof
    EP2931783A2|2015-10-21|Hydrocarbon polymers comprising a 2-oxo-1,3-dioxolan-4-yl end group, preparation and use thereof
    WO2018050993A1|2018-03-22|Hydrocarbon polymers with two 2-oxo-1,3-dioxolan-4-carboxylate end groups
    EP3688039A1|2020-08-05|Liquid hydrocarbon copolymers having two cyclocarbonate ether end groups
    FR3071502A1|2019-03-29|LIQUID HYDROCARBON COPOLYMERS WITH TWO ESTER CYCLOCARBONATE TERMINAL GROUPS
    同族专利:
    公开号 | 公开日
    EP3280706A1|2018-02-14|
    EP3280706B1|2019-05-22|
    FR3034770B1|2017-05-12|
    US20180072842A1|2018-03-15|
    US10723836B2|2020-07-28|
    ES2738681T3|2020-01-24|
    WO2016162627A1|2016-10-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1098953B|1959-09-29|1961-02-09|Basf Ag|Process for the preparation of 5-methylene-4, 4-dialkyl-1, 3-dioxolan-2-ones|
    WO2013144299A1|2012-03-29|2013-10-03|Basf Se|Polymerizable alkylidene-1,3-dioxolan-2-ones and use thereof|
    US20130331532A1|2012-03-29|2013-12-12|Basf Se|Polymerizable alkylidene-1,3-dioxolane-2-one and use thereof|
    WO2014091173A1|2012-12-14|2014-06-19|Bostik Sa|Hydrocarbon-based polymers comprising two end groups with 2-oxo-1,3-dioxolan-4-yl endings, preparation thereof and use thereof|
    EP2851379A1|2013-09-23|2015-03-25|BASF Coatings GmbH|Coating composition and coatings prepared therefrom which are curable at low temperatures as well as their use|
    EP2851403A1|2013-09-23|2015-03-25|BASF Coatings GmbH|Coating substance compounds andlow temperature curable coatings made therefrom and their use|
    DE1573954B1|1966-12-06|1970-04-23|Wafios Maschinen Wagner|Device for stretching and testing chain links|
    DE3433403A1|1984-09-12|1986-03-20|Basf Ag, 6700 Ludwigshafen|METHOD FOR PRODUCING 4,4-DISUBSTITUTED 5-METHYLENE-1,3-DIOXOLAN-2-ONES|
    EP0773948A4|1992-04-03|1998-09-02|California Inst Of Techn|High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof|
    GB9916235D0|1999-07-09|1999-09-15|Univ Durham|Process for polymerisation of olefins and novel polymerisable olefins|
    WO2007100891A1|2006-03-01|2007-09-07|Firestone Polymers, Llc|Polyester compositions containing metathesis polymers with reduced recycle color|
    US8283410B2|2009-03-30|2012-10-09|Isp Investments Inc.|Ring-opening metathesis polymerization of norbornene and oxanorbornene moieties and uses thereof|FR3057269B1|2016-10-07|2018-11-23|Bostik Sa|NOVEL HYDROCARBON POLYMERS WITH EXO-VINYLENE CYCLOCARBONATE TERMINAL GROUPS|
    FR3071501A1|2017-09-28|2019-03-29|Bostik Sa|LIQUID HYDROCARBON COPOLYMERS WITH TWO TERMINAL GROUPS ETHER CYCLOCARBONATE|
    FR3071502B1|2017-09-28|2020-06-19|Bostik Sa|LIQUID HYDROCARBON COPOLYMERS WITH TWO ESTER CYCLOCARBONATE TERMINAL GROUPS|
    法律状态:
    2016-03-09| PLFP| Fee payment|Year of fee payment: 2 |
    2016-10-14| PLSC| Search report ready|Effective date: 20161014 |
    2017-03-13| PLFP| Fee payment|Year of fee payment: 3 |
    2018-03-15| PLFP| Fee payment|Year of fee payment: 4 |
    2019-03-13| PLFP| Fee payment|Year of fee payment: 5 |
    2020-02-28| CA| Change of address|Effective date: 20200122 |
    2020-03-12| PLFP| Fee payment|Year of fee payment: 6 |
    2021-03-10| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1553103A|FR3034770B1|2015-04-10|2015-04-10|HYDROCARBON POLYMERS COMPRISING TWO EXO-VINYLENE CYCLOCARBONATE TERMINAL GROUPS|FR1553103A| FR3034770B1|2015-04-10|2015-04-10|HYDROCARBON POLYMERS COMPRISING TWO EXO-VINYLENE CYCLOCARBONATE TERMINAL GROUPS|
    ES16722280T| ES2738681T3|2015-04-10|2016-04-05|Hydrocarbon polymers comprising two exo-vinyl cyclocarbonate terminal groups|
    US15/565,334| US10723836B2|2015-04-10|2016-04-05|Hydrocarbon polymers comprising two exo-vinylene cyclic carbonate terminal groups|
    PCT/FR2016/050774| WO2016162627A1|2015-04-10|2016-04-05|Hydrocarbon polymers comprising two exo-vinylene cyclic carbonate terminal groups|
    EP16722280.1A| EP3280706B1|2015-04-10|2016-04-05|Hydrocarbon polymers comprising twoexo-vinylene cyclic carbonate terminal groups|
    [返回顶部]