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    • 专利摘要:
    CURABLE COMPOSITION, USE OF A POLY-ISOCIANURATE COMPOSITION, PROCESSES FOR THE MANUFACTURE OF A CURABLE COMPOSITION AND OF A MATERIAL CONTAINING POLY-ISOCIANURATE, AND, MATERIAL CONTAINING POLY-ISOCIANURATE. Stable polyisocyanate composition containing a compound with a -CO-NH-CO- structure group in an amount such that the ratio of the number of -CO-NH-CO- groups to the number of isocyanate groups is at most equal to 1. Curable composition containing this composition of polyisocyanate, lithium halide, urea and an epoxy resin.
    公开号:BR112014015899B1
    申请号:R112014015899-1
    申请日:2012-11-30
    公开日:2021-02-17
    发明作者:Christian Esbelin；Hugo Verbeke；Hans Godelieve Guido Verbeke
    申请人:Huntsman International Llc；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to a stable polyisocyanate composition, to a process for making that composition, to a curable composition in which the stable polyisocyanate composition according to the present invention is used, to a a process for making that curable composition, a polyisocyanurate material manufactured or obtainable from that curable composition, and a process for making such polyisocyanurate materials.
    [0002] [0002] Recently a curable composition has been proposed that includes a polyisocyanate, a lithium halide, a urea compound and an epoxy resin; see PCT / EP2010 / 054492.
    [0003] [0003] The use of lithium chloride and compounds containing urea groups has been described by Sheth, Aneja and Wilkes in Polymer (Polymer) 45 (2004) 5979-5984. They studied the influence of the degree of hydrogen bonding in the mediation of long-range connectivity and percolation of the hard segment phase in tri-segmented oligomeric polyurethanes model using LiCl as a molecular probe.
    [0004] [0004] In US 5086150 an isocyanate-terminated prepolymer is reacted with a diamine in the presence of a fairly high amount of LiCl to prepare an elastomer solution that is stable for at least two days. At the beginning of the reaction, the number of moles of lithium chloride per isocyanate equivalent is quite high; lithium chloride is used to act as a solubilizer. At the beginning of the reaction, the composition is not stable and does not contain urea and at the end of the reaction it is an elastomer and is no longer an isocyanate composition. The product obtained is an elastomer solution used to make threads and films.
    [0005] [0005] The polyisocyanate composition according to the present invention is very suitable for preparing a curable composition together with epoxy compounds.
    [0006] [0006] The use of isocyanates and epoxies together with LiCl has been described in Russian Chemical Reviews 52 (6) 1983, 576-593. The reaction is influenced by the nature of the catalyst. In the presence of metal halides, an activated complex is formed, which finally provides an oxazolidone. One of the secondary reactions is the formation of isocyanurate rings that decompose in the treatment with epoxides. In addition, it has been described in that publication that epoxides are capable of cleaving urea bonds with formation of oxazolidones.
    [0007] [0007] US 4658007 describes a process for preparing an oxazolidone-containing polymer using organoantimone iodide catalyst by reacting a polyisocyanate and a polyepoxide.
    [0008] [0008] US 5326833 describes a composition containing a polyisocyanate, an epoxide and a catalyst consisting of a solution of an alkali halide, such as LiCl, in a polyoxyalkylene compound. These compositions are able to gel quickly between 0 ° C and 70 ° C.
    [0009] [0009] Juan et al discuss in the Journal of East China University of Science and Technology Vol. 32, No 11, 2006, 1293-1294 the influence of LiCl on the morphological structure and properties of polyurethane-urea. They show that the viscosity of poly (urethane-urea) solutions first decreases and subsequently increases. The poly (urethane-urea) was manufactured by reacting polyepoxypropane glycol and diisocyanate isophorone with excess polyisocyanate.
    [0010] [00010] In US 3517039 acylated urea polyisocyanates are manufactured by reacting an organic diisocyanate with an organic monocarboxylic acid. These polyisocyanates are used in the preparation of polyurethanes, especially when small amounts of branching are desirable.
    [0011] [00011] In US 3,970,600 stable solutions of isocyanurate-polyisocyanates containing amide and / or acylurea groups have been described. They prevent deposition of fine or coarse crystalline solids on polyisocyanates containing isocyanurate groups. First a polyisocyanate is reacted with polybasic carboxylic acid to prepare a polyisocyanate with substituted amide and / or acyl urea groups. This polyisocyanate is then trimerized to form an isocyanurate-polyisocyanate and this conversion is stopped with the addition of acid.
    [0012] [00012] In JP 2-110123 an aliphatic diisocyanate is trimerized to prepare polyisocyanates having an isocyanurate structure using a catalyst and a deactivating agent once the desired degree of conversion has been obtained. The deactivating agent has the structure -CO-NH2 or -SO-NH2 and can be urea, methyl urea, 1,1-dimethyl urea, phenyl carbamate, ethylcarbamate or butylcarbamate. Subsequently, deactivated catalyst, excess diisocyanate and solvent, if used, are eliminated. Using this deactivating agent, the polyisocyanate containing polyisocyanurate structure has a lower degree of discoloration.
    [0013] [00013] WO 2008/068198 and US 2010/0022707 describe a process for preparing an oligomerized polyisocyanate using a catalyst in which a deactivator is used once the desired conversion has been achieved, followed by the removal of the non-polyisocyanate has been converted. The deactivator can be selected from among urea and compounds containing urea, among others.
    [0014] [00014] EP 585835 describes a process for preparing polyisocyanate mixtures containing isocyanurate and urethane groups by partial cyclisation of diisocyanates in the presence of a trimerization catalyst, deactivating the trimerization catalyst when the desired conversion is achieved, and subsequently reacting the polyisocyanate containing the resulting isocyanurate group with hydroxyl compounds and then separating the monomeric diisocyanate.
    [0015] [00015] Other descriptions related to partially trimerized polyisocyanate compositions using different methods to stop trimerization are: EP 447093, US 4284730, US 4537961, US 4697014, US 4743627, US 5124370, US 5221743 and US 7553963. None of these descriptions reveals the present invention or points in its direction.
    [0016] [00016] US 7071353 products for the reaction of isocyanates with carboxylic acids are described. First, amides are formed which then form acylureas by reaction with other isocyanate groups.
    [0017] [00017] US 4371544 describes the reaction product of phenylisocyanate and 1-ethyl, 1-methyl urea.
    [0018] [00018] Thermally activated PIR catalysis has been described in US 6127308.
    [0019] [00019] Urea and amides have been described as anti-blocking agents in US 5817732.
    [0020] [00020] US 4302351 describes isocyanurates and blocking agents containing acidic hydrogen.
    [0021] [00021] In GB 1463809 monosubstituted ureas and in US 4330656 N-methylurea were used as a catalyst.
    [0022] [00022] Choline type catalysts have been described in EP 1085030, US 6613863 and US 6875243.
    [0023] [00023] Surprisingly we have discovered a polyisocyanate composition containing a compound having a group -CO-NH-CO- which is stable and liquid at 20 ° C and ambient pressure and which can be used to make a curable composition useful for making a polyisocyanurate material at an elevated temperature and which has a long storage life at 20 ° C and ambient pressure.
    [0024] [00024] Therefore, the present invention relates to a stable polyisocyanate composition containing a compound having a -CO-NH-CO- group that is suitable for making a curable composition. The compound having a -CO-NH-CO- group is a "similar to imide" structure containing 2 carbonyl groups attached to a -NH- group.
    [0025] [00025] The compound having a -CO-NH-CO- group is present in an amount such that the ratio of groups -CO-NH-CO- to the number of isocyanate groups is at most 1, preferably at most 0.01 , more preferably at most 0.0015.
    [0026] [00026] According to one embodiment the compound having the -CO-NH-CO- group can be added to a polyisocyanate composition to create the stable polyisocyanate composition according to the invention.
    [0027] [00027] According to one embodiment, the compound having the -CO-NH-CO- group can be a compound having an acyl urea group with the -CO-NH-CO-NH- structure. Said compound having acylurea group can be the reaction product of a polyisocyanate with a compound comprising a carboxamide group having the structure -CO-NH2. However, compounds having an acylurea group according to the invention are not limited to reaction products of a compound containing a carboxamide with a polyisocyanate.
    [0028] [00028] In addition, the present invention relates to a process for preparing the stable polyisocyanate composition above, which process includes adding and mixing a compound comprising a -CO-NH-CO- group to a poly composition -isocyanate. The final concentration of the compound containing the -CO-NH-CO- group in the stable polyisocyanate composition is such that the ratio of -CO-NH-CO- groups to the number of isocyanate groups is at most 1, preferably at most 0 .01, more preferably at most 0.0015.
    [0029] [00029] In the case where the compound having a -CO-NH-CO- group is a compound having an acylurea group with the structure -CO-NH-CO-NH- and which is also a reaction product of a poly- isocyanate with a compound containing the carboxamide group with the -CO-NH2 structure, the compound having the carboxamide group with the -CO-NH2 structure can be added (mixed) to the polyisocyanate composition allowing the mixture to react, the amount of which compound containing carboxamide group is such that after the reaction has been carried out, the ratio of acylurea groups to the number of isocyanate groups is at most 1, preferably at most 0.01, more preferably at most 0.0015.
    [0030] [00030] The present invention further relates to the use of the stable polyisocyanate composition according to the present invention to improve the storage life of a curable polyisocyanate composition, to that curable polyisocyanate composition, the a process for making such a curable polyisocyanate composition, a polyisocyanurate material made from such a curable polyisocyanate composition and a process for making that polyisocyanurate material.
    [0031] [00031] In the context of the present invention the following terms have the following meaning: 1) isocyanate index or NCO index or index: The ratio of NCO groups to isocyanate-reactive hydrogen atoms present in a formulation, expressed as a percentage: [NCO] x 100 (%). [active hydrogen] In other words, the NCO index expresses the percentage of isocyanate actually used in a formulation with respect to the amount of isocyanate theoretically needed to react with the amount of isocyanate-reactive hydrogen used in a formulation. It should be noted that the isocyanate index, in this context, is considered from the point of view of the actual polymerization process that prepares the material involving the isocyanate ingredient and the isocyanate reactive ingredients. Any isocyanate groups consumed in a preliminary step to produce modified polyisocyanates (including the isocyanate derivatives referred to in the art as prepolymers) or any active hydrogens consumed in a preliminary step (for example reacted with isocyanate to produce modified polyols or polyamines) are not taken into account when calculating the isocyanate index. Only free isocyanate groups and free isocyanate reactive hydrogens (including those in water, if used) present in the actual polymerization stage are taken into account. 2) The expression “hydrogen atoms reactive to isocyanate”, in this context, for the purpose of calculating the isocyanate index refers to the total of active hydrogen atoms in the hydroxyl and amine groups present in the reactive compositions; this means that for the purpose of calculating the isocyanate index in the actual polymerization process a hydroxyl group is considered to include a reactive hydrogen, a primary amine group is considered to include a reactive hydrogen and a water molecule is considered to include two reactive hydrogens . 3) Reaction System: a combination of components in which the polyisocyanates are kept in one or more containers separate from the reactive isocyanate components. 4) The term “nominal mean hydroxyl functionality” (or “functionality” for short) is used in this context to indicate the average numerical functionality (number of hydroxyl groups per molecule) of the polyol or polyol composition assuming that this is the average numerical functionality ( number of active hydrogen atoms per molecule) of the initiator (s) used in its preparation although in practice it is often a little less because of some terminal unsaturation. 5) The word “average” refers to the numerical average, unless otherwise indicated. 6) “Liquid” means having a viscosity of less than 10 Pa.s measured according to ASTM D445-1 la at 20 ° C. 7) “Stable polyisocyanate composition” is a polyisocyanate composition according to the present invention, which does not change more than 10% of its initial NCO value when maintained at 80 ° C and ambient pressure for 10 minutes, the NCO value being determined under ambient conditions. As an example: a polyisocyanate composition having an NCO value of 25% by weight should have an NCO value in the range of 22.5-27.5% by weight after being kept at 80 ° C for 10 minutes to be considered stable, both NCO values being determined under ambient conditions.
    [0032] [00032] The compounds having a -CO-NH-CO- group according to the invention correspond to the formula RrCO-NH-CO-R2 in which R1 and R2, each independently of the other, are selected from 1) hydrogen ( H), 2) -NR3R4, 3) hydrocarbyl having 1-100 carbon atoms and optionally containing hydroxy, ether, halogen, carboxyl, oxygen, isocyanate and / or amine groups, in which R3 and R4 independently of each other, are selected between hydrogen, hydroxy, halogen and hydrocarbyl groups, hydrocarbyl groups those having 1-20 carbon atoms and optionally containing hydroxy, ether, halogen, carboxyl, isocyanate and / or amine groups, where R! and R2 can be linked to each other essentially forming a ring structure including the -CO-NH-CO- group, and where the hydrocarbyl groups in the compounds corresponding to the formula RrCO-NH-CO-R2 can be a combination of linear hydrocarbons , branched, saturated, unsaturated, cyclic and / or non-cyclic aliphatic, aromatic or araliphatic and mixtures of these compounds.
    [0033] [00033] Preferably the compound having a -CO-NH-CO- group according to the invention has a maximum molecular weight of 1500.
    [0034] [00034] In the case where R1 and R2 are attached to the -CO-NH-CO- group so that a ring structure is formed in the compound Ri-CO-NH-CO-R2 then R1 and R2 together with the group - CO-NH-CO- can form a 4- to 12-membered ring structure (in the case of a 4-membered ring structure there is no R2 involved). Examples of suitable compounds R1-CO-NH-CO-R2 having a ring structure are:
    [0035] [00035] The ring structure may contain 1 or more unsaturations and / or optionally 1 or more aromatic rings and / or optionally rings with hetero atoms. Examples of suitable compounds R1-CO-NH-CO-R2 in which R1 and R2 together with the -CO-NH-CO- group can form a 4- to 12-membered ring structure and which include unsaturations, aromatic rings and / or heteroatoms are provided below.
    [0036] [00036] According to one embodiment, the compound having a -CO-NH-CO- group can be a compound having an acyl urea group with the -CO-NH-CO-NH- structure. Said compound having an acylurea group according to the invention corresponds to the formula R6-CO-NH-CO-NH-R7 and can be the reaction product of a polyisocyanate containing reactive NCO groups and corresponding to the formula R7-NCO and a compound comprising a carboxamide group having the structure -CO-NH2. and corresponding to the formula NH2-CO-R6.
    [0037] [00037] The polyisocyanate compound containing reactive NCO groups corresponds to the formula R7-NCO in which R7 can be selected from hydrogen and hydrocarbyl groups, which hydrocarbyl groups have 1-20 carbon atoms and optionally include hydroxy, ether, halogen groups , carboxyl, isocyanate and / or amine and wherein said hydrocarbyl groups may be a combination of linear, branched, saturated, unsaturated, cyclic and / or non-cyclic aliphatic, aromatic or araliphatic and mixtures of these compounds.
    [0038] [00038] The carboxamide-containing compound, which can be used to manufacture the compound comprising an acylurea group having the structure -CO-NH-CO-NH- according to the present invention, is preferably selected from a compound according to with the formula NH2-CO-R6 where R6 is 1) hydrogen (-H), 2) -NR8R9, 3) hydrocarbyl having 1-20 carbon atoms and optionally containing hydroxy, ether, halogen and / or amine groups, or 4) -R10-CO-NH2, in which R8 and R9, independently of each other, are selected from hydrogen, hydroxy, halogen and hydrocarbyl groups, which hydrocarbyl groups have 1-10 carbon atoms and optionally include hydroxy groups, ether , halogen and / or amine and where R10 is a divalent hydrocarbon radical having up to 8 carbon atoms. Mixtures of these carboxamides can also be used. Preferably these carboxamides have a molecular weight of a maximum of 499.
    [0039] [00039] The hydrocarbyl groups in these carboxamides can be linear or branched, saturated or unsaturated and cyclic or non-cyclic; they can be aliphatic, aromatic or araliphatic.
    [0040] [00040] Most preferred carboxamides are those in which R6 is 1) -NR8R9, 2) alkyl having 1-10 carbon atoms and optionally containing 1-3 hydroxy and / or ether groups, 3) phenyl or 4) tolyl, where R8 and R9, independently of each other, are selected from hydrogen, hydroxy, phenyl, tolyl and alkyl having 1-6 carbon atoms and optionally containing a hydroxy group and / or an ether group. Mixtures of these more preferred compounds are also more preferred.
    [0041] [00041] Examples of very useful carboxamides (NE2-CO-R6) are as follows:
    [0042] [00042] At most preference, carbamide (urea) is used. It should be noted that in calculating the number of carboxamide equivalents, carbamide (urea) is considered to contain 2 carboxamide groups.
    [0043] [00043] The compound comprising an acylurea group having the structure -CO-NH-CO-NH- can be supplied and / or prepared beforehand and after preparation added to a polyisocyanate composition to form the stable polyisocyanate composition according to the invention. The polyisocyanate used to manufacture the acylurea compound can be the same or different from the polyisocyanate present in the stable polyisocyanate composition.
    [0044] [00044] Alternatively, the compound comprising an acylurea group with the structure -CO-NH-CO-NH- can be prepared by combining and mixing the compound containing the carboxamide group with structure -CO-NH2 to a composition of polyisocyanate composition and letting them react to form the compound having an acylurea group and to form the stable polyisocyanate composition according to the invention.
    [0045] [00045] If desired, the carboxamide-containing compound can be dissolved in a solvent before being reacted with the polyisocyanate. The solvent can be selected from a solvent that is not reactive with NCO groups or from solvents that are reactive with NCO groups such as mono, polyols. One or more solvents can be used. Examples of solvents have been provided additionally in this report.
    [0046] [00046] According to the invention, the reaction (the carboxamide with the polyisocyanate compound) is preferably carried out with stirring and nitrogen atmosphere. The reaction is preferably carried out at a temperature of 15 to 90 ° C and preferably 20-85 ° C. In general, the reaction is carried out for 1 minute to 5 hours and preferably for 1 minute to 1 hour.
    [0047] [00047] The polyisocyanate corresponding to the formula R7-NCO used to manufacture the acylurea compound corresponding to the formula R6-CO-NH-CO-NH-R7 can be the same or different from the polyisocyanate compound present in the stable polyester composition. isocyanate which is used to manufacture the curable polyisocyanate composition according to the invention.
    [0048] [00048] In general, the polyisocyanate compound (s) according to the present invention can be selected from aliphatic and, preferably, aromatic polyisocyanates. Preferred aliphatic polyisocyanates are hexamethylene diisocyanate, isophorone diisocyanate, methylene dicyclohexyl diisocyanate and cyclohexane diisocyanate and preferred aromatic polyisocyanates are toluene diisocyanate, naphthalene diisocyanate, tetramethylene di isocyanate, phenylene diisocyanate, tolidin diisocyanate and, in particular, methylene diphenyl diisocyanate (MDI) and polyisocyanate compositions containing methylene diphenyl diisocyanate (such as the so-called polymeric MDI, crude MDI, MDI modified by uretonimine and prepolymers having free isocyanate groups made of MDI and polyisocyanates containing MDI) and mixtures of these polyisocyanates. MDI and polyisocyanate compositions containing MDI are most preferred and especially those selected from 1) a diphenylmethane diisocyanate containing at least 35%, preferably at least 60% by weight of 4,4'-diphenylmethane diisocyanate (4 , 4'-MDI); 2) a polyisocyanate variant 1) modified by carbodiimide and / or uretonimine, the variant having an NCO value of 20% by weight or more; 3) a polyisocyanate variant 1) and / or 2) modified by urethane, the variant having an NCO value of 20% by weight or more and being the reaction product of an excess of polyisocyanate 1) and / or 2) and a polyol having a nominal average hydroxyl functionality of 2-4 and an average molecular weight of a maximum of 1000; 4) a diphenylmethane diisocyanate containing a homolog containing 3 or more isocyanate groups; 5) prepolymers having an NCO value of 5-30% by weight and the reaction product of any one or more of polyisocyanates 1) -4) and a polyol having a nominal average hydroxyl functionality of 2-4 and an average molecular weight of more than 1,000 and up to 8,000; and 6) mixtures of any of the aforementioned polyisocyanates.
    [0049] [00049] Polyisocyanate 1) includes at least 35% by weight of 4,4'-MDI. Such polyisocyanates are known in the art and include pure 4,4'-MDI and isomeric mixtures of 4,4'-MDI, 2,4'-MDI and 2,2'-MDI. It should be noted that the amount of 2,2'-MDI in isomeric mixtures is at an impurity level and will generally not exceed 2% by weight, the remainder being 4,4'-MDI and 2,4'-MDI. Polyisocyanates like these are known in the art and commercially available; for example SuprasecR MPR and 1306 ex Huntsman (Suprasec is a registered trademark of Huntsman Corporation or a subsidiary thereof which has been registered in one or more, but not all countries).
    [0050] [00050] The carbodiimide and / or uretonimine modified variants of the polyisocyanate 1) above are also known in the art and commercially available; e.g. SuprasecR 2020, ex Huntsman. Urethane modified variants of the polyisocyanate 1) above are also known in the art, see e.g. The ICI Polyurethanes Book by G. Woods 1990, 2nd edition, pages 32-35.
    [0051] [00051] Polyisocyanate 4) is also widely known and commercially available. These polyisocyanates are often called crude MDI or polymeric MDI. Examples are SuprasecR 2185, SuprasecR 5025 and SuprasecR DNR ex Huntsman.
    [0052] [00052] Prepolymers (polyisocyanate 5)) are also widely known and commercially available. Examples are SuprasecR 2054 and SuprasecR 2061, both ex Huntsman.
    [0053] [00053] Mixtures of the aforementioned polyisocyanates can also be used, see e.g. The ICI Polyurethanes Book by G. Woods 1990, 2nd edition pages 32-35. An example of such a commercially available polyisocyanate is SuprasecR 2021 ex Huntsman.
    [0054] [00054] The NCO value of the stable polyisocyanate composition after addition and / or formation (in situ) of the compound having a -CO-NH-CO- group according to the present invention can be in the range of 10 to 48 % by weight and preferably in the range of 20 to 33% by weight.
    [0055] [00055] The polyisocyanate composition according to the present invention obtained after addition and / or formation (in situ) of the compound having a -CO-NH-CO- group is stable and liquid and can be used to improve life storage of a curable polyisocyanate composition. Such a curable polyisocyanate composition is obtained by combining a lithium halide, a urea compound (not being an acylurea as described above) and an epoxy resin with the stable polyisocyanate composition according to the present invention.
    [0056] [00056] The lithium halide used in the curable polyisocyanate composition according to the present invention is used in an amount of 0.0001-0.04 and preferably 0.00015-0.025 and at most preferably 0, 0005-0.02 moles per equivalent of isocyanate and is preferably selected from lithium chloride and lithium bromide. Lithium chloride is most preferred.
    [0057] [00057] The urea compound used in the curable polyisocyanate composition according to the present invention is used in an amount such that the number of urea + biuret equivalents is 0.0001-0.4 and preferably 0.001-0, 2 and at most of the preference 0.001-0.05 per isocyanate equivalent. Most preferably the number of urea + biuret equivalents in the urea compound of the polyisocyanate composition per mol of lithium halide is in the range of 0.5-60 and most preferably 0.5-30. The urea compound must not contain other isocyanate-reactive groups (i.e., other than urea groups). When calculating the number of urea equivalents, the urea groups of the carboxamides are not taken into account.
    [0058] [00058] The urea compound used in the curable polyisocyanate composition according to the present invention has an average molecular weight of 500-15,000 and preferably 600-10,000 and most preferably 800-8000. These urea compounds are prepared by reacting polyisocyanates and amines (other than carboxamides having the structure R-CO-NH2).
    [0059] [00059] The polyisocyanates used to prepare this urea compound can be selected from the polyisocyanates mentioned above. The preferences mentioned above also apply here. Most preferably, polyisocyanates 1) and 2) and mixtures thereof are used. The polyisocyanate used to prepare the stable polyisocyanate composition according to the present invention and the polyisocyanate used to produce the urea compound can be the same or different.
    [0060] [00060] The amines used to prepare the urea compounds can be monoamines or polyamines. Preferably monoamines, optionally containing a small amount of polyamines, are used. The average amine functionality of these mixtures is preferably at most 1.2. At most preference, only monoamines are used. These amines are preferably primary amines.
    [0061] [00061] The molecular weight of the amines is selected in such a way that once reacted with the selected polyisocyanate the molecular weight of the obtained urea compound falls in the above ranges. In general, the molecular weight of the amines is in the range of 200-7500 and preferably 200-4500 and at most preferably 200-3000.
    [0062] [00062] Amines can be selected from those known in the art as amine-terminated hydrocarbons, polyesters, polyethers, polycaprolactones, polycarbonates, polyamides and mixtures thereof. Most preferably, amine-terminated polyoxyalkylene monoamines and more particularly polyoxyethylene polyoxypropylene monoamines. Preferably the oxypropylene content in these polyoxyalkylene monoamines is at least 50 and preferably at least 75% by weight calculated based on the total weight of the monoamine molecule. Preferably, the polyoxyalkylene monoamines have a monoalkyl group at the other end of the polymer chain, the alkyl group having 1-8 and preferably 1-4 carbon atoms. Such monoamines are known in the art. They are manufactured by alkoxylation of an alkylmonoalcohol having 1-8 carbon atoms and subsequent conversion of polyoxyalkylene monool to monoamine. These monoamines are commercially available. Examples are JeffamineR M-600 and M-2005, both ex Huntsman (Jeffamine is a registered trademark of Huntsman Corporation or a subsidiary of the same that has been registered in one or more, but not all countries). Mixtures of monoamines can also be used.
    [0063] [00063] In view of the above, a most preferred urea compound used in the polyisocyanate composition according to the present invention is a urea compound obtained by reacting a methylene diphenyl diisocyanate or a polyisocyanate containing methylene diphenyl diisocyanate or a mixture of these polyisocyanates with a polyoxyalkylene monoamine, containing oxypropylene groups in an amount of at least 75% by weight calculated based on the total weight of the monoamine molecule and having an average molecular weight of 200-3,000 and where the amine is a primary amine.
    [0064] [00064] Polyisocyanate and monoamine are combined and mixed and allowed to react. The reaction is exothermic and therefore does not require heating and / or catalysis, although heat and / or catalysis can be applied if this is considered convenient. For example, it may be convenient to preheat the polyisocyanate and / or monoamine to 40-60 ° C and then mix them. After mixing, the temperature of the reaction mixture is preferably maintained below 90 ° C to avoid side reactions, such as e.g. biuret formation. To ensure that the entire amine reacts, a slight excess of polyisocyanate can be used; performing the reaction at an index of 101-110 is therefore preferred. After a maximum of 1 hour the reaction can be considered complete and the urea compound is ready for use in the manufacture of the polyisocyanate composition according to the present invention.
    [0065] [00065] As a small excess of polyisocyanate is used in the preparation of the urea compound and as the urea compound in the next step is added to a relatively high amount of polyisocyanate, some of the urea groups could be converted to biuret groups. By controlling the reaction temperature and the temperature of the subsequent mixing steps, this biuret formation is avoided as much as possible. In general, the number of urea groups that are converted to biuret groups is less than 25% and preferably less than 10%.
    [0066] [00066] The epoxy resin used is preferably selected from any epoxy resin that is liquid at 20 ° C.
    [0067] [00067] Examples of epoxy resins are:
    [0068] [00068] Polyglycidyl and poly (β-methylglycidyl) esters, obtainable by reacting a compound having at least two carboxyl groups in the molecule and, respectively, epichlorohydrin and β-methylpichlorohydrin. The reaction is conveniently carried out in the presence of bases.
    [0069] [00069] Aliphatic polycarboxylic acids can be used as the compound having at least two in the molecule. Examples of such polycarboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid and dimerized or trimerized linoleic acid.
    [0070] [00070] However, cycloaliphatic polycarboxylic acids, such as, for example, tetrahydrophthalic acid, 4-methyltetrahydroic acid, hexahydrophthalic acid or 4-methylhexahydro hydrophthalic, can also be used.
    [0071] [00071] In addition, aromatic polycarboxylic acids, such as, for example, phthalic acid, isophthalic acid or terephthalic acid, can be used.
    [0072] [00072] II) Polyglycidyl or poly (β-methylglycidyl) ethers, obtainable by the reaction of a compound having at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups with epichlorohydrin or β-methylpichlorohydrin in alkaline conditions or in the presence of a catalyst acid with subsequent alkali treatment.
    [0073] [00073] Glycidyl ethers of this type are derived, for example, from acyclic alcohols, for example from ethylene glycol, diethylene glycol or higher poly (oxyethylene) glycols, propane-1,2-diol or poly (oxypropylene) glycols, propane- 1,3-diol, butane-1,4-diol, poly (oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1, 1,1-trimethylolpropane, pentaerythritol or sorbitol, and polyhepichlorohydrins. Other glycidyl ethers of this type are derived from cycloaliphatic alcohols, such as 1,4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane, or alcohols containing aromatic groups and / or other functional groups, such as N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) -diphenylmethane.
    [0074] [00074] Glycidyl ethers can also be based on mononuclear phenols, such as, for example, pt-butylphenol, resorcinol or hydroquinone, or on polynuclear phenols, such as, for example, bis (4-hydroxyphenyl) methane, 4,4'- dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (3,5- dibromo-4-hydroxyphenyl) propane.
    [0075] [00075] Other hydroxy compounds suitable for the preparation of glycidyl ethers are novolaca, obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols or bisphenols that are unsubstituted or substituted by chlorine atoms or C1-C9 groups -alkyl, such as, for example, phenol, 4-chlorophenol, 2-methylphenol or 4-t-butylphenol.
    [0076] [00076] III) Poly (N-glycidyl) compounds, obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least two amine hydrogen atoms. These amines are, for example, aniline, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane.
    [0077] [00077] Poly (N-glycidyl) compounds also include triglycidyl isocyanurate, Ν, Ν'-diglycidyl cycloalkylourea compounds, such as ethylene urea or 1,3-propylenourea, and diglycidyl derivatives of hydantoins, such as 5.5-dimethylhydantoin .
    [0078] [00078] IV) Poly (S-glycidyl) compounds, for example di-S-glycidyl derivatives, which are derived from dithols, such as, for example, ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.
    [0079] [00079] V) Cycloaliphatic epoxy resins, such as bis (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane or 3,4- epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.
    [0080] [00080] It is also possible to use epoxy resins in which the 1,2-epoxy groups are attached to different heteroatoms or functional groups; these compounds include, for example, the 4-aminophenol derivative Ν, Ν, Ο-triglycidyl, salicylic acid glycidyl ether-ester, N-glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethyl -hydantoin or 2-glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidyl-hydantoin-3-yl) propane.
    [0081] [00081] Particularly preferred are those mentioned in I and II and the most preferred are those mentioned in II.
    [0082] [00082] If an epoxy resin containing hydroxyl groups or other isocyanate-reactive hydrogens is used, then these hydroxyl groups and hydrogens will not be taken into account when calculating the index or the number of hydroxyl equivalents.
    [0083] [00083] The curable polyisocyanate composition according to the present invention is prepared by mixing the stable polyisocyanate composition according to the present invention, the compound urea, lithium halide, epoxy resin and optionally another poly -isocyanate in any order under ambient conditions or at elevated temperature, eg at 40-70 ° C. Preferably the lithium halide is pre-mixed with the urea compound optionally another polyisocyanate and this mixture is subsequently added to the stable polyisocyanate and mixed. Before mixing the lithium halide and the urea compound, it may be convenient to dissolve the lithium halide in a solvent, such as in an organic solvent such as an alcohol, e.g. methanol or ethanol. The dissolved lithium halide is then added to the urea compound. Subsequently, the solvent can be removed if desired. Pre-mixing and mixing are carried out under ambient conditions or at elevated temperature, e.g. at 40-70 ° C and are carried out with normal stirring. The relative amounts of the polyisocyanate, the urea compound and the lithium halide are chosen in such a way that the final polyisocyanate composition according to the invention has the relative amounts of isocyanate groups, urea groups and lithium halide as described above. Without wishing to be limited by any theory, it is believed that lithium halide is present in dissociated form, complexed with the urea group as a so-called bidentate complex. Finally, the epoxy resin is added and mixed in relative amounts such that the number of epoxy equivalents per isocyanate equivalent is in the range of 0.003-1 and preferably 0.003-0.5 and at most preferably 0.0050.25 and same conditions mentioned above.
    [0084] [00084] The curable composition thus obtained has a good storage life under ambient conditions. It is used to prepare a polyisocyanurate material preferably having a Tg (measured according to ASTM D4065) of at least 120 ° C allowing it to react at elevated temperature, preferably above 50 ° C and most preferably above 80 ° C Ç. Thus, the invention further relates to a polyisocyanurate material made by allowing the curable composition according to the present invention to react at an elevated temperature and to a polyisocyanurate material obtainable allowing the curable composition according to the present invention to react at an elevated temperature and to a process for producing these polyisocyanurate materials allowing the curable composition according to the present invention to react at elevated temperature. Preferably the reaction is carried out at an index greater than 100, preferably at least 300 (eg in a range of 300-100000) and most preferably at least 500. Preferably heat is applied to bring the curable composition to a temperature above 50 ° C and at most preferably above 80 ° C. The curable composition can then cure quickly (The so-called snap-cure) while the temperature increases further (the reaction is exothermic).
    [0085] [00085] The curable compositions according to the present invention can be used in a wide variety of composite processing methods to prepare a wide variety of composite materials. For example, they can be used to repair an object and in particular a pipe by applying them to the inner and / or outer surface of that object or pipe according to the so-called cured in place method. The curable compositions according to the present invention can be used in resin transfer molding to produce door panels or honeycomb structures, in vacuum-assisted resin infusion to manufacture structural automotive parts such as car hoods or rail tracks. chassis, in filament winding to produce pressure vessels or gas tanks and in pultrusion to manufacture fiber-reinforced composite ladders or to produce prepregs used in printed circuit boards and in sheet and mass molding processes. The polyisocyanurate composite materials according to the present invention can be used additionally in sports materials, in high volume production of automotive parts, in train parts, aerospace, marine applications, wind energy devices, window frames, structural parts, adhesives, packaging, encapsulants and insulators.
    [0086] [00086] Before curing, the curable composition can be fed into a mold to provide it in a certain shape or in an object cavity to provide the object with a polyisocyanurate interior or on a surface to provide this interface with a polyisocyanurate cover or can be used to repair an object and, in particular, a pipe to apply it to the interior and / or exterior surface of that object or pipe (examples of this pipe repair were described in US 4009063, 4366012 and 4622196) or can be used to glue materials as described in WO 2007/096216.
    [0087] [00087] Before the curable composition is cured, additives can be added to it or its constituents. Examples of additives are non-reactive solvents with isocyanate, polyols and monools, other catalysts, blowing agents, surfactants, water eliminators, such as alkylortoformate and in particular triisopropylortoformate, antimicrobial agents, flame retardants, smoke suppressants, stabilizers of UV, colorants, plasticizers, internal mold release agents, rheology modifiers, humectants, dispersants and fillers.
    [0088] [00088] The monool and / or polyol optionally used in the present invention preferably has an average nominal hydroxy functionality of 1-8 and an average molecular weight of 32-8000. Mixtures of monools and / or polyols can also be used.
    [0089] [00089] Examples of such monools are methanol, ethanol, propanol, butanol, phenol, cyclohexanol and hydrocarbon monools having an average molecular weight of 200-5,000 as aliphatic monools and polyether monools. Examples of polyols are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylol propane, sorbitol, sucrose, glycerol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, aromatic polyols and / or aliphatics having more atoms carbon than these compounds and having a molecular weight of up to 8000, polyester polyols having an average molecular weight of 200-8000, polyether polyester polyols having an average molecular weight of 200-8000 and polyether polyols having an average molecular weight of 200- 8000. Such monools and polyols are commercially available. Useful examples are Daltocel F555 and Daltocel F442, which are all Huntsman polyether triols, Voranol P400 and Alcupol R1610, which are polyether polyols from DOW and Repsol, respectively, and Priplast 1838 and 3196 which are polyester of high molecular weight polyols from Croda, and Capa 2043 polyol, a linear polyesterdiol with an average MW of about 400 from Perstorp, and polyols K-flex 188 and A308 which are polyester polyols from King Industries having an MW of around 500 and 430 respectively, and aromatic polyester polyols like Stepanpol PH56 and BC180 having average molecular weights of about 2,000 and 600 respectively, and Neodol 23E which is an aliphatic monool from Shell.
    [0090] [00090] Most preferred are polyester and polyether polyols having an average molecular weight of 200-6,000 and an average nominal functionality of 2-4.
    [0091] [00091] The solvent having no isocyanate-reactive groups, which optionally can be used, is preferably an organic solvent that is liquid at 20 ° C. Solvents having a viscosity at 20 ° C of 3,000 mPa.s or less measured according to ASTM D445-lla are considered to be liquid solvents. Most preferred are liquid, organic solvents that are capable of dissolving more than 1 mg of a certain compound containing the -CO-NH-CO- group per liter of solvent at 20 ° C.
    [0092] [00092] Those skilled in the art can certainly easily determine whether or not an organic liquid is suitable for use as a solvent in the present invention, with the above guidelines. Examples of suitable solvents are esters (such as ethyl acetate, propyl acetate, propylene carbonate, phthalate esters), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), aliphatic hydrocarbons (such as cyclohexane, heptane), chlorinated hydrocarbons (such as chloroform, dichloromethane), aromatic solvents (such as benzene, toluene), ethers (such as dimethyl ether, diethyl ether, dioxane, tetrahydrofuran) and mixtures thereof. At most preference, solvents are selected that have a low boiling point at ambient pressure or in a vacuum (so they can easily be removed by removing the curable composition). They should preferably be able to dissolve at least 10 g of carboxamide per kg of solvent. The amount of solvent can vary between wide ranges. The lower limit is determined by the type and amount of compound containing the desired carboxamide and its solubility in the selected solvent. The upper limit is determined by convenience and cost considerations: the lower the better. Preferred amounts are in the range of 0 to 50 and more preferably 0 to 25 and most preferably 0 to 10% by weight based on the weight of the epoxy resin composition.
    [0093] [00093] If desired, the polyisocyanurate material according to the present invention can be subjected to post-curing.
    [0094] [00094] The invention is illustrated with the following examples. EXAMPLES Chemicals used:
    [0095] [00095] Jeffamine M-600 ex Huntsman: a monofunctional primary polyoxyethylene polyoxypropylene amine having a molecular weight of about 560 and an oxypropylene / oxyethylene ratio of about 9/1. In these examples it is referred to as M-600.
    [0096] [00096] Suprasec 1306 ex Huntsman polyisocyanate: 4,4'-MDI, in these examples referred to as S1306.
    [0097] [00097] Suprasec 2020 ex-Huntsman polyisocyanate: a uretonimine modified polyisocyanate, in these examples indicated as S2020
    [0098] [00098] Polyol 3380 ex Perstorp .: Polyoxyethylene polyol initiated by TMP with an OH value of 380 mg KOH / g,
    [0099] [00099] Succinimide ex Sigma
    [0100] [000100] Carbamide (urea) 99% + ex Acros Organics
    [0101] [000101] 1,1-diethyl carbamide (diethyl urea) 97% ex Aldrich
    [0102] [000102] Polyglycol DME500 ex Clariant: PEG 500 dimethyl ether, in these examples indicated as DME 500
    [0103] [000103] Araldite DY-T, ex Huntsman, trimethylolpropane triglycidyl ether, indicated here as DY-T.
    [0104] [000104] Alcupol R1610, ex Repsol polyoxypropylene polyol initiated by glycerol with an OH value of 160 mg KOH / g
    [0105] [000105] Lithium chloride, anhydrous ex Acros Organics
    [0106] [000106] 96% Ethanol, ex Commercial Alcohols INC.
    [0107] [000107] Araldite®, Suprasec® and Jeffamine® are registered trademarks of Huntsman Corporation or a subsidiary thereof and are registered in one or more, but not all countries.
    [0108] [000108] Biuret formation was not observed in any of the examples. Examples 1-2: Preparation of compounds containing a -CO-NH-CO- group
    [0109] [000109] Examples 1-2 describe the preparation of compounds having a -CO-NH-CO- group according to the invention wherein the compound having a -CO-NH-CO- group is a compound having an acyl urea group with the structure -CO-NH-CO-NH- and wherein said compound is the product of reaction of a polyisocyanate with a compound comprising a carboxamide group with the structure -CO-NH2 Example 1
    [0110] [000110] To 90 (pep-parts by weight - parts by weight - pep) of Suprasec 2020 at 85 ° C (0.64 equivalents of isocyanate), 10 pep of a solution containing 10% by weight of carbamide (*) (0.033 carboxamide equivalents) in polyol 3380. After 20 minutes of reaction, a clear liquid reaction product containing an acyl urea group was obtained. (*) carbamide = urea = NH2-CO-NH2 Example 2
    [0111] [000111] At 80 peps of Suprasec 2020 at 85 ° C (0.56 isocyanate equivalents), 20 peps of a solution containing 10% by weight of 1,1-dimethyl were added in agitation and nitrogen atmosphere. carbamide (*) 500 (0.017 carboxamide equivalents) in DME 500. After 20 minutes, a clear liquid reaction product containing the compound with acylurea group was obtained. (*) 1.1 dimethyl carbamide = 1.1 dimethyl urea = NH2-CO-N (CH3) 2 Examples 3-11: Preparation of the stable polyisocyanate composition according to the invention
    [0112] [000112] The compound having a -CO-NH-CO- group is added to a polyisocyanate composition to create the stable polyisocyanate composition according to the invention.
    [0113] [000113] In examples 3-8, said compound is the reaction product of a polyisocyanate with a compound comprising a carboxamide group having the -CO-NH2 structure described in examples 1-2.
    [0114] [000114] In examples 9-11, said compound corresponds to succinimide.
    [0115] [000115] 1123.7 g Jeffamine M600, which were kept at 50 ° C, and 260 g S1306, which were also kept at 50 ° C, were mixed and allowed to react for 1 hour at 80 ° C with stirring, in order to form a urea compound.
    [0116] [000116] 23.9 g of lithium chloride were dissolved in 125.3 g of ethanol with stirring.
    [0117] [000117] This lithium chloride solution was added to the urea compound prepared above which was still maintained at 80 ° C. Stirring continued for about 15 minutes. A substantial amount of ethanol was then removed by distillation at 85-95 ° C. Examples 13-22: Preparation of curable compositions and polyisocyanurate materials according to the present invention.
    [0118] [000118] The compositions in Table 1 (example 3-11) were mixed with 5 peps of the urea / salt mixture prepared in example 12, 4 peps of an Araldite DY-T epoxy resin and 15 peps of Alcupol R1610 polyol for 5 minutes. 100 g of this curable composition was poured into a 120 ml glass container, which was closed with a screw cap and set at room temperature to determine the storage life following the temperature profile with a thermocouple placed in the liquid resin until (30 ° C) of temperature rise. 100 g of these curable compositions were allowed to cure in a closed, aluminum mold, 4 mm thick, for 1 hour at 120 ° C, in order to prepare polyisocyanurate polyurethane materials according to the present invention.
    [0119] [000119] The glass transition temperature (Tg) of the materials obtained was determined by Differential Mechanical Thermo Analysis (DMTA) in a TA Q800 device with a heating rate of 3 ° C / min and a frequency of 1 Hz (measured according to ASTM D 4065). Tg was defined as the first inflection point of the E 'curve (storage module) determined by the universal analysis program TA.
    [0120] [000120] A reference material, other than according to the invention, without the presence of a compound having the group -CO-NH-CO- was prepared with the same procedure (example 13).
    [0121] [000121] The ingredients used, the amounts in parts by weight, the pot lives, Tg of the cured materials, the equivalent ratio of group -CO-NH-CO- per isocyanate, equivalent ratio Urea + biocide per isocyanate, equivalent ratio LiCl for isocyanate, epoxy to isocyanate equivalent ratio, urea + lithium chloride equivalent ratio of the compositions are given in Table 2.
    [0122] [000122] The ingredients used, the amounts in parts by weight, the pot lives, Tg of the cured materials, the equivalent ratio group -CO-NH-CO- per isocyanate, equivalent ratio Urea + biuret per isocyanate, equivalent ratio LiCl per isocyanate, equivalent epoxy to isocyanate ratio, equivalent urea + biuret to lithium chloride ratio of the compositions are given in Table 2.
    [0123] [000123] Figures 1-3 illustrate the storage life measurements of the cured material according to the invention (examples 14-22) with significantly improved pot lives compared to comparative example 13.
    权利要求:
    Claims (22)
    [0001]
    Curable composition, characterized by the fact that it is suitable to produce a material comprising polyisocyanurate allowing said curable composition to react at an elevated temperature above 50 ° C, said curable composition obtained by a process comprising, combining and mixing: - a polyisocyanate composition containing a compound with a -CO-NH-CO- structure group in an amount such that the ratio of the number of -CO-NH-CO- groups to the number of isocyanate groups is at most 1 , and - a lithium halide, - a urea compound, having an average molecular weight of 500-15,000 and optionally containing biuret groups, and - an epoxy resin, where the number of moles of lithium halide per isocyanate equivalent is in the range of 0.0001-0.04 and the number of urea + biuret equivalents per isocyanate equivalent is in the range of 0.0001-0.4 and the number of epoxy equivalents per isocyanate equivalent is in the range of 0.003-1.
    [0002]
    Curable composition according to claim 1, characterized by the fact that it is suitable for producing a material comprising polyisocyanurate allowing said curable composition to react at an elevated temperature above 80 ° C.
    [0003]
    Curable composition according to claim 1, characterized by the fact that the ratio of the number of groups -CO-NH-CO- to the number of isocyanate groups in the polyisocyanate composition is at most 0.01.
    [0004]
    Curable composition according to claim 1, characterized by the fact that the ratio of the number of groups -CO-NH-CO- to the number of isocyanate groups in the polyisocyanate composition is at most 0.0015.
    [0005]
    Curable composition according to claim 1, characterized in that the polyisocyanate composition has an isocyanate value of 10 to 48% by weight.
    [0006]
    Curable composition according to claim 5, characterized in that the polyisocyanate composition has an isocyanate value of 20 to 33% by weight.
    [0007]
    Curable composition according to claim 1 or 2, characterized in that the compound comprising a group of structure -CO-NH-CO- corresponds to structure R1-CO-NH-CO-R2 in which R1 and R2, each independently on the other, they are selected from 1) hydrogen (H), 2) -NR3R4, 3) hydrocarbyl having 1-100 carbon atoms and optionally containing hydroxy, ether, halogen, carboxyl, oxygen, isocyanate and / or amine groups, where R3 and R4 independently of each other, are selected from hydrogen, hydroxy, halogen and hydrocarbyl groups that have hydrocarbyl groups having 1-20 carbon atoms and optionally containing hydroxy, ether, halogen, carboxyl, isocyanate and / or amine groups, where R1 and R2 can be linked to each other forming a ring structure including the -CO-NH-CO- group, and where the hydrocarbyl groups in the compounds corresponding to the formula R1-CO-NH-CO-R2 can be a combination of linear, branched, saturated, unsaturated, cyclical hydrocarbons and / or non-cyclic aliphatic, aromatic or araliphatic and mixtures of these compounds.
    [0008]
    Curable composition according to any one of claims 1 to 6, characterized in that the compound comprising a group with the structure -CO-NH-CO- corresponds to a compound comprising a group -CO-NH-CO-NH - which is a reaction product of a compound comprising a carboxamide group having the structure -CO-NH2 with a polyisocyanate compound containing a reactive NCO group.
    [0009]
    Curable composition according to any one of claims 1 to 6, characterized in that the compound comprising a group with the structure -CO-NH-CO- corresponds to R6-CO-NH-CO-NH-R7 and in which - the compound comprising a carboxamide group corresponds to NH2-CO-R6 and where R6 is 1) hydrogen (-H), 2) -NR8R9, 3) hydrocarbyl having 1-20 carbon atoms and optionally containing hydroxy groups, ether, halogen and / or amine, or 4) -R10-CO-NH2, where R8 and R9, independently of each other, are selected from hydrogen, hydroxy, halogen and hydrocarbyl groups that have 1-10 carbon atoms and optionally include groups hydroxy, ether, halogen and / or amine and where R10 is a divalent hydrocarbon radical having up to 8 carbon atoms and mixtures of these carboxamides, and - the compound comprising a reactive NCO group corresponds to R7-NCO and where R7 is selected from hydrocarbyl groups having 1-20 carbon atoms and optionally include hydroxy, ether, halogen, carboxyl, isocyanate and / or amine groups in which the said hydrocarbyl groups can be a combination of linear, branched, saturated, unsaturated, cyclic and / or non-cyclic aliphatic, aromatic or araliphatic and mixtures of these compounds.
    [0010]
    Curable composition according to any one of claims 1 to 6, characterized in that the compound comprising a -CO-NH-CO- group corresponds to R6-CO-NH-CO-NH-R7 which is produced by adding a compound comprising a carboxamide group with the structure -CO-NH2 to a polyisocyanate composition and allowing the mixture to react to form the compound corresponding to R.6-CO-NH-CO-NH-R7 in the polyisocyanate composition, where R6 is selected from 1) -NR8R9, 2) alkyl having 1-10 carbon atoms and optionally containing 13 hydroxy and / or ether groups, 3) phenyl or 4) tolyl in which R8 and R9, independently of each other, are selected from hydrogen, hydroxy, phenyl, tolyl and alkyl having 1-6 carbon atoms and optionally containing a hydroxy group and / or an ether and mixtures of these compounds.
    [0011]
    Curable composition according to claim 7, characterized in that R1 and R2 together with the -CO-NH-CO- group form a ring structure with 4 to 12 members including the -CO-NH-CO- group.
    [0012]
    Curable composition according to any one of the preceding claims, characterized by the fact that the urea compound is free from other isocyanate reactive groups other than urea groups and in which the number of urea + biuret equivalents per isocyanate equivalent is 0.001-0 , 2 and in which the urea compound was prepared by reaction of a methylene diphenyl diisocyanate or a polyisocyanate containing a methylene diphenyl diisocyanate or a mixture of these polyisocyanates with a polyoxyalkylene monoamine containing oxypropylene groups in an amount of hair minus 50% by weight calculated based on the total weight of the monoamine molecule and having an average molecular weight of 200-3,000 and where the amine is a primary amine and where the number of urea + biuret equivalents per mol of halide of lithium is 0.5-60.
    [0013]
    Curable composition according to any one of the preceding claims, characterized in that the composition includes a toluene diisocyanate, a methylene diphenyl diisocyanate or a polyisocyanate composition containing a methylene diphenyl diisocyanate or a mixture of these poly- isocyanates.
    [0014]
    Curable composition according to any one of the preceding claims, characterized by the fact that the amount of lithium halide is 0.00015-0.025 moles per equivalent of isocyanate.
    [0015]
    Curable composition according to any one of the preceding claims, characterized by the fact that lithium halide is lithium chloride.
    [0016]
    Use of a polyisocyanate composition comprised in the curable composition as defined in claim 1, characterized by the fact that it is for improving the storage life of a curable polyisocyanate composition.
    [0017]
    Process for the manufacture of a curable composition as defined in any one of claims 1 to 15, characterized in that it is by combining and mixing a polyisocyanate composition containing a compound with a group of structure -CO-NH-CO- in an amount such that the ratio of the number of groups -CO-NH-CO- to the number of isocyanate groups is a maximum of 1 with a lithium halide, and a urea compound, having an average molecular weight of 500-15,000 and optionally containing biuret groups, and an epoxy resin, where the number of moles of lithium halide per isocyanate equivalent is in the range of 0.0001-0.04 and the number of urea + biuret equivalents per isocyanate equivalent is in the range 0.0001-0.4 and the number of epoxy equivalents per isocyanate equivalent is in the range of 0.003-1.
    [0018]
    Process according to claim 17, characterized in that the ratio of the number of groups -CO-NH-CO- to the number of isocyanate groups in the polyisocyanate composition is at most 0.01.
    [0019]
    Process according to claim 17, characterized in that the ratio of the number of groups -CO-NH-CO- to the number of isocyanate groups in the polyisocyanate composition is a maximum of 0.0015.
    [0020]
    Material containing polyisocyanurate, characterized in that it is produced leaving a curable composition as defined in any one of claims 1 to 15 to react at an elevated temperature above 50 ° C.
    [0021]
    Process for the manufacture of a material containing polyisocyanurate as defined in claim 20, characterized in that it leaves the curable composition as defined in any of claims 1 to 15 to react at an elevated temperature above 50 ° C.
    [0022]
    Process according to claim 21, characterized in that the curable composition is allowed to react at an elevated temperature above 80 ° C.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014015899B1|2021-02-17|curable composition, use of a polyisocyanate composition, processes for making a curable composition and a material containing polyisocyanurate, and, material containing polyisocyanurate
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    US10689503B2|2020-06-23|Epoxy resin composition
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    CA2854689C|2016-04-05|Curable polyisocyanate composition comprising an epoxy resin
    US9631043B2|2017-04-25|Intermediate polyisocyanurate comprising materials
    BR112015029130B1|2020-10-06|POLY-ISOCIANATE COMPOSITION, PROCESSES FOR MANUFACTURING A POLYISOCIANATE COMPOSITION AND FOR ADDITIONALLY CURING POLY-ISOCIANURATE, AND, POLYISOCIANURATES
    同族专利:
    公开号 | 公开日
    KR101850580B1|2018-05-31|
    CA2857613C|2016-07-12|
    WO2013098034A1|2013-07-04|
    MX2014007826A|2014-08-01|
    JP2015504110A|2015-02-05|
    US20140371406A1|2014-12-18|
    MX344744B|2017-01-05|
    PL2797974T3|2020-11-16|
    CN104159942A|2014-11-19|
    RU2584948C2|2016-05-20|
    CN104159942B|2016-10-12|
    BR112014015899A2|2017-06-13|
    US9382375B2|2016-07-05|
    BR112014015899A8|2017-07-04|
    KR20140108572A|2014-09-11|
    EP2797974B1|2020-07-15|
    EP2797974A1|2014-11-05|
    CA2857613A1|2013-07-04|
    RU2014130998A|2016-02-20|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-10-27| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2021-02-02| B09A| Decision: intention to grant|
    2021-02-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11195897|2011-12-28|
    EP11195897.1|2011-12-28|
    PCT/EP2012/074048|WO2013098034A1|2011-12-28|2012-11-30|Curable composition comprising a polyisocyanate composition|
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