CN1036404C - Polyurethane complementary networks adhesive and its making method - Google Patents
Polyurethane complementary networks adhesive and its making method Download PDFInfo
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- CN1036404C CN1036404C CN90103865A CN90103865A CN1036404C CN 1036404 C CN1036404 C CN 1036404C CN 90103865 A CN90103865 A CN 90103865A CN 90103865 A CN90103865 A CN 90103865A CN 1036404 C CN1036404 C CN 1036404C
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Abstract
The present invention discloses adhesive for thermoplastic polyurethane elastic body interconnection networks, which comprises acrylic ester containing active double-bond monomers, organic isocyanate, a polyurethane elastic body prepolymer which is genenated from liner polyester, an initiator, a catalyst, a solvent and other modifiers. The present invention is mainly used for bonding various soft materials (plastics, artificial leather, synthetic leather, leather, rubber, etc.), can be widely used for shoe making industry, packing industry and rubber and plastic product industry, and can also be used as sealant and a plasticizer.
Description
The present invention is a kind of polyurethane complementary networks adhesive and preparation method.In more detail, it is to be main raw material with isocyanic ester, polyester and esters of acrylic acid, is prepared into a kind of Polyurethane Thermoplastic Elastomer complementary networks adhesive.Be mainly used in bonding various soft material (for example: plastics, leatheroid, synthetic leather, leather, rubber, paper etc.).It can be widely used in shoemaking industry, packaging industry, rubber, plastics industry.The present invention also can bonded metal, timber etc., also can do the toughner of sealing agent and plastics.
Characteristics such as this Polyurethane Thermoplastic Elastomer complementary networks adhesive has that quick solidifying, bonding strength height, viscosity can be regulated, easy to use, excellent storage stability, price are low.
At present, the polyurethane adhesive kind of domestic production, the trade mark are a lot of, but all can not satisfy the needs of shoemaking industry, particularly do not have a kind of tackiness agent can satisfy the needs of injection moulded shoes, sneakers.Injection moulded shoes, sneakers are to adopt leatheroid, polyvinyl chloride, urethane to process mostly.The polyurethane adhesive of domestic production at present, first dual-component polyurethane adhesive.During use, need weighing constantly, constantly prepare tackiness agent, widely apply in both being unsuitable for producing, more be unsuitable for serialization production.It two is one-component polyurethane adhesives, adopts bulk polymerization, and bonding strength is not high.The bonding strength of polyurethane adhesive increases with level of response increase, molecular weight.But mass polymerization increases with level of response, and viscosity sharply increases, and stirs very difficultly, forces the stopping of reaction, and it is enough big to cause molecular weight not to be increased to, and the bonding strength of tackiness agent is not high.
In addition, because reaction system viscosity is big, stir difficulty, the temperature of reaction and the level of response of each several part are inconsistent in the system, react not exclusively, and residual NCO root is more, has seriously influenced the stability of tackiness agent, and storage period is short.Generally speaking, be less than six months the storage period of tackiness agent.
Outside, in the reaction later stage, viscosity is very big in the reactor, and the terminal point of reaction is difficult to control, the adhesive quality instability of production.Because the interior viscosity of reactor is big, sticking still phenomenon is serious, influences thermal conduction again, and the cleaning reaction still is taken a lot of work, required great effort, and has reduced production efficiency.
Adopt solution method to prepare polyurethane adhesive, need to use active big special reagent.Document U.S.P 3,310,533, DE2149836, DE2515766, EP0007594 etc., once disclosure employing effective catalyst ferric acetyl acetonade etc. is held amino chainextender with the very big special type of some activity, these reagent prices are all very expensive, and reaction also needs to reduce pressure and steams original solvent in the later stage, uses intensive polar solvent first and second ketones instead.Not only improved cost and facility investment, and production efficiency is low.Document adopts the monoamine reaction to remove the NCO root of residual minute quantity, though can improve the stability of product, to having been reduced by the surfactivity of adhesives, bonding strength has also reduced.
There is reported in literature to adopt rolling press to carry out solid end hydroxyl polyester and solid vulcabond mixing, heated polymerizable makes adhesion type polyurethane then, its shortcoming is solid and solid reaction, the molecular impact chance is few, react inhomogeneous, molecular weight does not increase yet, and labour intensity is big, production environment is poor, is unsuitable for producing.
The objective of the invention is to overcome the characteristics of above-mentioned prior art, provide a kind of can bonding urethane, the one-component polyurethane adhesive of polyvinyl chloride, easy to use, need not often weighing proportioning, be applicable to produce and widely apply and the tackiness agent of needs is produced in serialization.
Another object of the present invention is to be to provide a kind of bonding strength height, stay-in-grade polyurethane adhesive.The bonding strength of polyurethane adhesive is that the increase with level of response increases.Within the specific limits, molecular weight increases, and bonding strength increases.Because reaction of the present invention in earlier stage, the monomer (esters of acrylic acid) that contains activity double key plays diluting effect, reaction system viscosity is lower, stirs easily, and level of response is controlled easily, generate after the mixture of polyurethane prepolymer and esters of acrylic acid prepolymer, at high temperature finish polyreaction simultaneously, form in the high-molecular weight urethane, running through linear propylene's acid ester polymer, so the present invention has the bonding strength height, stay-in-grade advantage.
Another purpose of the present invention provides a kind of excellent storage stability and don't reduces its polyurethane adhesive active and bonding strength.Owing to have the active NCO base of minute quantity in the product, so kept the activity of tackiness agent.Added extraordinary one package stabilizer in the tackiness agent, made it have the stable characteristics of long storage again.
In order to achieve the above object, the Polyurethane Thermoplastic Elastomer complementary networks adhesive of the present invention inferior tin of polyurethane elastomer prepolymer, initiator peroxidation diisopropyl benzene, octoate catalyst, mineral filler aerosil, organic tackifier supervinyi chloride resin, solvent ethyl acetate and other the improving agent that comprise the monomer esters of acrylic acid that contains the organic isocyanate activity double key, generate with linear polyester.
Any and combination of the organic isocyanate that the present invention adopts.For example tolylene diisocyanate (pure 2.4 bodies or 2.4 bodies and 2.6 body ratios are that 80: 20 or 2.4 bodies and 2.6 body ratios are 65: 35), diphenylmethanediisocyanate, many phenyl polymethine isocyanic ester etc.
The monomer that contains activity double key that the present invention adopts is a kind of of esters of acrylic acid, methacrylic acid lower alkyl esters and combination thereof.For example, a kind of and combination wherein such as methyl methacrylate, methyl acrylate, vinylbenzene, vinyl cyanide or methacrylic acid.Its consumption is to contain active double bond monomer: organic isocyanate and linear polyester sum=1: 5~20.
The linear polyester that the present invention adopts is monounsaturated dicarboxylic acid and dibasic alcohol polycondensation and get.Monounsaturated dicarboxylic acid can be any and combination such as hexanodioic acid, nonane diacid, and dibasic alcohol can be any and combination such as glycol ether, 1,4 butyleneglycol.The molecular weight of polyester is 1000~5000, preferably 1000~3000, and its consumption is the NCO base: OH base=(0.9~1.2): 1.The initiator that the present invention adopts is can produce active any initiator and combination thereof of travelling base at 60~160 ℃.For example any and combination such as organo-peroxide, azo-compound.Initiator amount is 0.5~5% weight of active double bond monomer, preferably 1~2% weight.
The catalyzer that the present invention adopts is a kind of and combination, for example stannous octoate of various tertiary amines, tin, nickel, cobalt, zincum salts compound.Catalyst levels is 0.01~0.1% weight of reactant summation.
The mineral filler that the present invention adopts is any of the little mineral filler of density and combination thereof.For example, any and combination such as aerosil, light calcium carbonate.
The organic tackifier that the present invention adopts is any of organic resin or rubber and combination thereof.For example supervinyi chloride resin, chloroprene rubber, ancient marlon resin is any and the combination.
The stablizer that the present invention adopts is any and combination thereof of Benzoyl chloride or bismaleimides.
The solvent that the present invention adopts be can dissolve polyurethane resin all kinds of SOLVENTS any and combination thereof.For example any and combination such as ethyl acetate, toluene, acetone.
In addition, the present invention can add other various properties-correcting agent, for example dyestuff, color, lubricant etc. according to concrete purposes.
Purpose of the present invention can also reach by following measure, and the preparation method of Polyurethane Thermoplastic Elastomer complementary networks adhesive promptly of the present invention comprises following each step:
(1) fusion of linear polyester resin: in the reactor that agitator and reflux are housed, add successively and contain active double bond monomer, methyl methacrylate, butyl acrylate and 1, the inferior tin of linear polyester that 4-butyleneglycol, ethylene glycol polycondensation generate and octoate catalyst, be heated to about 70 ℃, make the complete fusion of linear polyester and stir.
(2) preparation of Polyurethane Thermoplastic Elastomer prepolymer and acrylic ester prepolymer: under stirring condition, constantly add organic diisocyanate, controlled temperature is no more than 110 ℃, after organic diisocyanate adds, under 60~110 ℃ of conditions, reacted 30~90 minutes, control NCO base content is less than 2.5% weight.Cool to about 70 ℃, add the free-radical initiator Diisopropyl azodicarboxylate, under 60~80 ℃ of conditions, stir, reacted 10~40 minutes, stop to stir, discharging is poured in the charging tray, obtains white solid after the cooling.
NCO content test method: test with reference to ASTM D1638 standard method.
(3) preparation of Polyurethane Thermoplastic Elastomer: will fill the charging tray of white solid, and put into baking oven, temperature rises to 130~170 ℃, heats one hour to five hours, takes out charging tray, and white that obtains or light yellow solid are Polyurethane Thermoplastic Elastomer.
(4) preparation of Polyurethane Thermoplastic Elastomer complementary networks adhesive: Polyurethane Thermoplastic Elastomer is refined glue to mooney viscosity 40 following fragmentations through rubber mixing machine, put into solvent ethyl acetate, airtight, soaking at room temperature is more than one day, restir 3~12 hours, it is dissolved fully, if any not molten thing on a small quantity, remove by filter.Add the mineral filler aerosil again, organic tackifier ancient marlon resin, stablizer Benzoyl chloride and other various properties-correcting agent.So just, obtained Polyurethane Thermoplastic Elastomer complementary networks adhesive of the present invention.
The Polyurethane Thermoplastic Elastomer complementary networks adhesive that the present invention makes, outward appearance are white or flaxen liquid.The normal temperature storage phase can reach more than 1 year.Bonding with synthetic leather, 180 degree stripping strengths all are that synthetic leather destroys greater than 20N/cm.With the bonding strength on rotary hose surface greater than 60N/cm.
The Polyurethane Thermoplastic Elastomer complementary networks adhesive of manufacturing of the present invention is can bonding urethane, the one-component polyurethane adhesive of polyvinyl chloride, easy to use, need not often weighing proportioning, and be suitable for producing and widely apply and the needs of serialization production.
The tackiness agent of manufacturing of the present invention is a kind of bonding strength height, stay-in-grade polyurethane adhesive.Reaction of the present invention contains monomer (esters of acrylic acid an etc.) diluting effect of activity double key in earlier stage, and reaction system viscosity is low, stirs easily, and level of response is controlled easily.Generate the mixture of polyurethane prepolymer and esters of acrylic acid prepolymer, at high temperature finish polyreaction simultaneously, formed bonding strength height, stay-in-grade polyurethane adhesive.
The tackiness agent of manufacturing of the present invention is a kind of excellent storage stability and don't the polyurethane adhesive that reduces active and bonding strength.Owing to have the active NCO base of minute quantity in the product, kept the activity of tackiness agent.Added extraordinary one package stabilizer in the tackiness agent again, made it have the stable characteristics of long storage again.
The elastomerics of manufacturing of the present invention has certain activity and high tenacity, with various thermoplastic materials good consistency is arranged, and can be used as the toughner of macromolecular material, various coating, sealing agent and hot melt adhesive etc.
Polyurethane Thermoplastic Elastomer complementary networks adhesive embodiment of the present invention is as follows:
Embodiment 1
In the there-necked flask that agitator and reflux condensing tube are housed, add successively 15.5 the gram methyl methacrylates, by 1,4-butyleneglycol, ethylene glycol and hexanodioic acid prepare, hydroxyl value is 35.42, acid number is 3.60 hydroxyl telechelic polyester (trade mark SBG type-3, place of production Wuxi County is opened Jing Juanzhicailiaochang) 287.7 grams (about 0.1MOL), stannous octoate 0.03 gram.Be heated to 70 ℃, make the complete fusion of hydroxyl telechelic polyester, and constantly stir.Under continuous agitation condition, add tolylene diisocyanate (TDI) (weight ratio of 2.4 bodies and 2.6 bodies is 80: 20 a mixture) 20.9 grams (about 0.12MOL), the control feed rate, make temperature of reaction be no more than 110 ℃, after adding TDI, heat up, continue reaction 30 minutes at 100~110 ℃, treat NCO content less than 2.5% weight, stop heating, temperature is reduced to 70 ℃, add initiator benzoyl peroxide 0.15 gram, stir,, stop to stir 70~80 ℃ of reactions 30 minutes, pour in the charging tray, obtain white solid after the cooling.
NCO content test method: test with reference to ASTM D1638 standard method.
With filling the charging tray of white solid, put into baking oven, temperature rises to 160~170 ℃, heats one hour, takes out charging tray, and the white solid that obtains is Polyurethane Thermoplastic Elastomer of the present invention.NCO content 0.29%, molecular weight is more than 50,000.
Polyurethane Thermoplastic Elastomer 160 grams are refined glue to mooney viscosity 40 following fragmentations through rubber mixing machine, put into 840 gram solvent ethyl acetates, airtight, soak after one day under the room temperature, stirred 4 hours, it is dissolved fully, if not molten on a small quantity thing is arranged, can remove by filter.Add mineral filler aerosil 5.6 grams again, 613 powder (the copolymer of 5% methacrylic acid and 95% methyl methacrylate, Shanghai Pen Making Chemical Factory produces) 20% chloroformic solution, 10 grams, stablizer Benzoyl chloride 1.0 grams, stir, just can obtain the Polyurethane Thermoplastic Elastomer complementary networks adhesive.
Above-mentioned resulting Polyurethane Thermoplastic Elastomer complementary networks adhesive outward appearance is the transparent liquid of white, and the storage at normal temperature phase can reach more than 1 year, and is bonding with synthetic leather, and 180 degree are peeled off bonding strength greater than 20N/cm, and synthetic leather is destroyed.With the bonding strength on rotary hose surface greater than 60N/cm.
Embodiment 2
In the there-necked flask that agitator and reflux condensing tube are housed, add butyl methacrylate 21.0 gram successively, by 1, that 4-butyleneglycol, ethylene glycol and hexanodioic acid prepare, hydroxyl value 52.31, acid number is 4.12 hydroxyl polyester (trade mark CMA-244, place of production Yantai Synthetic Leather General Factory) 210.7 grams (about 0.1MOL), stannous octoate 0.23 gram is heated to 60~70 ℃, makes the complete fusion of polyester.
Under continuous agitation condition, add tolylene diisocyanate (TDI) (weight ratio of 2.4 bodies and 2.6 bodies is 80: 20 a mixture) 17.4 grams (0.1MOL), the control feed rate makes temperature of reaction be no more than 80 ℃.Add after the TDI, heat up, under 80~90 ℃ of conditions, reacted 50 minutes, stop heating.Add peroxidation diisopropyl benzene (CUP) 0.35 gram, after stirring, 60~70 ℃ of reactions 40 minutes, stop to stir, discharging is poured in the charging tray, obtains white solid after the cooling.
The charging tray that fills white solid is put into baking oven, and temperature rises to 140~150 ℃, heats 2 hours, takes out charging tray, obtains light yellow solid, is Polyurethane Thermoplastic Elastomer.Analysis draws: NCO content 0.02%, molecular weight is more than 70,000.
With Polyurethane Thermoplastic Elastomer, pulverizing below 40 through rubber mixing machine refining glue to mooney viscosity is pellet, takes out 160 grams, adds in the 840 gram industrial ethyl acetates, and airtight, immersion was stirred 4 hours after one day under the room temperature, and it is dissolved fully.If not molten on a small quantity thing is arranged, can remove by filter.Add aerosil 6 grams again, supervinyi chloride resin (chemical plant, Jinxi produces, coating HG2-344-66), 20% acetone soln, 24 grams, stablizer bismaleimides 0.036 gram stirs, and just can obtain the Polyurethane Thermoplastic Elastomer complementary networks adhesive.
The result of use of embodiment 2 is substantially the same manner as Example 1.
NCO content test method: test with reference to ASTM D1638 standard method.
Embodiment 3
With methyl methacrylate 23.0 grams, vinylbenzene 5.0 grams, methacrylic acid 3.0 grams, by 1, the 4-butyleneglycol: the hydroxyl value of the mixing dibasic alcohol of glycol ether=3: 1 (weight ratio) and hexanodioic acid preparation is 78.25, acid number is that 4.51 linear polyester 149.4 grams (about 0.1MOL) and stannous octoate 0.1 restrain, triethylamine 0.03 gram, add and be equipped with in the there-necked flask of agitator and reflux condensing tube, be heated to 60~70 ℃, make linear polyester (Yantai Synthetic Leather General Factory produces, trade mark MX-706) fusion fully.
Under agitation condition, add tolylene diisocyanate (TDI, pure 2,4 bodies) 15.7 grams (0.09mol), the control feed rate makes temperature of reaction be no more than 70 ℃, after adding TDI, under 60~70 ℃ of conditions, reacted 90 minutes, add Diisopropyl azodicarboxylate 0.2 gram, after stirring, 70~80 ℃ were reacted 10 minutes, stop to stir, discharging is poured in the charging tray, obtains white solid after the cooling.
White waxy solid is put into baking oven, and temperature rises to 130~140 ℃, heats 5 hours, takes out charging tray, obtains white solid.Be Polyurethane Thermoplastic Elastomer.
Analysis draws: NCO content 0.01%, molecular weight is more than 60,000.
With this Polyurethane Thermoplastic Elastomer 150 grams,, add in the 850 gram acetone to mooney viscosity 40 below and broken through rubber mixing machine refining glue, airtight, soaking at room temperature stirred 8 hours after 2 days, and it is dissolved fully, as if a small amount of insolubles is arranged, can remove by filter.Add aerosil 10 grams, LDJ-240 chloroprene rubber 20%, toluene solution 55 grams again, stablizer bismaleimides 0.02 gram, vulcanization accelerator tetramethyl-thiuram disulfide 0.1 gram, stir, just can obtain the Polyurethane Thermoplastic Elastomer complementary networks adhesive.
The result of use of embodiment 3 is substantially the same manner as Example 1.
NCO content test method: test with reference to ASTM D1638 standard method.
Claims (5)
1. a Polyurethane Thermoplastic Elastomer complementary networks adhesive is characterized in that containing weight percent Polyurethane Thermoplastic Elastomer 14.08%~15.74%, mineral filler 0.55%~0.94%, organic tackifier 0.19%~1.03%, stablizer 0.002%~0.1%, solvent 80.59%~81.76%;
Above-described Polyurethane Thermoplastic Elastomer is to be made by organic isocyanate, the monomer that contains activity double key, linear polyester, initiator, catalyzer, and its mass fraction is: contain active double bond monomer: organic isocyanate and linear polyester sum=1: 5~20, initiator: contain active double bond monomer=0.5~5: 100, catalyzer: reactant summation=0.001~0.1: 100;
Pure 2,4 bodies of organic isocyanate wherein, 2,4 bodies: 2,6 bodies=80: 20,2,4 bodies: 2, the tolylene diisocyanate of 6 bodies=65: 35, diphenylmethanediisocyanate, many phenyl polymethine isocyanic ester;
The monomer that contains activity double key wherein is a kind of of esters of acrylic acid, methacrylic acid lower alkyl esters, and wherein a kind of of methyl methacrylate, methyl acrylate or vinylbenzene, vinyl cyanide, methacrylic acid arranged;
Linear polyester wherein is monounsaturated dicarboxylic acid and dibasic alcohol polycondensation and get, monounsaturated dicarboxylic acid is any and combination thereof of hexanodioic acid, nonane diacid, dibasic alcohol is any and combination thereof of glycol ether, 1,4 butyleneglycols, and the molecule content of linear polyester is 1000~5000;
Initiator wherein is any initiator that can produce active radical at 60~160 ℃, have organo-peroxide, azo-compound any;
Catalyzer wherein is various tertiary amines, pink salt compound stannous octoate;
Said organic tackifier be organic resin or rubber any, have supervinyi chloride resin, chloroprene rubber, ancient marlon resin any;
Said stablizer is any of Benzoyl chloride or bismaleimides.
2. Polyurethane Thermoplastic Elastomer complementary networks adhesive according to claim 1 is characterized in that its said mineral filler is any and combination thereof of the little mineral filler aerosil of density, light calcium carbonate.
3. Polyurethane Thermoplastic Elastomer complementary networks adhesive according to claim 1, it is characterized in that its said solvent be can dissolve polyurethane all kinds of SOLVENTS ethyl acetate, toluene, acetone any and the combination thereof of resin.
4. Polyurethane Thermoplastic Elastomer complementary networks adhesive according to claim 1 is characterized in that it can add various properties-correcting agent, has dyestuff, pigment, lubricant, vulcanization accelerator.
5. the preparation method of a Polyurethane Thermoplastic Elastomer complementary networks adhesive, its feature is made up of following each step:
(1) fusion of linear polyester resin: in the reactor that agitator and reflux are housed, add successively and contain active double bond monomer methyl methacrylate, butyl acrylate and by 1, the inferior tin of linear polyester that 4-butyleneglycol, ethylene glycol, hexanodioic acid polycondensation generate and octoate catalyst, be heated to 70 ℃, make the complete fusion of linear polyester;
(2) preparation of Polyurethane Thermoplastic Elastomer prepolymer and acrylic ester prepolymer: under stirring condition, constantly add organic diisocyanate, controlled temperature is no more than 110 ℃, after organic diisocyanate adds, under 60~110 ℃ of conditions, reacted 30~90 minutes, control NCO base content cools to 70 ℃ less than 2.5% weight, add the initiator Diisopropyl azodicarboxylate, under 60~80 ℃ of conditions, stir, reacted 10~40 minutes, stop to stir, discharging is poured in the charging tray, obtains white solid after the cooling;
(3) preparation of Polyurethane Thermoplastic Elastomer: will fill the charging tray of white solid, and put into baking oven, temperature rises to 130~170 ℃, heats 1 hour to 5 hours, takes out charging tray, and white that obtains or faint yellow solid are Polyurethane Thermoplastic Elastomer;
(4) preparation of Polyurethane Thermoplastic Elastomer complementary networks adhesive: Polyurethane Thermoplastic Elastomer is refined glue to mooney viscosity 40 following fragmentations, put into solvent ethyl acetate, airtight, room temperature condition soaked one day down, restir 3~12 hours, it is dissolved fully, if any not molten thing on a small quantity, remove by filter, add the mineral filler aerosil again, the organic tackifier ancient marlon resin, the stablizer Benzoyl chloride, vulcanization accelerator tetramethyl-thiuram disulfide and other various properties-correcting agent stir, and have so just obtained the Polyurethane Thermoplastic Elastomer complementary networks adhesive.
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CN90103865A CN1036404C (en) | 1990-05-22 | 1990-05-22 | Polyurethane complementary networks adhesive and its making method |
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CN1036404C true CN1036404C (en) | 1997-11-12 |
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Cited By (2)
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WO2022136068A1 (en) | 2020-12-22 | 2022-06-30 | Covestro Deutschland Ag | A method for stably storing an isocyanate composition |
EP4036138A1 (en) | 2021-01-28 | 2022-08-03 | Covestro Deutschland AG | A method for stably storing an isocyanate composition |
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CN1045971C (en) * | 1993-01-19 | 1999-10-27 | 江苏石油化工学院 | Method for preparation of polyurethane acrylic ester copolymerized emulsion |
US5827926A (en) * | 1996-11-08 | 1998-10-27 | Minnesota Mining And Manufacturing Company | Moisture-curable, hot-melt composition |
CN1095492C (en) * | 1997-03-19 | 2002-12-04 | 湖北大学 | Process for producing adhesive for polyurethane shoes by solution method |
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JPS6218416A (en) * | 1985-07-16 | 1987-01-27 | Showa Highpolymer Co Ltd | Curable composition |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2022136068A1 (en) | 2020-12-22 | 2022-06-30 | Covestro Deutschland Ag | A method for stably storing an isocyanate composition |
EP4036138A1 (en) | 2021-01-28 | 2022-08-03 | Covestro Deutschland AG | A method for stably storing an isocyanate composition |
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CN1056701A (en) | 1991-12-04 |
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