CN104031240B - A kind of polyurethane adhesive and preparation method thereof - Google Patents
A kind of polyurethane adhesive and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention provides a kind of polyurethane adhesive and preparation method thereof, adhesive comprises: methyl diphenylene diisocyanate, styrene-grafted PPG, epoxy resin, methyl tosylate, polypropylene glycol, polyoxypropylene pentaerythrite ether, amine catalyst, IPD, zeolite, castor oil, N-ethyl-N-phenyl zinc dithiocarbamate, resorcinol, triphenylphosphine, silane coupler and emulsifying agent; First methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol, polyoxypropylene pentaerythrite ether and zeolite are mixed after closing and added resorcinol and triphenylphosphine, after stirring, the mixture of styrene-grafted PPG, IPD, castor oil, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupler and emulsifying agent is added, to obtain final product. Adhesive of the present invention has excellent yellowing resistance, ageing resistance, heat resistance, anti-hydrolytic performance and adhesive strength.
Description
Technical field
The invention belongs to adhesive technology field, be specifically related to a kind of polyurethane adhesive and preparation method thereof.
Background technology
Polyurethane (PU) adhesive refers to and in strand, contains urethano (NHCOO-) and/or NCO (NCO)The adhesive of class. Polyurethane adhesive is mainly divided into polyisocyanates and the large class of polyurethane two, divides polyurethane by occupation modeAdhesive can be divided into two kinds of one pack system and bi-components. Polarity, the chemism of NCO and urethano are all very strong, therefore rightThe material (glass, metal etc.) of porous material (leather, foam etc.) and any surface finish has good chemical bonding power. And poly-Ammonia ester gum stick has the advantages such as pliability is good, vibration resistance is good, shock-resistant, wear-resisting, adhesion strength is large, and purposes is more and more widerGeneral.
Polyurethane adhesive is generally divided into one-component polyurethane adhesive and dual-component polyurethane adhesive. One-component gathers ammoniaThe general operation of ester gum stick is convenient, but in process of production, generally all can add organic solvent, does not meet environmental requirement; SimultaneouslyOne-component polyurethane adhesive is generally NCO group end capping, easy and airborne moisture content reaction in storage process, cause skinning,The phenomenons such as caking, the storage life is shorter; One-component polyurethane adhesive does not generally add catalyst or only adds denier in additionCatalyst, thereby curing rate is slower, in low temperature environment, even wants more than 24 hours could solidify especially.
Traditional no-solvent type dual-component polyurethane adhesive, does not add organic solvent aborning, meets environmental requirement;Because two components are separately deposited, the storage life is longer, but after two components mix by stoicheiometry, general working life is too short, specialAt high temperature season, after glue mixes, viscosity increases very fast, causes the later stage to use difficulty, a large amount of glue scrap maybe can not form goodGood bonding, produce a large amount of defective works. Even at low temperature season, although extend working life, also extend same hardening time, shadowRing client's production efficiency, although add conventional catalyst (organo-bismuth, organotin, amine etc.) can accelerate curing rate,Make equally to become working life very short, affect later stage operation.
Summary of the invention
The object of this invention is to provide a kind of polyurethane adhesive and preparation method thereof, this adhesive not only has excellentYellowing resistance, ageing resistance, also have better heat resistance, anti-hydrolytic performance and adhesive strength.
Polyurethane adhesive, comprises in weight portion: 100～200 parts of methyl diphenylene diisocyanates, styrene-grafted20～30 parts of PPGs, 30～90 parts of epoxy resin, 5～12 parts of methyl tosylates, 3～15 parts of polypropylene glycols, poly-1～7 part, oxypropylene pentaerythrite ether, 2～6 parts of amine catalysts, 0.5～3.2 part of IPD, 0.2～0.7 part, zeolite,0.4～1.5 part of castor oil, 0.1～0.7 part of N-ethyl-N-phenyl zinc dithiocarbamate, 0.3～2.5 part of resorcinol,0.2～1.8 part of triphenylphosphine, 1～5 part of silane coupler, 2～6 parts of emulsifying agents.
As the further improvement of foregoing invention, described epoxy resin is bisphenol A epoxide resin.
As the further improvement of foregoing invention, described silane coupler be a kind of in KH-550 or KH-560 orThe mixture of two kinds.
As the further improvement of foregoing invention, described emulsifying agent is lauryl sodium sulfate.
As the further improvement of foregoing invention, described amine catalyst is triethylene diamine, tetrem alkene triamine or five etheneA kind of in tetramine.
The preparation method of above-mentioned polyurethane adhesive, comprises the following steps:
Step 1, by methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, poly-the third twoAlcohol and polyoxypropylene pentaerythrite ether are poured in stirred tank, then add zeolite to stir, and then stirred tank are heated toAfter 100～120 DEG C, add resorcinol and triphenylphosphine, stir, be cooled to room temperature and obtain mixture I;
Step 2, by styrene-grafted PPG, IPD, castor oil, N-ethyl-N-phenyl two sulfo-sCarbaminate, silane coupler and emulsifying agent are poured in stirred tank, then stirred tank are heated to after 100～120 DEG C, coolingObtain mixture II to room temperature;
Step 3, mixes mixture I and mixture II, is heated to 70～90 DEG C, after insulation 2～8h, is cooled to room temperature,Obtain polyurethane adhesive.
As the further improvement of foregoing invention, in described step 1, stirred tank keeps vacuum at-0.08～-0.1MPa.
As the further improvement of foregoing invention, in described step 3, heating process is temperature programming, 5 DEG C of intensifications per hour.
Polyurethane adhesive of the present invention not only has excellent yellowing resistance, ageing resistance, also has better heat-resistingPerformance, anti-hydrolytic performance and adhesive strength; Except the use of triphen, there is high-environmental performance side by side, meet International Environmental Protection standard.
Detailed description of the invention
Embodiment 1
Polyurethane adhesive, comprises in weight portion: 100 parts of methyl diphenylene diisocyanates, styrene-grafted polyethers20 parts of polyalcohols, 30 parts of bisphenol A epoxide resins, 5 parts of methyl tosylates, 3 parts of polypropylene glycols, polyoxypropylene pentaerythrite ether1 part, 2 parts of triethylene diamines, 0.5 part of IPD, 0.2 part, zeolite, 0.4 part of castor oil, N-ethyl-N-phenyl two sulfo-s0.1 part of carbaminate, 0.3 part of resorcinol, 0.2 part of triphenylphosphine, 1 part of silane resin acceptor kh-550, dodecyl sulphate2 parts, sodium.
First by methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol andPolyoxypropylene pentaerythrite ether is poured in stirred tank, then adds zeolite to stir, and stirred tank is heated and is evacuated toVacuum is-0.08MPa that when temperature reaches after 100 DEG C, continuation keeps vacuum 2h, adds resorcinol and triphenylphosphine, stirsEvenly, continue to vacuumize 0.5h, be cooled to room temperature and obtain mixture I; By styrene-grafted PPG, IPD,Castor oil, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupler and emulsifying agent are poured in stirred tank, then to stirringMix still and be heated to after 100 DEG C, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, often little5 DEG C of Shi Shengwen, are heated to 90 DEG C, after insulation 2h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 2
Polyurethane adhesive, comprises in weight portion: 115 parts of methyl diphenylene diisocyanates, styrene-grafted polyethers23 parts of polyalcohols, 35 parts of bisphenol A epoxide resins, 7 parts of methyl tosylates, 5 parts of polypropylene glycols, polyoxypropylene pentaerythrite ether2 parts, 3 parts of tetrem alkene triamines, 0.8 part of IPD, 0.3 part, zeolite, 0.6 part of castor oil, N-ethyl-N-phenyl two sulfo-s0.2 part of carbaminate, 0.5 part of resorcinol, 0.4 part of triphenylphosphine, silane coupler KH-5602 part, dodecyl sulphate3 parts, sodium.
First by methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol andPolyoxypropylene pentaerythrite ether is poured in stirred tank, then adds zeolite to stir, and stirred tank is heated and is evacuated toVacuum is-0.1MPa that, when temperature reaches after 120 DEG C, continuation keeps vacuum 0.5h, adds resorcinol and triphenylphosphine, stirsMix evenly, continue to vacuumize 2h, be cooled to room temperature and obtain mixture I; By styrene-grafted PPG, IPD,Castor oil, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupler and emulsifying agent are poured in stirred tank, then to stirringMix still and be heated to after 120 DEG C, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, often little5 DEG C of Shi Shengwen, are heated to 70 DEG C, after insulation 8h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 3
Polyurethane adhesive, comprises in weight portion: 135 parts of methyl diphenylene diisocyanates, styrene-grafted polyethers25 parts of polyalcohols, 42 parts of bisphenol A epoxide resins, 8 parts of methyl tosylates, 7 parts of polypropylene glycols, polyoxypropylene pentaerythrite ether3 parts, five 5 parts of ethene tetramines, 1.5 parts of IPDs, 0.4 part, zeolite, 0.9 part of castor oil, N-ethyl-N-phenyl two sulfo-s0.3 part of carbaminate, 0.8 part of resorcinol, 0.6 part of triphenylphosphine, 2 parts of silane couplers, 4 parts of lauryl sodium sulfate.
Above-mentioned silane coupler be KH-550 and KH-560 mixture, its weight ratio is 3:7.
First by methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol andPolyoxypropylene pentaerythrite ether is poured in stirred tank, then adds zeolite to stir, and stirred tank is heated and is evacuated toVacuum is-0.09MPa that when temperature reaches after 110 DEG C, continuation keeps vacuum 1h, adds resorcinol and triphenylphosphine, stirsEvenly, continue to vacuumize 1h, be cooled to room temperature and obtain mixture I; By styrene-grafted PPG, IPD, castorSesame oil, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupler and emulsifying agent are poured in stirred tank, then to stirringStill is heated to after 110 DEG C, is cooled to room temperature and obtains mixture II; Mixture I and mixture II are mixed, temperature programming, per hourHeat up 5 DEG C, be heated to 80 DEG C, after insulation 5h, be cooled to room temperature, obtain polyurethane adhesive.
Embodiment 4
Polyurethane adhesive, comprises in weight portion: 185 parts of methyl diphenylene diisocyanates, styrene-grafted polyethers27 parts of polyalcohols, 70 parts of bisphenol A epoxide resins, 10 parts of methyl tosylates, 12 parts of polypropylene glycols, polyoxypropylene pentaerythrite6 parts, ether, 5 parts of tetrem alkene triamines, 2.8 parts of IPDs, 0.6 part, zeolite, 1.1 parts of castor oil, N-ethyl-N-phenyl two sulphurFor 0.6 part of carbaminate, 2.2 parts of resorcinols, 1.6 parts of triphenylphosphines, 4 parts of silane resin acceptor kh-550s, dodecyl sulphur5 parts, acid sodium.
First by methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol andPolyoxypropylene pentaerythrite ether is poured in stirred tank, then adds zeolite to stir, and stirred tank is heated and is evacuated toVacuum is-0.08MPa that, when temperature reaches after 100 DEG C, continuation keeps vacuum 0.5h, adds resorcinol and triphenylphosphine, stirsMix evenly, continue to vacuumize 0.5h, be cooled to room temperature and obtain mixture I; By styrene-grafted PPG, isophorone twoAmine, castor oil, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupler and emulsifying agent are poured in stirred tank, then rightStirred tank is heated to after 100 DEG C, is cooled to room temperature and obtains mixture II; Mixture I and mixture II are mixed, temperature programming, everyHour heat up 5 DEG C, be heated to 70 DEG C, insulation 2h after, be cooled to room temperature, obtain polyurethane adhesive.
Embodiment 5
Polyurethane adhesive, comprises in weight portion: 146 parts of methyl diphenylene diisocyanates, styrene-grafted polyethers24 parts of polyalcohols, 75 parts of bisphenol A epoxide resins, 10 parts of methyl tosylates, 11 parts of polypropylene glycols, polyoxypropylene pentaerythrite3 parts, ether, five 5 parts of ethene tetramines, 2.4 parts of IPDs, 0.3 part, zeolite, 1.2 parts of castor oil, N-ethyl-N-phenyl two sulphurFor 0.5 part of carbaminate, 1.5 parts of resorcinols, 1.2 parts of triphenylphosphines, silane coupler KH-5603 part, dodecyl sulphur4 parts, acid sodium.
First by methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol andPolyoxypropylene pentaerythrite ether is poured in stirred tank, then adds zeolite to stir, and stirred tank is heated and is evacuated toVacuum is-0.1MPa that when temperature reaches after 120 DEG C, continuation keeps vacuum 2h, adds resorcinol and triphenylphosphine, stirsEvenly, continue to vacuumize 2h, be cooled to room temperature and obtain mixture I; By styrene-grafted PPG, IPD, castorSesame oil, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupler and emulsifying agent are poured in stirred tank, then to stirringStill is heated to after 120 DEG C, is cooled to room temperature and obtains mixture II; Mixture I and mixture II are mixed, temperature programming, per hourHeat up 5 DEG C, be heated to 90 DEG C, after insulation 8h, be cooled to room temperature, obtain polyurethane adhesive.
Embodiment 6
Polyurethane adhesive, comprises in weight portion: 200 parts of methyl diphenylene diisocyanates, styrene-grafted polyethers0 part of polyalcohol, 90 parts of bisphenol A epoxide resins, 12 parts of methyl tosylates, 15 parts of polypropylene glycols, polyoxypropylene pentaerythrite7 parts, ether, 6 parts of triethylene diamines, 3.2 parts of IPDs, 0.7 part, zeolite, 1.5 parts of castor oil, N-ethyl-N-phenyl two sulphurFor 0.7 part of carbaminate, 2.5 parts of resorcinols, 1.8 parts of triphenylphosphines, 5 parts of silane couplers, lauryl sodium sulfate 6Part.
Above-mentioned silane coupler be KH-550 and KH-560 mixture, its weight ratio is 6:4.
First by methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol andPolyoxypropylene pentaerythrite ether is poured in stirred tank, then adds zeolite to stir, and stirred tank is heated and is evacuated toVacuum is-0.08MPa that, when temperature reaches after 105 DEG C, continuation keeps vacuum 1.5h, adds resorcinol and triphenylphosphine, stirsMix evenly, continue to vacuumize 1h, be cooled to room temperature and obtain mixture I; By styrene-grafted PPG, IPD,Castor oil, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupler and emulsifying agent are poured in stirred tank, then to stirringMix still and be heated to after 115 DEG C, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, often little5 DEG C of Shi Shengwen, are heated to 85 DEG C, after insulation 6h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 7
The difference of the present embodiment and embodiment 5 is: in polyurethane adhesive, do not contain polyoxypropylene pentaerythrite ether, toolBody is as follows:
Polyurethane adhesive, comprises in weight portion: 146 parts of methyl diphenylene diisocyanates, styrene-grafted polyethers24 parts of polyalcohols, 75 parts of bisphenol A epoxide resins, 10 parts of methyl tosylates, 11 parts of polypropylene glycols, five 5 parts of ethene tetramines, different2.4 parts of phorone diamines, 0.3 part, zeolite, 1.2 parts of castor oil, 0.5 part of N-ethyl-N-phenyl zinc dithiocarbamate, isophthalic1.5 parts of diphenol, 1.2 parts of triphenylphosphines, silane coupler KH-5603 part, 4 parts of lauryl sodium sulfate.
First methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol are fallenEnter in stirred tank, then add zeolite to stir, stirred tank is heated and is evacuated to vacuum is-0.1MPa to work as temperatureDegree reaches after 120 DEG C, continues to keep vacuum 2h, adds resorcinol and triphenylphosphine, stirs, and continues to vacuumize 2h, coldBut obtain mixture I to room temperature; By styrene-grafted PPG, IPD, castor oil, N-ethyl-N-phenyl twoZinc thiocarbamate, silane coupler and emulsifying agent are poured in stirred tank, then stirred tank are heated to after 120 DEG C, coolingObtain mixture II to room temperature; Mixture I and mixture II are mixed, temperature programming, 5 DEG C of intensifications per hour, are heated to 90 DEG C, protectAfter temperature 8h, be cooled to room temperature, obtain polyurethane adhesive.
Embodiment 1 to 7 products obtained therefrom is carried out to harmful substance test with reference to GB19340-2003, and result is as follows:
Embodiment 1 to 7 gained sample is carried out to performance test, and result is as follows:
From above result, the polyurethane adhesive of this method does not only detect environmentally hazardous triphen, free tolueneVulcabond and halogenated hydrocarbons; There are excellent gluing effect, resistance to ag(e)ing, heat resistance, hydrolytic resistance and yellowing resistance simultaneously. RealExecute in example 7 and do not contain polyoxypropylene pentaerythrite ether, affected the properties of adhesive, this may be because polyoxypropylene seasonPenta tetrol ether has effectively improved the adhesion strength of adhesive, and makes it have better heat resistance, resistance to xanthochromia shape and ageing resistance.
Claims (8)
1. a polyurethane adhesive, comprises in weight portion: 100～200 parts of methyl diphenylene diisocyanates, styrene connects20～30 parts of branch PPGs, 30～90 parts of epoxy resin, 5～12 parts of methyl tosylates, 3～15 parts of polypropylene glycols,1～7 part, polyoxypropylene pentaerythrite ether, 2～6 parts of amine catalysts, 0.5～3.2 part of IPD, zeolite 0.2～0.7Part, 0.4～1.5 part of castor oil, 0.1～0.7 part of N-ethyl-N-phenyl zinc dithiocarbamate, resorcinol 0.3～2.5Part, 0.2～1.8 part of triphenylphosphine, 1～5 part of silane coupler, 2～6 parts of emulsifying agents.
2. polyurethane adhesive according to claim 1, is characterized in that: described epoxy resin is bisphenol A epoxide resin.
3. polyurethane adhesive according to claim 1, is characterized in that: described silane coupler be KH-550 orThe mixture of a kind of in KH-560 or two kinds.
4. polyurethane adhesive according to claim 1, is characterized in that: described emulsifying agent is lauryl sodium sulfate.
5. polyurethane adhesive according to claim 1, is characterized in that: described amine catalyst is triethylene diamine, fourA kind of in ethene triamine or five ethene tetramines.
6. the preparation method of the polyurethane adhesive described in claim 1 to 5 any one, is characterized in that: comprise the following steps:
Step 1, by methyl diphenylene diisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol andPolyoxypropylene pentaerythrite ether is poured in stirred tank, then adds zeolite to stir, then to stirred tank be heated to 100～After 120 DEG C, add resorcinol and triphenylphosphine, stir, be cooled to room temperature and obtain mixture I;
Step 2, by styrene-grafted PPG, IPD, castor oil, N-ethyl-N-phenyl two sulfo-aminosZinc formate, silane coupler and emulsifying agent are poured in stirred tank, then stirred tank are heated to, after 100～120 DEG C, be cooled to chamberThe warm mixture II that obtains;
Step 3, mixes mixture I and mixture II, is heated to 70～90 DEG C, after insulation 2～8h, is cooled to room temperature, obtains poly-Ammonia ester gum stick.
7. the preparation method of polyurethane adhesive according to claim 6, is characterized in that: in described step 1, stirred tank is protectedHold vacuum at-0.08～-0.1MPa.
8. the preparation method of polyurethane adhesive according to claim 6, is characterized in that: heating process in described step 3For temperature programming, 5 DEG C of intensifications per hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410302396.5A CN104031240B (en) | 2014-06-27 | 2014-06-27 | A kind of polyurethane adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410302396.5A CN104031240B (en) | 2014-06-27 | 2014-06-27 | A kind of polyurethane adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN104031240A CN104031240A (en) | 2014-09-10 |
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| CN104629671B (en) * | 2015-02-25 | 2016-08-24 | 宁波江东飞创电子科技有限公司 | A kind of modified polyurethane sealant |
| CN106634787A (en) * | 2016-12-10 | 2017-05-10 | 林开浩 | High-solid-content polyurethane adhesive for composite board and preparation method of high-solid-content polyurethane adhesive |
| CN116199856B (en) * | 2023-03-08 | 2024-05-07 | 安徽开捷汽车部件有限公司 | Preparation method of high-hardness flame-retardant polyurethane foaming raw material |
| CN117089143B (en) * | 2023-10-19 | 2024-04-09 | 广东腾业科技有限公司 | Low-energy-consumption recyclable blend and application thereof in production of all-plastic foam pump head |
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| JP4110397B2 (en) * | 2002-12-03 | 2008-07-02 | 日本ポリウレタン工業株式会社 | Polyisocyanate solution and adhesive and paint using the same |
| WO2012104935A1 (en) * | 2011-01-31 | 2012-08-09 | 三洋化成工業株式会社 | Polyol composition for production of polyurethane resins, and polyurethane resin producing process using same |
| CN102408865B (en) * | 2011-09-27 | 2013-10-23 | 英特沃斯(北京)科技有限公司 | Double-component polyurethane adhesive and preparation method thereof |
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