CN104031240A - Polyurethane adhesive and preparation method thereof - Google Patents
Polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN104031240A CN104031240A CN201410302396.5A CN201410302396A CN104031240A CN 104031240 A CN104031240 A CN 104031240A CN 201410302396 A CN201410302396 A CN 201410302396A CN 104031240 A CN104031240 A CN 104031240A
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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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- 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
- C08G18/32—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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- 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
- C08G18/58—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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- 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 polyurethane adhesive and a preparation method thereof. The polyurethane adhesive comprises diphenylmethane diisocyanate, styrene grafted polyether polyol, epoxide resin, methyl p-toluenesulfonate, polypropylene glycol, polyoxypropylene pentaerythritol ester, an amine catalyst, isophorone diamine, zeolite, castor oil, N-ethyl-N-zinc phenyl dithiocarbamate, resorcinol, triphenylphosphine, a silane coupling agent and an emulsifying agent. The preparation method comprises the following steps of: firstly mixing the diphenylmethane diisocyanate, the amine catalyst, the epoxide resin, the methyl p-toluenesulfonate, the polypropylene glycol, the polyoxypropylene pentaerythritol ester and the zeolite, and then adding the resorcinol and the triphenylphosphine; stirring, and then adding a mixture of the styrene grafted polyether polyol, the isophorone diamine, the castor oil, the N-ethyl-N-zinc phenyl dithiocarbamate, the silane coupling agent and the emulsifying agent to obtain the polyurethane adhesive. The polyurethane adhesive provided by the invention has the advantages of excellent yellowing resistance, ageing resistance, heat resistant property, hydrolysis resistant property and bonding 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
Urethane (PU) tackiness agent refers to the tackiness agent that contains urethano (NHCOO-) and/or isocyanate group (NCO) class in molecular chain.Polyurethane adhesive is mainly divided into polyisocyanates and the large class of urethane two, by use-pattern, divides polyurethane adhesive can be divided into two kinds of single component and two-packs.The polarity of isocyanate group and urethano, chemically reactive are all very strong, therefore the material (glass, metal etc.) of porous material (leather, foam etc.) and any surface finish are had to good chemical bonding power.And polyurethane adhesive has the advantages such as snappiness is good, vibration resistance is good, shock-resistant, wear-resisting, cohesive strength is large, purposes is more and more extensive.
Polyurethane adhesive is generally divided into one-component polyurethane adhesive and dual-component polyurethane adhesive.One-component polyurethane adhesive general operation is convenient, but in process of production, generally all can add organic solvent, does not meet environmental requirement; One-component polyurethane adhesive is generally NCO group end capping simultaneously, and in storage process, easy and airborne moisture content reaction, causes the phenomenons such as skinning, caking, and the shelf lives is shorter; One-component polyurethane adhesive does not generally add catalyzer or only adds the catalyzer of denier in addition, thereby curing speed is slower, in low temperature environment, even wants 24 hours above could solidifying 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 shelf lives is longer, but after two components mix by stoicheiometry, general working life is too short, at high temperature season, after glue mixes, viscosity increases very fast especially, cause the later stage to use difficulty, a large amount of glue is scrapped maybe and can not be formed good bonding, produces a large amount of unacceptable products.Even at low temperature season, although extend working life, also extend same set time, affect client's production efficiency, although add conventional catalyst (organo-bismuth, organotin, amine etc.) can accelerate curing speed, 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 tackiness agent not only has excellent yellowing resistance, resistance to deterioration, also has better resistance toheat, anti-hydrolytic performance and bonding strength.
Polyurethane adhesive, in weight part, comprise: 100～200 parts of diphenylmethanediisocyanates, 20～30 parts of styrene-grafted polyether glycols, 30～90 parts of epoxy resin, 5～12 parts of methyl tosylates, 3～15 parts of polypropylene glycols, 1～7 part of polyoxypropylene pentaerythritol ester, 2～6 parts of amine catalysts, 0.5～3.2 part of isophorone diamine, 0.2～0.7 part, zeolite, 0.4～1.5 part of Viscotrol C, 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 coupling agent, 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 coupling agent is the mixture of a kind of in KH-550 or KH-560 or two kinds.
As the further improvement of foregoing invention, described emulsifying agent is sodium lauryl sulphate.
As the further improvement of foregoing invention, described amine catalyst is a kind of in triethylene diamine, tetrem alkene triamine or five ethene tetramines.
The preparation method of above-mentioned polyurethane adhesive, comprises the following steps:
Step 1, diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol and polyoxypropylene pentaerythritol ester are poured in stirring tank, add again zeolite to stir, then stirring tank is heated to after 100～120 ℃, add Resorcinol and triphenylphosphine, stir, be cooled to room temperature and obtain mixture I;
Step 2, styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 100～120 ℃, is cooled to room temperature and obtains mixture II;
Step 3, mixes mixture I and mixture II, is heated to 70～90 ℃, after insulation 2～8h, is cooled to room temperature, obtains polyurethane adhesive.
As the further improvement of foregoing invention, in described step 1, stirring tank keeps vacuum tightness at-0.08～-0.1Mpa.
As the further improvement of foregoing invention, in described step 3, heat-processed is temperature programming, 5 ℃ of intensifications per hour.
Polyurethane adhesive of the present invention not only has excellent yellowing resistance, resistance to deterioration, also has better resistance toheat, anti-hydrolytic performance and bonding strength; Except the use of triphen, there is high-environmental performance side by side, meet International Environmental Protection standard.
Embodiment
Embodiment 1
Polyurethane adhesive, in weight part, comprise: 100 parts of diphenylmethanediisocyanates, 20 parts of styrene-grafted polyether glycols, 30 parts of bisphenol A epoxide resins, 5 parts of methyl tosylates, 3 parts of polypropylene glycols, 1 part of polyoxypropylene pentaerythritol ester, 2 parts of triethylene diamines, 0.5 part of isophorone diamine, 0.2 part, zeolite, 0.4 part of Viscotrol C, 0.1 part of N-ethyl-N-phenyl zinc dithiocarbamate, 0.3 part of Resorcinol, 0.2 part of triphenylphosphine, 1 part of silane resin acceptor kh-550,2 parts of sodium lauryl sulphate.
First diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol and polyoxypropylene pentaerythritol ester are poured in stirring tank, add again zeolite to stir, stirring tank is heated and is evacuated to vacuum tightness and be-0.08Mpa, when temperature reaches after 100 ℃, continue to keep vacuum 2h, add Resorcinol and triphenylphosphine, stir, continue to vacuumize 0.5h, be cooled to room temperature and obtain mixture I; Styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 100 ℃, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, 5 ℃ of intensifications per hour, are heated to 90 ℃, after insulation 2h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 2
Polyurethane adhesive, in weight part, comprise: 115 parts of diphenylmethanediisocyanates, 23 parts of styrene-grafted polyether glycols, 35 parts of bisphenol A epoxide resins, 7 parts of methyl tosylates, 5 parts of polypropylene glycols, 2 parts of polyoxypropylene pentaerythritol esters, 3 parts of tetrem alkene triamines, 0.8 part of isophorone diamine, 0.3 part, zeolite, 0.6 part of Viscotrol C, 0.2 part of N-ethyl-N-phenyl zinc dithiocarbamate, 0.5 part of Resorcinol, 0.4 part of triphenylphosphine, silane coupling agent KH-5602 part, 3 parts of sodium lauryl sulphate.
First diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol and polyoxypropylene pentaerythritol ester are poured in stirring tank, add again zeolite to stir, stirring tank is heated and is evacuated to vacuum tightness and be-0.1Mpa, when temperature reaches after 120 ℃, continue to keep vacuum 0.5h, add Resorcinol and triphenylphosphine, stir, continue to vacuumize 2h, be cooled to room temperature and obtain mixture I; Styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 120 ℃, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, 5 ℃ of intensifications per hour, are heated to 70 ℃, after insulation 8h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 3
Polyurethane adhesive, in weight part, comprise: 135 parts of diphenylmethanediisocyanates, 25 parts of styrene-grafted polyether glycols, 42 parts of bisphenol A epoxide resins, 8 parts of methyl tosylates, 7 parts of polypropylene glycols, 3 parts of polyoxypropylene pentaerythritol esters, five 5 parts of ethene tetramines, 1.5 parts of isophorone diamines, 0.4 part, zeolite, 0.9 part of Viscotrol C, 0.3 part of N-ethyl-N-phenyl zinc dithiocarbamate, 0.8 part of Resorcinol, 0.6 part of triphenylphosphine, 2 parts of silane coupling agents, 4 parts of sodium lauryl sulphate.
Above-mentioned silane coupling agent be KH-550 and KH-560 mixture, its weight ratio is 3:7.
First diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol and polyoxypropylene pentaerythritol ester are poured in stirring tank, add again zeolite to stir, stirring tank is heated and is evacuated to vacuum tightness and be-0.09Mpa, when temperature reaches after 110 ℃, continue to keep vacuum 1h, add Resorcinol and triphenylphosphine, stir, continue to vacuumize 1h, be cooled to room temperature and obtain mixture I; Styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 110 ℃, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, 5 ℃ of intensifications per hour, are heated to 80 ℃, after insulation 5h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 4
Polyurethane adhesive, in weight part, comprise: 185 parts of diphenylmethanediisocyanates, 27 parts of styrene-grafted polyether glycols, 70 parts of bisphenol A epoxide resins, 10 parts of methyl tosylates, 12 parts of polypropylene glycols, 6 parts of polyoxypropylene pentaerythritol esters, 5 parts of tetrem alkene triamines, 2.8 parts of isophorone diamines, 0.6 part, zeolite, 1.1 parts of Viscotrol C, 0.6 part of N-ethyl-N-phenyl zinc dithiocarbamate, 2.2 parts of Resorcinols, 1.6 parts of triphenylphosphines, 4 parts of silane resin acceptor kh-550s, 5 parts of sodium lauryl sulphate.
First diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol and polyoxypropylene pentaerythritol ester are poured in stirring tank, add again zeolite to stir, stirring tank is heated and is evacuated to vacuum tightness and be-0.08Mpa, when temperature reaches after 100 ℃, continue to keep vacuum 0.5h, add Resorcinol and triphenylphosphine, stir, continue to vacuumize 0.5h, be cooled to room temperature and obtain mixture I; Styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 100 ℃, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, 5 ℃ of intensifications per hour, are heated to 70 ℃, after insulation 2h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 5
Polyurethane adhesive, in weight part, comprise: 146 parts of diphenylmethanediisocyanates, 24 parts of styrene-grafted polyether glycols, 75 parts of bisphenol A epoxide resins, 10 parts of methyl tosylates, 11 parts of polypropylene glycols, 3 parts of polyoxypropylene pentaerythritol esters, five 5 parts of ethene tetramines, 2.4 parts of isophorone diamines, 0.3 part, zeolite, 1.2 parts of Viscotrol C, 0.5 part of N-ethyl-N-phenyl zinc dithiocarbamate, 1.5 parts of Resorcinols, 1.2 parts of triphenylphosphines, silane coupling agent KH-5603 part, 4 parts of sodium lauryl sulphate.
First diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol and polyoxypropylene pentaerythritol ester are poured in stirring tank, add again zeolite to stir, stirring tank is heated and is evacuated to vacuum tightness and be-0.1Mpa, when temperature reaches after 120 ℃, continue to keep vacuum 2h, add Resorcinol and triphenylphosphine, stir, continue to vacuumize 2h, be cooled to room temperature and obtain mixture I; Styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 120 ℃, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, 5 ℃ of intensifications per hour, are heated to 90 ℃, after insulation 8h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 6
Polyurethane adhesive, in weight part, comprise: 200 parts of diphenylmethanediisocyanates, 0 part of styrene-grafted polyether glycol, 90 parts of bisphenol A epoxide resins, 12 parts of methyl tosylates, 15 parts of polypropylene glycols, 7 parts of polyoxypropylene pentaerythritol esters, 6 parts of triethylene diamines, 3.2 parts of isophorone diamines, 0.7 part, zeolite, 1.5 parts of Viscotrol C, 0.7 part of N-ethyl-N-phenyl zinc dithiocarbamate, 2.5 parts of Resorcinols, 1.8 parts of triphenylphosphines, 5 parts of silane coupling agents, 6 parts of sodium lauryl sulphate.
Above-mentioned silane coupling agent be KH-550 and KH-560 mixture, its weight ratio is 6:4.
First diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol and polyoxypropylene pentaerythritol ester are poured in stirring tank, add again zeolite to stir, stirring tank is heated and is evacuated to vacuum tightness and be-0.08Mpa, when temperature reaches after 105 ℃, continue to keep vacuum 1.5h, add Resorcinol and triphenylphosphine, stir, continue to vacuumize 1h, be cooled to room temperature and obtain mixture I; Styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 115 ℃, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, 5 ℃ of intensifications per hour, are heated to 85 ℃, 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 pentaerythritol ester, specific as follows:
Polyurethane adhesive, comprises in weight part: 146 parts of diphenylmethanediisocyanates, 24 parts of styrene-grafted polyether glycols, 75 parts of bisphenol A epoxide resins, 10 parts of methyl tosylates, 11 parts of polypropylene glycols, five 5 parts of ethene tetramines, 2.4 parts of isophorone diamines, 0.3 part, zeolite, 1.2 parts of Viscotrol C, 0.5 part of N-ethyl-N-phenyl zinc dithiocarbamate, 1.5 parts of Resorcinols, 1.2 parts of triphenylphosphines, silane coupling agent KH-5603 part, 4 parts of sodium lauryl sulphate.
First diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol are poured in stirring tank, add again zeolite to stir, stirring tank is heated and is evacuated to vacuum tightness and be-0.1Mpa, when temperature reaches after 120 ℃, continue to keep vacuum 2h, add Resorcinol and triphenylphosphine, stir, continue to vacuumize 2h, be cooled to room temperature and obtain mixture I; Styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 120 ℃, be cooled to room temperature and obtain mixture II; Mixture I and mixture II are mixed, temperature programming, 5 ℃ of intensifications per hour, are heated to 90 ℃, after insulation 8h, are cooled to room temperature, obtain polyurethane adhesive.
Embodiment 1 to 7 products obtained therefrom is carried out to objectionable impurities test with reference to GB19340-2003, and result is as follows:
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Benzene | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect |
| Toluene+dimethylbenzene | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect |
| Free toluene diisocyanate | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect |
| Normal hexane | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect |
| Methylene dichloride | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect |
| 1,2-ethylene dichloride | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect |
| Vinyl trichloride | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect |
| Trieline | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect | Do not detect |
| Total volatile organism | 682 | 680 | 686 | 684 | 682 | 690 | 695 |
Embodiment 1 to 7 gained sample is carried out to performance test, and result is as follows:
From above result, the polyurethane adhesive of present method does not only detect environmentally hazardous triphen, free toluene diisocyanate and halohydrocarbon; There are excellent gluing effect, ageing resistance, thermotolerance, hydrolytic resistance and yellowing resistance simultaneously.In embodiment 7, do not contain polyoxypropylene pentaerythritol ester, affected the properties of tackiness agent, this may be because polyoxypropylene pentaerythritol ester has effectively improved the cohesive strength of tackiness agent, and makes it have better thermotolerance, resistance to xanthochromia shape and resistance to deterioration.
Claims (8)
1. a polyurethane adhesive, in weight part, comprise: 100～200 parts of diphenylmethanediisocyanates, 20～30 parts of styrene-grafted polyether glycols, 30～90 parts of epoxy resin, 5～12 parts of methyl tosylates, 3～15 parts of polypropylene glycols, 1～7 part of polyoxypropylene pentaerythritol ester, 2～6 parts of amine catalysts, 0.5～3.2 part of isophorone diamine, 0.2～0.7 part, zeolite, 0.4～1.5 part of Viscotrol C, 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 coupling agent, 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 coupling agent is the mixture of a kind of in KH-550 or KH-560 or two kinds.
4. polyurethane adhesive according to claim 1, is characterized in that: described emulsifying agent is sodium lauryl sulphate.
5. polyurethane adhesive according to claim 1, is characterized in that: described amine catalyst is a kind of in triethylene diamine, tetrem alkene 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, diphenylmethanediisocyanate, amine catalyst, epoxy resin, methyl tosylate, polypropylene glycol and polyoxypropylene pentaerythritol ester are poured in stirring tank, add again zeolite to stir, then stirring tank is heated to after 100～120 ℃, add Resorcinol and triphenylphosphine, stir, be cooled to room temperature and obtain mixture I;
Step 2, styrene-grafted polyether glycol, isophorone diamine, Viscotrol C, N-ethyl-N-phenyl zinc dithiocarbamate, silane coupling agent and emulsifying agent are poured in stirring tank, then stirring tank is heated to after 100～120 ℃, is cooled to room temperature and obtains mixture II;
Step 3, mixes mixture I and mixture II, is heated to 70～90 ℃, after insulation 2～8h, is cooled to room temperature, obtains polyurethane adhesive.
7. the preparation method of polyurethane adhesive according to claim 6, is characterized in that: in described step 1, stirring tank keeps vacuum tightness at-0.08～-0.1Mpa.
8. the preparation method of polyurethane adhesive according to claim 6, is characterized in that: in described step 3, heat-processed is temperature programming 5 ℃ of intensifications per hour.
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| CN104629671A (en) * | 2015-02-25 | 2015-05-20 | 孙高雷 | 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 |
| CN116199856A (en) * | 2023-03-08 | 2023-06-02 | 安徽开捷汽车部件有限公司 | Preparation method of high-hardness flame-retardant polyurethane foaming raw material |
| CN117089143A (en) * | 2023-10-19 | 2023-11-21 | 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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| CN103261261A (en) * | 2011-01-31 | 2013-08-21 | 三洋化成工业株式会社 | Polyol composition for production of polyurethane resins, and polyurethane resin producing process using same |
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| JP2004231931A (en) * | 2002-12-03 | 2004-08-19 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate solution, as well as adhesive and coating material using the same |
| CN103261261A (en) * | 2011-01-31 | 2013-08-21 | 三洋化成工业株式会社 | Polyol composition for production of polyurethane resins, and polyurethane resin producing process using same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104629671A (en) * | 2015-02-25 | 2015-05-20 | 孙高雷 | Modified polyurethane sealant |
| 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 |
| CN116199856A (en) * | 2023-03-08 | 2023-06-02 | 安徽开捷汽车部件有限公司 | Preparation method of high-hardness flame-retardant polyurethane foaming raw material |
| 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 |
| CN117089143A (en) * | 2023-10-19 | 2023-11-21 | 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 |
| 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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| CN104031240B (en) | 2016-05-11 |
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Effective date of registration: 20161130 Address after: 201514 Shanghai city Jinshan District Zhangyan town Qin village seven groups Patentee after: SHANGHAI HANSI INDUSTRIAL CO., LTD. Address before: 214000 Jiangsu province Wuxi chonganou Liberation Road No. 688 Patentee before: Wuxi City Chong'an District Technology Entrepreneurship Service Center |