CN110894414A - High-water-resistance polyurethane adhesive - Google Patents
High-water-resistance polyurethane adhesive Download PDFInfo
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- CN110894414A CN110894414A CN201911091727.4A CN201911091727A CN110894414A CN 110894414 A CN110894414 A CN 110894414A CN 201911091727 A CN201911091727 A CN 201911091727A CN 110894414 A CN110894414 A CN 110894414A
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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
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
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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
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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/65—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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/70—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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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J175/06—Polyurethanes from polyesters
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Abstract
The invention relates to an adhesive, in particular to a high-water-resistance polyurethane adhesive, which comprises oligomer polyol, diphenylmethane-4, 4' -diisocyanate, a micromolecule chain extender, an internal cross-linking agent, an external cross-linking agent, an auxiliary agent, a catalyst, a solvent, a surfactant, carbodiimide and an antioxidant, solves the problems of poor adhesive strength, poor mechanical structure, insufficient elasticity and looseness of glue used in the sponge manufacturing process in the prior art, and has better initial adhesive strength, final adhesive strength, proper opening time, good water resistance and mechanical property by selecting a reasonable polyurethane adhesive formula. The polyurethane adhesive prepared by the method has good cohesiveness to all components in the sponge as sponge adhesive, and the prepared sponge has good elasticity, compactness and difficult degumming.
Description
Technical Field
The invention relates to an adhesive, in particular to a high-water-resistance polyurethane adhesive.
Background
The polyurethane is a general name of polyurethane formate, and refers to a general name of a polymer of which a molecular main chain contains a repeating unit chain amine ester group (-NHCOO-). The polyurethane adhesive is an adhesive taking polyurethane as a base material, contains polar groups such as amine ester groups, isocyanate groups and carbamido groups, can form covalent bonds and hydrogen bonds with materials with active hydrogen, and can meet the bonding with different materials such as metal, plastic, wood and the like by adjusting the formula of the polyurethane. The low-temperature performance of the polyurethane adhesive is superior to that of other types of adhesives, and in addition, the polyurethane adhesive also has good wear resistance, water resistance, oil resistance, solvent resistance, chemical resistance and the like, so that the polyurethane adhesive is widely applied to the fields of textiles, furniture, buildings, automobiles and the like.
In recent years, the concept of furniture consumption is changing and breaking through, and the pursuit of functionality in the past is developing into personalization, fashion, functionality, decoration, beauty and environmental protection, so the speed of furniture updating is also gradually increasing. Because Polyurethane (PU) sponge is used in a large amount in the production of furniture products, the demand of furniture products such as mattresses, sofas and the like on PU sponge keeps steadily increasing among compositions. The polyurethane adhesive is the glue commonly used in the preparation process of the sponge, and the composition of the polyurethane adhesive and the proportion among the components have very important influence on the performance of the sponge. At present, the problems often encountered in the sponge manufacturing process are: the polyurethane glue used in the sponge manufacturing process has poor bonding strength, so that the sponge has poor mechanical structure, insufficient elasticity and very loose property.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a high-water-resistance polyurethane adhesive, which aims to solve the problems that the bonding strength of glue used in the sponge manufacturing process is poor, the mechanical structure of the sponge is poor, the elasticity is insufficient and the sponge is very loose in the prior art. The polyurethane adhesive prepared by the method has good cohesiveness to all components in the sponge as sponge adhesive, and the prepared sponge has good elasticity, compactness and difficult degumming.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a high-water-resistance polyurethane adhesive comprises the following components in parts by weight: comprises 110 parts of oligomer polyalcohol 105-;
the oligomer polyol comprises poly adipic acid-1, 2-propylene glycol ester diol and polypropylene oxide diol;
the molecular weight of the poly adipic acid-1, 2-propylene glycol ester diol is 2000;
the molecular weight of the polyoxypropylene diol is 1000;
the weight ratio of the poly adipic acid-1, 2-propylene glycol ester diol to the polypropylene oxide diol is 20: 1;
the small molecular chain extender comprises isophorone diamine and 1, 6-hexanediol, and the weight ratio of the isophorone diamine to the 1, 6-hexanediol is 1: 1;
the auxiliary agent comprises ethylene oxide, nano silicon dioxide and a silane coupling agent, the weight ratio of the ethylene oxide to the nano silicon dioxide to the silane coupling agent is 10:1:3, and the particle size of the nano silicon dioxide is 50-100 nm.
The internal crosslinking agent comprises hexanetriol and trimethylolpropane, and the weight ratio of hexanetriol to trimethylolpropane is 2: 3.
The external cross-linking agent is trimeric isocyanate.
The solvent is ethyl acetate.
The catalyst is one of organic tin catalyst, organic bismuth catalyst and tertiary amine catalyst.
The surfactant is one of acrylate and organosilicon.
The antioxidant is a mixture of 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol and tri (4-octylphenyl) phosphite ester, and the weight ratio of the 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol to the tri (4-octylphenyl) phosphite ester is 3: 1.
The high-water-resistance polyurethane adhesive is synthesized according to the following preparation steps:
(1) purifying the solvent for later use;
(2) dehydrating 110 portions of 105-membered oligomer polyol at 110 ℃ for 2h, cooling to 55 ℃, adding 20-40 portions of diphenylmethane-4, 4' -diisocyanate, gradually heating to 80 ℃ for reaction for 2h to obtain a prepolymer, cooling to 70 ℃, adding 50-80 portions of dehydrated solvent, dissolving and dispersing the prepolymer in the solvent at the rotation speed of 1500rpm, and defoaming in vacuum for 20s until no rising liquid level exists in the mixture;
(3) adding 10-20 parts of micromolecule chain extender and 3-5 parts of surfactant into the defoamed solution obtained in the step (2), quickly and uniformly stirring at the rotating speed of 800rpm, continuously adding 0.5-2 parts of internal cross-linking agent, 1-3 parts of external cross-linking agent, 10-15 parts of auxiliary agent and 3-5 parts of surfactant, quickly and uniformly stirring at the rotating speed of 800rpm, sequentially adding 5-7 parts of carbodiimide and 1-2 parts of antioxidant, quickly and uniformly stirring at the rotating speed of 800rpm, then adding 1-2 parts of catalyst, and quickly stirring at the rotating speed of 1500rpm for reaction;
(4) preheating a mold brushed with a release agent at 120 ℃ for 20min, pouring the solution finally reacted in the step (3) into the mold, covering the mold when the mold is dipped by a glass rod and can be drawn continuously, pressurizing at 10MPa for vulcanization for 2h, taking out the mold after vulcanization, taking out a sample, and vulcanizing at 100 ℃ for 10h again to obtain the polyurethane adhesive.
The invention has the beneficial effects that:
(1) the high-water-resistance polyurethane adhesive provided by the invention has better initial adhesion strength, final adhesion strength and proper open time.
(2) The high-water-resistance polyurethane adhesive provided by the invention has good water resistance and mechanical properties, the water resistance rate (2h) can be less than 1%, the tensile strength can reach 38MPa, and the shear strength can reach 10 MPa.
Detailed Description
Example 1
(1) Purifying ethyl acetate solvent at 77 deg.c;
(2) the preparation method comprises the following steps of (1) dehydrating a mixture of 105 parts of polyester polyol with the weight ratio of poly adipic acid-1, 2-propylene glycol ester diol to polypropylene oxide diol being 20:1, wherein the molecular weight of the poly adipic acid-1, 2-propylene glycol ester diol is 2000, the molecular weight of the polypropylene oxide diol is 1000, dehydrating the mixture for 2 hours at 110 ℃, cooling the mixture to 55 ℃, adding 20 parts of diphenylmethane-4, 4' -diisocyanate, gradually heating the mixture to 80 ℃ to react for 2 hours to obtain a prepolymer, cooling the prepolymer to 70 ℃, adding 50 parts of dehydrated ethyl acetate, dissolving and dispersing the prepolymer in the ethyl acetate at the rotating speed of 1500rpm, and defoaming the mixture in vacuum for 20 seconds until no rising liquid level exists in the mixture;
(3) adding 10 parts of a mixture of isophorone diamine and 1, 6-hexanediol with a weight ratio of 1:1 and 3 parts of polyether modified polysiloxane (specific gravity 1.042) into the solution of the defoamed prepolymer obtained in the step (2) in sequence, stirring uniformly at 800rpm, continuously adding 0.5 part of an internal crosslinking agent in which hexanetriol and trimethylolpropane are mixed with a weight ratio of 2:3, 1 part of an external crosslinking agent of isocyanurate, 10 parts of ethylene oxide with a weight ratio of 10:1:3, a mixture of silica and a silane coupling agent with a particle size of 50nm, wherein the silane coupling agent is KH550, stirring uniformly at 800rpm, adding 5 parts of carbodiimide and 1 part of a mixture of 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol and tris (4-octylphenyl) phosphite with a weight ratio of 3:1 in sequence, rapidly stirring uniformly at the rotating speed of 800rpm, adding 1 part of catalyst dibutyltin dilaurate, and rapidly stirring for reaction at the rotating speed of 1500 rpm;
(4) preheating a mold brushed with a release agent at 120 ℃ for 20min, pouring the solution finally reacted in the step (3) into the mold, covering the mold when the mold is dipped by a glass rod and can be drawn continuously, pressurizing at 10MPa for vulcanization for 2h, taking out the mold after vulcanization, taking out a sample, and vulcanizing at 100 ℃ for 10h again to obtain the polyurethane adhesive.
Example 2
(1) Purifying ethyl acetate solvent at 77 deg.c;
(2) 106 parts of polyester polyol mixture with the weight ratio of poly adipic acid-1, 2-propylene glycol ester diol to polypropylene oxide diol being 20:1, wherein the molecular weight of the poly adipic acid-1, 2-propylene glycol ester diol is 2000, the molecular weight of the polypropylene oxide diol is 1000, the mixture is dehydrated for 2 hours at 110 ℃, the temperature is reduced to 55 ℃, 30 parts of diphenylmethane-4, 4' -diisocyanate is added, the temperature is gradually increased to 80 ℃ for reaction for 2 hours to obtain prepolymer, the temperature is reduced to 70 ℃, 60 parts of dehydrated ethyl acetate is added, the prepolymer is dissolved and dispersed in the ethyl acetate at the rotating speed of 1500rpm, and the mixture is defoamed in vacuum for 20 seconds until no rising liquid level exists in the mixture;
(3) adding 15 parts of a mixture of isophorone diamine and 1, 6-hexanediol with a weight ratio of 1:1 and 4 parts of polyether modified polysiloxane (specific gravity 1.043) into the solution of the defoamed prepolymer obtained in the step (2) in turn, stirring uniformly at 800rpm, continuously adding 1 part of a mixed internal crosslinking agent of hexanetriol and trimethylolpropane with a weight ratio of 2:3, 2 parts of an external crosslinking agent of isocyanurate, 11 parts of ethylene oxide, and an auxiliary agent of silica and a silane coupling agent with a weight ratio of 10:1:3 in turn, wherein the particle size of the silica is 60nm, the silane coupling agent is KH560, stirring uniformly at 800rpm, adding 6 parts of carbodiimide and 1.5 parts of a mixture of 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol and tris (4-octylphenyl) phosphite with a weight ratio of 3:1, rapidly stirring uniformly at the rotating speed of 800rpm, then adding 1.5 parts of catalyst bismuth isooctanoate, and rapidly stirring for reaction at the rotating speed of 1500 rpm;
(4) preheating a mold brushed with a release agent at 120 ℃ for 20min, pouring the solution finally reacted in the step (3) into the mold, covering the mold when the mold is dipped by a glass rod and can be drawn continuously, pressurizing at 10MPa for vulcanization for 2h, taking out the mold after vulcanization, taking out a sample, and vulcanizing at 100 ℃ for 10h again to obtain the polyurethane adhesive.
Example 3
(1) Purifying ethyl acetate solvent at 77 deg.c;
(2) 107 parts of polyester polyol mixture with the weight ratio of the poly adipic acid-1, 2-propylene glycol ester diol to the polypropylene oxide diol being 20:1, wherein the molecular weight of the poly adipic acid-1, 2-propylene glycol ester diol is 2000, the molecular weight of the polypropylene oxide diol is 1000, the mixture is dehydrated at 110 ℃ for 2 hours, the temperature is reduced to 55 ℃, 40 parts of diphenylmethane-4, 4' -diisocyanate is added, the temperature is gradually increased to 80 ℃ for reaction for 2 hours to obtain prepolymer, the temperature is reduced to 70 ℃, 70 parts of dehydrated ethyl acetate is added, the prepolymer is dissolved and dispersed in the ethyl acetate at the rotating speed of 1500rpm, and the mixture is defoamed in vacuum for 20 seconds until no rising liquid level exists in the mixture;
(3) adding 20 parts by weight of a mixture of isophorone diamine and 1, 6-hexanediol and 5 parts by weight of butyl acrylate into the solution of the defoamed prepolymer obtained in the step (2) in turn, stirring uniformly at the rotation speed of 800rpm, continuously adding 1.5 parts by weight of an internal crosslinking agent of hexanetriol and trimethylolpropane mixed in a ratio of 2:3, 3 parts by weight of an external crosslinking agent of isocyanurate, 12 parts by weight of ethylene oxide and an auxiliary agent of silica and a silane coupling agent in a ratio of 10:1:3 in turn, wherein the particle diameter of the silica is 70nm, the silane coupling agent is KH570, stirring uniformly at the rotation speed of 800rpm, adding 7 parts by weight of carbodiimide and 2 parts by weight of a mixture of 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol and tris (4-octylphenyl) phosphite in a ratio of 3:1, rapidly stirring uniformly at the rotation speed of 800rpm, then adding 2 parts of catalyst triethylamine, and rapidly stirring for reaction at the rotation speed of 1500 rpm;
(4) preheating a mold brushed with a release agent at 120 ℃ for 20min, pouring the solution finally reacted in the step (3) into the mold, covering the mold when the mold is dipped by a glass rod and can be drawn continuously, pressurizing at 10MPa for vulcanization for 2h, taking out the mold after vulcanization, taking out a sample, and vulcanizing at 100 ℃ for 10h again to obtain the polyurethane adhesive.
Example 4
(1) Purifying ethyl acetate solvent at 77 deg.c;
(2) 108 parts of a mixture of polyester polyol with the weight ratio of poly adipic acid-1, 2-propylene glycol ester diol to polypropylene oxide diol being 20:1, wherein the molecular weight of the poly adipic acid-1, 2-propylene glycol ester diol is 2000, the molecular weight of the polypropylene oxide diol is 1000, the mixture is dehydrated at 110 ℃ for 2 hours, the temperature is reduced to 55 ℃, 30 parts of diphenylmethane-4, 4' -diisocyanate is added, the temperature is gradually increased to 80 ℃ for reaction for 2 hours to obtain a prepolymer, the temperature is reduced to 70 ℃, 80 parts of dehydrated ethyl acetate is added, the prepolymer is dissolved and dispersed in the ethyl acetate at the rotating speed of 1500rpm, and the mixture is defoamed in vacuum for 20 seconds until no rising liquid level exists in the mixture;
(3) adding 15 parts of a mixture of isophorone diamine and 1, 6-hexanediol with the weight ratio of 1:1 and 4 parts of butyl acrylate into the solution of the defoamed prepolymer obtained in the step (2) in sequence, stirring uniformly at the rotating speed of 800rpm, continuously adding 2 parts of an internal crosslinking agent of hexanetriol and trimethylolpropane with the weight ratio of 2:3, 2 parts of an external crosslinking agent of isocyanurate, 13 parts of ethylene oxide with the weight ratio of 10:1:3, an auxiliary agent of silica and a silane coupling agent, wherein the particle size of the silica is 80nm, the silane coupling agent is KH550, stirring uniformly at the rotating speed of 800rpm, adding 6 parts of carbodiimide and 1 part of a mixture of 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol and tris (4-octylphenyl) phosphite with the weight ratio of 3:1, rapidly stirring uniformly at the rotating speed of 800rpm, then adding 1 part of catalyst dibutyltin dilaurate, and rapidly stirring for reaction at the rotating speed of 1500 rpm;
(4) preheating a mold brushed with a release agent at 120 ℃ for 20min, pouring the solution finally reacted in the step (3) into the mold, covering the mold when the mold is dipped by a glass rod and can be drawn continuously, pressurizing at 10MPa for vulcanization for 2h, taking out the mold after vulcanization, taking out a sample, and vulcanizing at 100 ℃ for 10h again to obtain the polyurethane adhesive.
Example 5
(1) Purifying ethyl acetate solvent at 77 deg.c;
(2) the preparation method comprises the following steps of (1) dehydrating a mixture of 109 parts of polyester polyol with a weight ratio of 20:1 of poly-1, 2-propylene glycol adipate to poly-propylene glycol, wherein the molecular weight of the poly-1, 2-propylene glycol adipate is 2000, the molecular weight of the poly-propylene glycol is 1000, dehydrating the mixture for 2 hours at 110 ℃, cooling the mixture to 55 ℃, adding 30 parts of diphenylmethane-4, 4' -diisocyanate, gradually heating the mixture to 80 ℃ to react for 2 hours to obtain a prepolymer, cooling the prepolymer to 70 ℃, adding 70 parts of dehydrated ethyl acetate, dissolving and dispersing the prepolymer in the ethyl acetate at a rotating speed of 1500rpm, and defoaming the mixture in vacuum for 20 seconds until no liquid level rises in the mixture;
(3) adding 15 parts of a mixture of isophorone diamine and 1, 6-hexanediol and 5 parts of trimethylolpropane triacrylate in a weight ratio of 1:1 into the solution of the defoamed prepolymer obtained in the step (2) in sequence, stirring uniformly at the rotation speed of 800rpm, continuously adding 1 part of an internal crosslinking agent formed by mixing hexanetriol and trimethylolpropane in a weight ratio of 2:3, 2 parts of an external crosslinking agent of isocyanurate, 14 parts of ethylene oxide in a weight ratio of 10:1:3, an auxiliary agent formed by mixing silica and a silane coupling agent, wherein the particle size of the silica is 90nm, the silane coupling agent is KH550, stirring uniformly at the rotation speed of 800rpm, adding 7 parts of carbodiimide and 2 parts of a mixture of 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol and tris (4-octylphenyl) phosphite in a weight ratio of 3:1, rapidly stirring uniformly at the rotating speed of 800rpm, then adding 1 part of catalyst dimethylcyclohexylamine, and rapidly stirring for reaction at the rotating speed of 1500 rpm;
(4) preheating a mold brushed with a release agent at 120 ℃ for 20min, pouring the solution finally reacted in the step (3) into the mold, covering the mold when the mold is dipped by a glass rod and can be drawn continuously, pressurizing at 10MPa for vulcanization for 2h, taking out the mold after vulcanization, taking out a sample, and vulcanizing at 100 ℃ for 10h again to obtain the polyurethane adhesive.
Example 6
(1) Purifying ethyl acetate solvent at 77 deg.c;
(2) the preparation method comprises the following steps of (1) dehydrating 110 parts of polyester polyol with the weight ratio of poly adipic acid-1, 2-propylene glycol ester diol to polypropylene oxide diol being 20:1, wherein the molecular weight of the poly adipic acid-1, 2-propylene glycol ester diol is 2000, the molecular weight of the polypropylene oxide diol is 1000 at 110 ℃ for 2 hours, cooling to 55 ℃, adding 40 parts of diphenylmethane-4, 4' -diisocyanate, gradually heating to 80 ℃ for reaction for 2 hours to obtain a prepolymer, cooling to 70 ℃, adding 80 parts of dehydrated ethyl acetate, dissolving and dispersing the prepolymer in the ethyl acetate at the rotating speed of 1500rpm, and defoaming in vacuum for 20 seconds until no rising liquid level exists in the mixture;
(3) adding 10 parts by weight of a mixture of isophorone diamine and 1, 6-hexanediol and 3 parts by weight of 2-dodecyl acrylate into the solution of the defoamed prepolymer obtained in the step (2) in turn, stirring uniformly at the rotation speed of 800rpm, continuously adding 0.5 part by weight of an internal crosslinking agent of hexanetriol and trimethylolpropane mixed, 1 part by weight of an external crosslinking agent of isocyanurate, 15 parts by weight of ethylene oxide, silica and an auxiliary agent of a silane coupling agent mixed in a weight ratio of 10:1:3 in turn, wherein the particle size of the silica is 100nm, the silane coupling agent is KH570, stirring uniformly at the rotation speed of 800rpm, adding 7 parts by weight of carbodiimide and 2 parts by weight of a mixture of 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol and tris (4-octylphenyl) phosphite in a weight ratio of 3:1, rapidly stirring uniformly at the rotation speed of 800rpm, adding 1 part of catalyst N-methylmorpholine, and rapidly stirring for reaction at the rotation speed of 1500 rpm;
(4) preheating a mold brushed with a release agent at 120 ℃ for 20min, pouring the solution finally reacted in the step (3) into the mold, covering the mold when the mold is dipped by a glass rod and can be drawn continuously, pressurizing at 10MPa for vulcanization for 2h, taking out the mold after vulcanization, taking out a sample, and vulcanizing at 100 ℃ for 10h again to obtain the polyurethane adhesive.
The properties of the materials prepared in examples 1-6 were tested as shown in tables 1 and 2 below:
the mechanical property test of the polyurethane adhesive prepared by the method is carried out according to the GB/T528-2009 standard;
the open time test of the polyurethane adhesive prepared by the method is carried out according to the GB/T3477.57-2002 standard: and coating the glue solution on a smooth flat plate, controlling the thickness of the glue layer to be 0.1mm, and recording the time(s) when the surface of the glue layer has viscosity by using a stopwatch.
TABLE 1
TABLE 2
| Examples | Open time/s | Water resistance (2 h)/%) |
| Example 1 | 120 | 1％ |
| Example 2 | 126 | 0.8％ |
| Example 3 | 121 | 1％ |
| Example 4 | 125 | 1.2％ |
| Example 5 | 122 | 0.8％ |
| Example 6 | 121 | 0.6％ |
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. A high-water-resistance polyurethane adhesive is characterized in that (by weight portion): comprises 110 parts of oligomer polyalcohol 105-;
the oligomer polyol comprises poly adipic acid-1, 2-propylene glycol ester diol and polypropylene oxide diol;
the molecular weight of the poly adipic acid-1, 2-propylene glycol ester diol is 2000;
the molecular weight of the polyoxypropylene diol is 1000;
the weight ratio of the poly adipic acid-1, 2-propylene glycol ester diol to the polypropylene oxide diol is 20: 1;
the small molecular chain extender comprises isophorone diamine and 1, 6-hexanediol, and the weight ratio of the isophorone diamine to the 1, 6-hexanediol is 1: 1;
the auxiliary agent comprises ethylene oxide, nano silicon dioxide and a silane coupling agent, the weight ratio of the ethylene oxide to the nano silicon dioxide to the silane coupling agent is 10:1:3, and the particle size of the nano silicon dioxide is 50-100 nm.
2. The highly water resistant polyurethane adhesive of claim 1, wherein: the internal crosslinking agent comprises hexanetriol and trimethylolpropane, and the weight ratio of hexanetriol to trimethylolpropane is 2: 3.
3. The highly water resistant polyurethane adhesive of claim 1, wherein: the external cross-linking agent is trimeric isocyanate.
4. The highly water resistant polyurethane adhesive of claim 1, wherein: the solvent is ethyl acetate.
5. The highly water resistant polyurethane adhesive of claim 1, wherein: the catalyst is one of organic tin catalyst, organic bismuth catalyst and tertiary amine catalyst.
6. The highly water resistant polyurethane adhesive of claim 1, wherein: the surfactant is one of acrylate and organosilicon.
7. The highly water resistant polyurethane adhesive of claim 1, wherein: the antioxidant is a mixture of 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol and tri (4-octylphenyl) phosphite ester, and the weight ratio of the 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol to the tri (4-octylphenyl) phosphite ester is 3: 1.
8. The highly water resistant polyurethane adhesive of claim 1, wherein: the preparation method comprises the following steps:
(1) purifying the solvent for later use;
(2) dehydrating 110 portions of 105-membered oligomer polyol at 110 ℃ for 2h, cooling to 55 ℃, adding 20-40 portions of diphenylmethane-4, 4' -diisocyanate, gradually heating to 80 ℃ for reaction for 2h to obtain a prepolymer, cooling to 70 ℃, adding 50-80 portions of dehydrated solvent, dissolving and dispersing the prepolymer in the solvent at the rotation speed of 1500rpm, and defoaming in vacuum for 20s until no rising liquid level exists in the mixture;
(3) adding 10-20 parts of micromolecule chain extender and 3-5 parts of surfactant into the defoamed solution obtained in the step (2), quickly and uniformly stirring at the rotating speed of 800rpm, continuously adding 0.5-2 parts of internal cross-linking agent, 1-3 parts of external cross-linking agent and 10-15 parts of auxiliary agent, quickly and uniformly stirring at the rotating speed of 800rpm, sequentially adding 5-7 parts of carbodiimide and 1-2 parts of antioxidant, quickly and uniformly stirring at the rotating speed of 800rpm, then adding 1-2 parts of catalyst, and quickly stirring at the rotating speed of 1500rpm for reaction;
(4) preheating a mold brushed with a release agent at 120 ℃ for 20min, pouring the solution finally reacted in the step (3) into the mold, covering the mold when the mold is dipped by a glass rod and can be drawn continuously, pressurizing at 10MPa for vulcanization for 2h, taking out the mold after vulcanization, taking out a sample, and vulcanizing at 100 ℃ for 10h again to obtain the polyurethane adhesive.
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