CN110093137A - A kind of reaction thickening type two component polyurethane glass bonded adhesives and preparation method thereof - Google Patents
A kind of reaction thickening type two component polyurethane glass bonded adhesives and preparation method thereof Download PDFInfo
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- CN110093137A CN110093137A CN201910380195.XA CN201910380195A CN110093137A CN 110093137 A CN110093137 A CN 110093137A CN 201910380195 A CN201910380195 A CN 201910380195A CN 110093137 A CN110093137 A CN 110093137A
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3284—Hydroxyamines containing at least three hydroxy groups containing four hydroxy groups
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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
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols 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
- C08G18/6629—Compounds of groups C08G18/42, 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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- 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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- 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
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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
- C09J175/08—Polyurethanes from polyethers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The present invention relates to bonded adhesives technical fields, and in particular to a kind of reaction thickening type two component polyurethane glass bonded adhesives and preparation method thereof.The preparation method is that 5-20min is mixed in 1:0.8-1.2 with volume ratio by component A and component B, then glass bonded adhesives is made；The component A includes dual-component polyurethane performed polymer 40-75%, polymethylene multi-phenenyl isocyanate 1-15%, reinforced filling A20-40%, catalyst A0.1-2%, adhesion promoters A0.1-2% and deicer 0.1-2%；The component B includes low activity crosslinking agent 30-65%, high activity crosslinking agent 1-10%, reinforced filling B20-40%, plasticizer B10-25%, catalyst B0.1-2% and adhesion promoters B0.1-2%.Preparation Method of the invention is easy to operate, easy to control, and production cost is low, and product quality is high, can be used for being mass produced.
Description
Technical field
The present invention relates to bonded adhesives technical fields, and in particular to a kind of reaction thickening type two component polyurethane glass bonded adhesives
And preparation method thereof.
Background technique
The fast development of auto industry, the quickening of general assembly beat, automobile main frame maker to glass Fast Installation, quickly positioning,
It is low-temperature fast-curing etc. to put forward new requirements.Glass bonding generallys use mono-component polyurethane glass bonded adhesives at present, due to
One-component polyurethane is influenced by temperature and steam, and the curing rate and initial bond strenght of sealant promote limited extent.
For this purpose, two component polyurethane glass bonded adhesives slowly becomes the Main way of research, west card uses Booster system
It is prepared for two component polyurethane glass bonded adhesives, is glued curing agent box using common mono-component polyurethane glass bonding is led to
And short static mixer is generally preheated using colloid and is cooperated electronic strong since mono-component polyurethane glass adhesiveness is higher
The promotion of power glue rifle is glued.
And Chinese patent CN201510086461.X disclose it is a kind of fastly admittedly high-strength bi-component polyurethane adhesive glue and its
Preparation method is made of component A and component B that volume proportion is 1:0.9-1.1, wherein the raw material composition of component A includes double groups
The raw material composition of part base polyurethane prepolymer for use as, ball-shaped silicon micro powder, precipitated calcium carbonate aerosil, component B includes polyethers ternary
Alcohol, two adjacent chlorodiphenyl amine methane, dioctyl phthalate, castor oil, precipitated calcium carbonate, ball-shaped silicon micro powder, self-control dispersing agent,
Carbon black, fumed silica, defoaming agent, silane coupling agent and dibutyl tin dilaurate, but since the two-component glass is bonded
The high thixotroping of glue, high-consistency performance can not solve the problems, such as construction when both mixing difficulty it is big, simultaneously because excessively strengthen shearing
Intensity necessarily causes elongation at break insufficient in the design process, is not suitable for the soft elastic adhesive of vehicle glass.
And common bi-component sebific duct pushes together using bi-component, and long static mixer is cooperated to ensure to mix on head
Uniformly.If A, the viscosity of component B reaches the viscosity for leading to common mono-component polyurethane glass cement, it is difficult to be uniformly mixed, and more
The case where easily there is glue rifle to be difficult to squeeze out construction, or even will appear booster.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of reaction thickening types
The preparation method of two component polyurethane glass bonded adhesives, the preparation method is easy to operate, easy to control, reduces production cost,
Product quality is high, and the dual-component polyurethane performed polymer in component A is reacted with the high activity crosslinking agent in component B, divides in the short time
Sub- amount increases rapidly, and viscosity increases, and keeps glass bonded adhesives sizing completion post Newton obtained longer, can guarantee that glass is pacified
The operating time is filled, reaches main engine plants' technical property requirements after one solidification, can be used for being mass produced.
Another object of the present invention is to provide a kind of reaction thickening type two component polyurethane glass bonded adhesives, the glass is viscous
Meeting the component A and component B of glue, respectively initial viscosity is low, both can make to be easily mixed uniformly, it is ensured that construction feasibility, and after mixing
Viscosity increases rapidly, and gel time is longer, can guarantee that glass installs the operating time, and have the characteristics of quick positioning, bonds
Intensity is high.
The purpose of the invention is achieved by the following technical solution: a kind of reaction thickening type two component polyurethane glass bonded adhesives
Preparation method, by component A and component B with volume ratio be 1:0.8-1.2 5-20min is mixed, then be made glass bonded adhesives.
The present invention is by the way that component A and component B to be mixed with volume ratio for the ratio of 1:0.8-1.2, preparation manipulation letter
It is single, it is easy to control, can the component A and component B of initial viscosity is low (being lower than 500,000 mPas) be uniformly mixed, it is ensured that glass is viscous
The construction Combination of glue is connect, and the bonded adhesives of viscosity higher (not less than 2,000,000 mPas) can be made after stirring 5-20min, is glued
Knotting strength, high tensile shear strength is good, and bonded adhesives obtained can be made to need the oneself viscosity of colloid to support glass in glass bonding
Certain gravity, it is ensured that the thickness of adhesive layer provides buffer function for the vibration of glass.
Preferably, the component A includes the component of following mass percent:
The present invention prepares component A by using the raw material of mentioned kind, component A obtained can be made to have preferably initial viscous
Degree is no more than 500,000 mPas, it is ensured that can be uniformly mixed with component B, guarantee the construction Combination of glass bonded adhesives, and stir 5-
The bonded adhesives of viscosity higher (not less than 2,000,000 mPas) can be made after 20min, adhesion strength, high tensile shear strength is good.Its
In, primary raw material of the dual-component polyurethane performed polymer of use as bonded adhesives, promote under the catalytic crosslinking of catalyst A its with
The cross-linked polymeric of polymethylene multi-phenenyl isocyanate forms stable network structure polymer, and polymethylene polyphenyl is different
- NCO in cyanate strand can form interfacial bond and combine, to glass with a variety of functional group reactions containing active hydrogen
Substrate has extremely strong adhesion property；And the reinforced filling A used can promote the mixing dispersion degree of material, and can improve component
The mechanical performances such as the tensile shear strength of A；And the adhesive accelerant A and the compatibility of other raw materials used is preferable, can improve object
Crosslinking coupling reaction between material controls the initial viscosity of component A less than 500,000 mPas, and keeps it mixed with component B
It is bonded adhesiveness and is not less than 2,000,000 mPas, improve the cohesive force and adhesion strength of sealant and substrate surface；And what is used removes
Aqua can remove the residual moisture in component A, eliminate blistering and the pin-hole phenomena of subsequent bonded adhesives obtained, improve its wearability
And adhesiveness, improve adhesion strength.
Preferably, the component B includes the component of following mass percent:
The present invention prepares component B, and strict control low activity crosslinking agent and high activity by using the raw material of mentioned kind
The mixing dosage of crosslinking agent can make component B obtained have preferable initial viscosity, be no more than 500,000 mPas, it is ensured that can be with
Component B is uniformly mixed, and guarantees the construction Combination of glass bonded adhesives, and can be made that viscosity is higher (to be not less than after stirring 5-20min
2000000 mPas) bonded adhesives, adhesion strength, high tensile shear strength is good；If the dosage of high activity crosslinking agent is excessive, low work
Property crosslinking agent dosage it is very few, component B initial viscosity obtained can be made higher, be not easy to be uniformly mixed with component A, both reduced
Construction degree of mixing；And the reinforced filling B used can promote the mixing dispersion degree of material, and the stretching that can improve component B is cut
The mechanical performances such as shearing stress；And the mobility of the plasticizer B energy polymer molecular chain used, make component B that there is preferable plasticity,
Adhesive obtained has preferable degree of circumnutating and flexibility after mixing it with component A, is easy to be glued, and utilize its degree of circumnutating
Buffer function is provided with flexibility for the vibration of glass；And the adhesive accelerant B and the compatibility of other raw materials used is preferable, energy
The crosslinking coupling reaction between material is improved, controls the initial viscosity of component B less than 500,000 mPas, and keeps it mixed with component A
Bonding adhesiveness after conjunction is not less than 2,000,000 mPas, improves the cohesive force and adhesion strength of sealant and substrate surface；
Preferably, the dual-component polyurethane performed polymer is prepolymer of the NCO content in 4-15%, viscosity 8000-
18000mPa·s；The NCO mass fraction of the polymethylene multi-phenenyl isocyanate is 30.5-32%, and average functionality is
2.5-2.7, viscosity 100-300mPas；The deicer is trimethyl orthoformate, oxazole alkanes deicer and tosyl
At least one of isocyanates.
The NCO content and viscosity and component B that the present invention passes through dual-component polyurethane performed polymer in strict control component A
NCO mass fraction, average functionality and the viscosity of middle polymethylene multi-phenenyl isocyanate, can be such that component A mixes with component B
- NCO after uniformly can form interfacial bond and combine, have to glass baseplate with a variety of functional group reactions containing active hydrogen
Extremely strong adhesion property；And by using the deicer of mentioned kind, the residual moisture in component A can be removed, subsequent system is eliminated
The blistering of the bonded adhesives obtained and pin-hole phenomena improve its wearability and adhesiveness, improve the bonding of bonded adhesives on the glass substrate
Intensity；Wherein, the oxazole alkanes deicer that uses and the degree of functionality with isocyanates indirect reaction is 2, by moisture-sensitive
Oxazolidine decomposition, consume moisture, carry out the moisture in removing system, and dual-component polyurethane performed polymer and more methylenes can be promoted
The cross-linking reaction of Quito phenyl isocyanate；The p-Methyl benzenesulfonyl isocyanate used is monofunctional isocyanates, activity
It is higher, it is preferentially anti-with polyether Glycols, polyether-tribasic alcohol, the moisture in polyisocyanates in dual-component polyurethane performed polymer
It answers, generates carbamate, do not increase the viscosity of system, and then realize the effect of moisture in removing system, and to methylbenzene
During reaction of moisture in sulfonyl isocyanate and system, the carbon dioxide of generation is removed by subsequent vacuum removal bubble
It goes；And the triethyl orthoformate used can be slightly soluble in the moisture in water and decomposing solution, realize the consumption and removal of system moisture.
Preferably, the dual-component polyurethane performed polymer includes the raw material of following mass percent:
Preferably, the dual-component polyurethane performed polymer is made by following steps:
According to weight percent dosage, polyether Glycols, polyether-tribasic alcohol and plasticizer A are added to vacuum reaction device
In, it is dehydrated 2-4h in the case where temperature is 100-120 DEG C of vacuum condition, mixture moisture content≤100ppm is controlled, then cools down
To after 50-85 DEG C, polyisocyanates is added under conditions of nitrogen protection and reacts 1-4h, dual-component polyurethane performed polymer is made.
The present invention prepares dual-component polyurethane performed polymer, polyether Glycols, polyethers three by using the raw material of mentioned kind
First alcohol forms two-component system, and the plasticity of the two is improved by plasticizer A, and in advance by polyether Glycols, polyether-tribasic alcohol
It mixes, and high-temperature vacuum dehydration, can make in polyisocyanates-NCO base and the system of subsequent addition with plasticizer A three
- OH reaction, without in system moisture generate side reaction, improve dual-component polyurethane performed polymer purity and stability.
Preferably, the molecular weight of the polyether Glycols is 1000-4000, and the molecular weight of polyether-tribasic alcohol is 5000-
6000；The polyisocyanates be toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate and
At least one of hexamethylene diisocyanate.
The present invention passes through the molecular weight of strict control polyether Glycols and polyether-tribasic alcohol, and the two can be made to be cross-linked to form stabilization
Dual-component polyurethane performed polymer；And the polyisocyanates type used, activity are high, it can be with polyether Glycols, polyether-tribasic alcohol
Efficiently crosslinking forms the dual-component polyurethane performed polymer of stabilizing network structure.
Preferably, the plasticizer A and plasticizer B be dioctyl phthalate, dibutyl phthalate, oneself two
At least one of dimethyl phthalate and dibutyl adipate.
For the present invention by using the plasticizer of mentioned kind, the compatibility in system is good, and it is poly- to effectively improve two-component
The plasticity of urethane performed polymer and component B improves viscosity, degree of circumnutating and the flexibility of bonding agent obtained, make it easier to sizing in
On glass baseplate, and there is excellent gelling ability, is able to satisfy sizing requirement when installation glass.
Preferably, the component A is made by following steps:
Step (1): according to mass percent meter, by dual-component polyurethane performed polymer, polymethylene multi-phenenyl isocyanate
Mixing, stirs 10-30min under conditions of temperature is 25-45 DEG C, vacuum degree is 0.09 ± 0.005MPa, and pre-composition is made 1.；
Step (2): according to mass percent meter, by reinforced filling A under conditions of temperature is 105-120 DEG C at drying
Reason, is then cooled to 30-50 DEG C, and be added to pre-composition made from step (1) 1. in, 1-2h is mixed, pre-composition is made
②；
Step (3): according to mass percent meter, under the conditions of nitrogen protection, to pre-composition made from step (2) 2. in plus
Enter catalyst A, adhesion promoters A and deicer, stirring 1-1.5h is continuesd to mix under conditions of temperature is 25-45 DEG C, then
Component A is made in discharging, spare.
The present invention is by first mixing dual-component polyurethane performed polymer, polymethylene multi-phenenyl isocyanate, in a vacuum
Reaction can promote the degree of mixing and group cross-linked stable of the two, then add the reinforced filling A being dried and improve body
The dispersion degree of system and the tensile shear strength of component A, and dry reinforced filling A avoids introducing moisture from causing-NCO base and moisture
Side reaction occurs；It is eventually adding the process that catalyst A promotes reaction, the material degree of cross linking of adhesion promoters A regulation component A is added
And initial viscosity, the moisture in deicer removal system is added, avoids moisture and the-NCO of system base that side reaction influence group occurs
Divide the quality of A.
Preferably, the reinforced filling A and reinforced filling B is carbon black, activated Calcium carbonate, powdered whiting, gas phase two
At least one of silica, silicon powder, PVC powder, titanium dioxide and precipitated calcium carbonate；The catalyst A and catalyst B is two
At least one in dibutyl tin laurate, stannous octoate, tin dilaurate dihexyl tin, isooctyl acid bismuth and dimorpholine triethyl group ether
Kind；The adhesion promoters A and adhesion promoters B is γ-methyl-prop monomethacryloxypropyl trimethyl oxysilane, N- phenyl-γ-
In aminopropyl trimethoxysilane, γ-aminopropyltrimethoxysilane and γ-(2,3- glycidyl) propyl trimethoxy silicane
At least one.
For the present invention by using the reinforced filling of mentioned kind, compatibility is good, can promote the dispersing uniformity of material, and energy
The intensity of component A, B and the tensile shear strength of bonded adhesives obtained are improved, makes it easier to be glued；And the catalyst kind used
Class can effectively facilitate the reaction process of each material in component A and component B, improve cross-linked polymeric efficiency, and do not produce to cross-linking process
It is raw to influence, by-product is not generated with material；And the adhesion promoters used, the cross-linking polymerization of promotion system can be made to stablize
Carry out, improve the degree of cross linking of storeroom, and component A can be regulated and controled, the initial viscosity of component B is respectively less than 500,000 mPas, subsequent
Mixing glue during have it is uniformly mixed, will not PhastGel, meet sizing technique requirement.
Preferably, the low activity crosslinking agent be molecular weight in the polyether Glycols of 1800-2200, molecular weight in 4800-
5200 polyether-tribasic alcohol, hydroxyl value the polyester diol of 100-105mgKOH/g, hydroxyl value 160-170mgKOH/g castor-oil plant
At least one of oil polyalcohol；The high activity crosslinking agent is trimethylolpropane, tetrahydroxypropyl ethylenediamine, 1,4- butanediol
At least one of with aspartate；The active hydrogen ratio of the low activity crosslinking agent and high activity crosslinking agent is 1:0.8-
1.2。
The present invention is by using the low activity crosslinking agent of above-mentioned secondary hydroxyl polyethers and the small molecule of primary hydroxyl or amino
High activity crosslinking agent, and the molecular weight and hydroxyl numerical value that strict control low activity crosslinking agent is various types of, with high activity crosslinking agent it
Between there is preferable active hydrogen ratio, cross-linking reaction can be stablized with high activity crosslinking agent, avoid component B obtained subsequent and component
B causes viscosity to increase when mixing too fast or too slow, and gel time is too short or too long, and then the sizing for not being able to satisfy glass installation is wanted
It asks.
Preferably, the component B is made by following steps:
Step 1: according to mass percent meter, by low activity crosslinking agent, high activity crosslinking agent, reinforced filling B and plasticizer B
Mixing, stirs 2-4h under conditions of temperature is 85-95 DEG C, vacuum degree is 0.09 ± 0.005MPa, is cooled to 25-45 DEG C, system
Obtain mixture 1；
Step 2: according to mass percent meter, under the conditions of nitrogen protection, being added and urge into mixture 1 made from step 1
Agent B, adhesion promoters B continues to mix stirring 1-1.5h under conditions of temperature is 25-45 DEG C, then discharge, component is made
B, it is spare；
The present invention, which passes through, first mixes low activity crosslinking agent, high activity crosslinking agent, reinforced filling B and plasticizer B, and in height
It is stirred to react under conditions of temperature, vacuum, both low activity crosslinking agent, high activity crosslinking agent cross-linking reaction, both reinforced filling B's
The lower mixing dispersion degree for promoting storeroom of effect, and plasticizer B can improve the plasticity of system, have component B obtained preferable
Circumnutating property and flexibility, be easy to be glued with the component A bonded adhesives being mixed to prepare.Be eventually adding catalyst B promote reaction into
The material degree of cross linking and initial viscosity of adhesion promoters B regulation component B is added in journey, has component B obtained lower initial
Viscosity is easily mixed uniformly with component A, and the higher bonded adhesives of viscosity formed.
Another object of the present invention is achieved through the following technical solutions: a kind of reaction thickening type two component polyurethane glass is viscous
Glue is connect, the preparation method for reacting thickening type two component polyurethane glass bonded adhesives from the above mentioned is made, the component A and component B
Initial viscosity be ten thousand mPas of 15-50, the viscosity for mixing bonded adhesives after 5-20min is ten thousand mPas of 200-450, when gel
Between be 1-1.5h.
Present invention bonded adhesives as made from above-mentioned processing step and raw material, the initial viscosity of component A and component B therein
Respectively less than 500,000 mPas are easily mixed stirring, can make to be easy to mixed glue during glue, and then can after 5-20min is mixed
The bonded adhesives that viscosity is greater than 2,000,000 mPas is made, it is higher with the cohesive force of glass baseplate, and gel time is suitable for, not because solidifying
The glue time is too fast and causes installation not in time, also not because gel time is excessively slow cause to bond it is unstable.
The beneficial effects of the present invention are: the preparation method of present invention reaction thickening type two component polyurethane glass bonded adhesives
It is easy to operate, it is easy to control, reduce production cost, product quality is high, by by component A and component B with volume ratio for 1:
The ratio of 0.8-1.2 is mixed, and can make the high activity crosslinking agent in the dual-component polyurethane performed polymer and component B in component A
Reaction, molecular weight increases rapidly in the short time, and viscosity increases, make glass bonded adhesives sizing obtained complete post Newton compared with
It is long, it can guarantee that glass is installed the operating time, reach main engine plants' technical property requirements after one solidification, can be used for being mass produced.
Present invention bonded adhesives as made from above-mentioned processing step and raw material, the initial viscosity of component A and component B therein
Respectively less than 500,000 mPas are easily mixed stirring, can make to be easy to mixed glue during glue, and then can after 5-20min is mixed
The bonded adhesives that viscosity is greater than 2,000,000 mPas is made, it is higher with the cohesive force of glass baseplate, and gel time is suitable for, not because solidifying
The glue time is too fast and causes installation not in time, does not also cause to bond unstable because gel time is excessively slow, can guarantee glass
Be installed, the gravity for needing the oneself viscosity of colloid to support glass certain in glass bonding, it is ensured that adhesive layer operating time
Thickness provides buffer function for the vibration of glass, can be used for being mass produced.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, comprising the following steps:
Step 1: prepare two component polyurethane bonded adhesives performed polymer: by 100g molecular weight be 2000 polyether Glycols,
The polyether-tribasic alcohol and 100g dioctyl phthalate that 260g molecular weight is 5000 are added in vacuum reaction device, 120
It is dehydrated 4h under the conditions of DEG C Temperature Vacuum, mixture moisture content≤100ppm is controlled, after being then cooled to 85 DEG C, in nitrogen protection
Under the conditions of be added 70g diphenylmethane diisocyanate react 4h, be made dual-component polyurethane performed polymer.
Step 2: preparation component A: by dual-component polyurethane performed polymer made from 424g step 1, the more benzene of 95g polymethylene
Based isocyanate is added in reaction unit, stirs under conditions of temperature is 45 DEG C, vacuum degree is 0.09 ± 0.005MPa
Pre-composition is made 1. in 30min；The item for being again 120 DEG C in temperature by 120g carbon black, 120g activated Calcium carbonate, 38g powdered whiting
Be dried under part, be then cooled to 45 DEG C, and be added to pre-composition 1. in, 2h is mixed, pre-composition is made 2.；In nitrogen
Under protective condition, to pre-composition 2. in be added 2.4g isooctyl acid bismuth, 2.4g N- phenyl-γ-aminopropyltrimethoxysilane and
2.4g oxazole alkanes deicer discharges after continueing to mix stirring 1h under the conditions of temperature is 45 DEG C, and component A is made, spare.
Step 3: preparation component B: polyether-tribasic alcohol, 72g castor oil polyhydric alcohol, 64g that 264g molecular weight is 5000 are gathered
The 1,4- butanediol addition reaction of ester dihydric alcohol, 120g carbon black, 64g activated Calcium carbonate, 168g dioctyl phthalate, 24g
In device, after stirring 4h under conditions of temperature is 95 DEG C, vacuum degree is 0.09 ± 0.005MPa, 45 DEG C are cooled to, is made mixed
Close material 1；Under the conditions of nitrogen protection, 2.4g isooctyl acid bismuth, 2.4gN- phenyl-γ-aminopropyl trimethoxy are added into mixture 1
Base silane discharges after continueing to mix stirring 1.5h under conditions of temperature is 45 DEG C, and component B is made, spare.
Step 4: preparation reaction thickening type two component polyurethane glass bonded adhesives: by component A and step made from step 2
Component B made from three is that 20min is mixed in 1:1.0 with volume ratio, then reacts thickening type two component polyurethane glass bonded adhesives.
Embodiment 2
A kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, comprising the following steps:
Step 1: prepare two component polyurethane bonded adhesives performed polymer: by 120g molecular weight be 2000 polyether Glycols,
The polyether-tribasic alcohol and 110g dioctyl phthalate that 270g molecular weight is 5000 are added in vacuum reaction device, 120
It is dehydrated 4h under the conditions of DEG C Temperature Vacuum, mixture moisture content≤100ppm is controlled, after being then cooled to 85 DEG C, in nitrogen protection
Under the conditions of be added 70g diphenylmethane diisocyanate react 4h, be made dual-component polyurethane performed polymer.
Step 2: preparation component A: by dual-component polyurethane performed polymer made from 488g step 1, the more benzene of 56g polymethylene
Based isocyanate is added in reaction unit, stirs under conditions of temperature is 45 DEG C, vacuum degree is 0.09 ± 0.005MPa
Pre-composition is made 1. in 30min；The item for being again 120 DEG C in temperature by 130g carbon black, 110g activated Calcium carbonate, 56g powdered whiting
Be dried under part, be then cooled to 45 DEG C, and be added to pre-composition 1. in, 2h is mixed, pre-composition is made 2.；In nitrogen
Under protective condition, to pre-composition 2. in be added 2.4g isooctyl acid bismuth, 2.4gN- phenyl-γ-aminopropyltrimethoxysilane and
2.4g oxazole alkanes deicer discharges after continueing to mix stirring 1h under the conditions of temperature is 45 DEG C, and component A is made, spare.
Step 3: preparation component B: polyether-tribasic alcohol, 72g castor oil polyhydric alcohol, 64g that 328g molecular weight is 5000 are gathered
Ester dihydric alcohol, 120g carbon black, 64g activated Calcium carbonate, 120g dioctyl phthalate, 24g trimethylolpropane alcohol are added anti-
It answers in device, after stirring 4h under conditions of temperature is 95 DEG C, vacuum degree is 0.09 ± 0.005MPa, is cooled to 45 DEG C, be made
Mixture 1；Under the conditions of nitrogen protection, 2.4g isooctyl acid bismuth, 2.4gN- phenyl-γ-aminopropyl front three are added into mixture 1
Oxysilane discharges after continueing to mix stirring 1.5h under conditions of temperature is 45 DEG C, and component B is made, spare.
Step 4: preparation reaction thickening type two component polyurethane glass bonded adhesives: by component A and step made from step 2
Component B made from three is that 20min is mixed in 1:1.0 with volume ratio, then reacts thickening type two component polyurethane glass bonded adhesives.
Embodiment 3
A kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, comprising the following steps:
Step 1: prepare two component polyurethane bonded adhesives performed polymer: by 100g molecular weight be 2000 polyether Glycols,
The polyether-tribasic alcohol and 110g dioctyl phthalate that 260g molecular weight is 5000 are added in vacuum reaction device, 120
It is dehydrated 4h under the conditions of DEG C Temperature Vacuum, mixture moisture content≤100ppm is controlled, after being then cooled to 85 DEG C, in nitrogen protection
Under the conditions of be added 70g diphenylmethane diisocyanate react 4h, be made dual-component polyurethane performed polymer.
Step 2: preparation component A: dual-component polyurethane performed polymer made from 442g step 1,118g polymethylene is more
Phenyl isocyanate is added in reaction unit, stirs under conditions of temperature is 45 DEG C, vacuum degree is 0.09 ± 0.005MPa
Pre-composition is made 1. in 30min；112g carbon black, 128g activated Calcium carbonate are dried under conditions of temperature is 120 DEG C again,
Then be cooled to 45 DEG C, and be added to pre-composition 1. in, 2h is mixed, pre-composition is made 2.；Under the conditions of nitrogen protection, to
Pre-composition is 2. middle to be added 2.4g isooctyl acid bismuth, 2.4gN- phenyl-γ-aminopropyltrimethoxysilane and the water removal of 2.4g oxazole alkanes
Agent discharges after continueing to mix stirring 1h under the conditions of temperature is 45 DEG C, and component A is made, spare.
Step 3: preparation component B: polyether-tribasic alcohol, 72g castor oil polyhydric alcohol, 64g that 328g molecular weight is 5000 are gathered
Ester dihydric alcohol, 110g carbon black, 74g activated Calcium carbonate, 120g dioctyl phthalate, 32g tetrahydroxypropyl ethylenediamine are added anti-
It answers in device, after stirring 4h under conditions of temperature is 95 DEG C, vacuum degree is 0.09 ± 0.005MPa, is cooled to 45 DEG C, be made
Mixture 1；Under the conditions of nitrogen protection, 2.4g isooctyl acid bismuth, 2.4gN- phenyl-γ-aminopropyl front three are added into mixture 1
Oxysilane discharges after continueing to mix stirring 1.5h under conditions of temperature is 45 DEG C, and component B is made, spare.
Step 4: preparation reaction thickening type two component polyurethane glass bonded adhesives: by component A and step made from step 2
Component B made from three is that 20min is mixed in 1:1.0 with volume ratio, then reacts thickening type two component polyurethane glass bonded adhesives.
Embodiment 4
A kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, comprising the following steps:
Step 1: prepare two component polyurethane bonded adhesives performed polymer: by 120g molecular weight be 2000 polyether Glycols,
The polyether-tribasic alcohol and 110g dibutyl phthalate that 270g molecular weight is 5000 are added in vacuum reaction device, 120
It is dehydrated 4h under the conditions of DEG C Temperature Vacuum, mixture moisture content≤100ppm is controlled, after being then cooled to 85 DEG C, in nitrogen protection
Under the conditions of be added 70g toluene di-isocyanate(TDI) react 4h, be made dual-component polyurethane performed polymer.
Step 2: preparation component A: by dual-component polyurethane performed polymer made from 464g step 1, the more benzene of 56g polymethylene
Based isocyanate is added in reaction unit, stirs under conditions of temperature is 45 DEG C, vacuum degree is 0.09 ± 0.005MPa
Pre-composition is made 1. in 30min；Again by 100g carbon black, 120g activated Calcium carbonate, 16g fumed silica, 44g powdered whiting
Be dried under conditions of temperature is 120 DEG C, be then cooled to 45 DEG C, and be added to pre-composition 1. in, 2h, system is mixed
Obtain pre-composition 2.；Under the conditions of nitrogen protection, 2.4g isooctyl acid bismuth, 2.4gN- phenyl-γ-aminopropyl is added to pre-composition is 2. middle
Trimethoxy silane and 2.4g oxazole alkanes deicer discharge after continueing to mix stirring 1h under the conditions of temperature is 45 DEG C, are made
Component A, it is spare.
Step 3: preparation component B: polyether-tribasic alcohol, 72g castor oil polyhydric alcohol, 64g that 264g molecular weight is 5000 are gathered
Ester dihydric alcohol, 120g carbon black, 84g activated Calcium carbonate, 84g dioctyl phthalate, 48g39g tetrahydroxypropyl ethylenediamine add
Enter in reaction unit, after stirring 4h under conditions of temperature is 95 DEG C, vacuum degree is 0.09 ± 0.005MPa, be cooled to 45 DEG C,
Mixture 1 is made；Under the conditions of nitrogen protection, 2.4g isooctyl acid bismuth, 2.4gN- phenyl-γ-aminopropyl are added into mixture 1
Trimethoxy silane discharges after continueing to mix stirring 1.5h under conditions of temperature is 45 DEG C, and component B is made, spare.
Step 4: preparation reaction thickening type two component polyurethane glass bonded adhesives: by component A and step made from step 2
Component B made from three is that 20min is mixed in 1:1.0 with volume ratio, then reacts thickening type two component polyurethane glass bonded adhesives.
Embodiment 5
A kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, comprising the following steps:
Step 1: prepare two component polyurethane bonded adhesives performed polymer: by 85.5g molecular weight be 4000 polyether Glycols,
The polyether-tribasic alcohol and 171g dimethyl adipate that 285g molecular weight is 5000 are added in vacuum reaction device, in 110 DEG C of temperature
It is dehydrated 2h under degree vacuum condition, mixture moisture content≤100ppm is controlled, after being then cooled to 68 DEG C, in nitrogen protection condition
The lower isophorone diisocyanate that 28.5g is added reacts 3h, and dual-component polyurethane performed polymer is made.
Step 2: preparation component A: by dual-component polyurethane performed polymer made from 322g step 1,120.75g polymethylene
More phenyl isocyanates are added in reaction unit, stir under conditions of temperature is 35 DEG C, vacuum degree is 0.09 ± 0.005MPa
Pre-composition is made 1. in 20min；It is again 112 DEG C in temperature by 112g silicon powder, 128g activated Calcium carbonate, 73.95g titanium dioxide
Under the conditions of be dried, be then cooled to 50 DEG C, and be added to pre-composition 1. in, 2h is mixed, pre-composition is made 2.；In nitrogen
Under the conditions of gas shielded, 16.1g dibutyl tin dilaurate, 16.1g γ-methyl-prop monomethacryloxypropyl front three is added to pre-composition is 2. middle
Base oxysilane and 16.1g trimethyl orthoformate discharge after continueing to mix stirring 1.25h under the conditions of temperature is 35 DEG C, are made
Component A, it is spare.
Step 3: preparation component B: by 50g molecular weight be 1800 polyether Glycols, 80g molecular weight be 5200 polyethers
Polyester diol that castor oil polyhydric alcohol that trihydroxylic alcohol, 52g hydroxyl value are 160mgKOH/g, 52g hydroxyl value are 105mgKOH/g, 120g
Powdered whiting, 86g fumed silica, 106g silicon powder, 75g dibutyl phthalate, 49.8g dimethyl adipate,
78g tetrahydroxypropyl ethylenediamine is added in reaction unit, stirs under conditions of temperature is 90 DEG C, vacuum degree is 0.09 ± 0.005MPa
After mixing 2h, 35 DEG C are cooled to, mixture 1 is made；Under the conditions of nitrogen protection, into mixture 1 be added 15.6g stannous octoate,
15.6g γ-(2,3- glycidyl) propyl trimethoxy silicane goes out after continueing to mix stirring 1h under conditions of temperature is 45 DEG C
Component B is made in material, spare.
Step 4: preparation reaction thickening type two component polyurethane glass bonded adhesives: by component A and step made from step 2
Component B made from three is that 20min is mixed in 1:0.8 with volume ratio, then reacts thickening type two component polyurethane glass bonded adhesives.
Embodiment 6
A kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, comprising the following steps:
Step 1: prepare two component polyurethane bonded adhesives performed polymer: by 171g molecular weight be 1000 polyether Glycols,
The polyether-tribasic alcohol and 142.5g dibutyl adipate that 171g molecular weight is 6000 are added in vacuum reaction device, at 100 DEG C
It is dehydrated 3h under the conditions of Temperature Vacuum, mixture moisture content≤100ppm is controlled, after being then cooled to 50 DEG C, in nitrogen protection item
The hexamethylene diisocyanate that 85.5g is added under part reacts 1h, and dual-component polyurethane performed polymer is made.
Step 2: preparation component A: by the more methylenes of dual-component polyurethane performed polymer, 37.84g made from 603.75g step 1
Quito phenyl isocyanate is added in reaction unit, stirs under conditions of temperature is 25 DEG C, vacuum degree is 0.09 ± 0.005MPa
10min is mixed, pre-composition is made 1.；It is again 105 DEG C in temperature by 82g fumed silica, 56g precipitated calcium carbonate, 23gPVC powder
Under conditions of be dried, be then cooled to 30 DEG C, and be added to pre-composition 1. in, 1.5h is mixed, pre-composition is made 2.；
Under the conditions of nitrogen protection, 0.805g tin dilaurate dihexyl tin, 0.805gN- phenyl-γ-ammonia third is added to pre-composition is 2. middle
Base trimethoxy silane and 0.805g tosyl isocyanates go out after continueing to mix stirring 1.5h under the conditions of temperature is 15 DEG C
Component A is made in material, spare.
Step 3: preparation component B: by 121g molecular weight be 2200 polyether Glycols, 228g molecular weight be 4800 it is poly-
Ether trihydroxylic alcohol, 86g hydroxyl value be the castor oil polyhydric alcohol of 170mgKOH/g, 74g hydroxyl value 100mgKOH/g polyester diol, 86
Precipitated calcium carbonate, 28gPVC powder, 42g titanium dioxide, 77.64g dioctyl phthalate, 30g dibutyl adipate, the Tianmen 7.8g
Aspartic acid ester is added in reaction unit, after stirring 3h under conditions of temperature is 85 DEG C, vacuum degree is 0.09 ± 0.005MPa, drop
Mixture 1 is made to 25 DEG C in temperature；Under the conditions of nitrogen protection, into mixture 1 be added 0.78g dimorpholine triethyl group ether,
0.78g γ-aminopropyltrimethoxysilane discharges after continueing to mix stirring 1.25h under conditions of temperature is 25 DEG C, group is made
Divide B, it is spare.
Step 4: preparation reaction thickening type two component polyurethane glass bonded adhesives: by component A and step made from step 2
Component B made from three is that 5min is mixed in 1:1.2 with volume ratio, then reacts thickening type two component polyurethane glass bonded adhesives.
Comparative example 1
A kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, comprising the following steps:
Step 1: it prepares two component polyurethane bonded adhesives performed polymer: being 2000 polyether Glycols, 260g by 100g molecular weight
The dioctyl phthalate of polyether-tribasic alcohol, 110g that molecular weight is 5000 is added in vacuum reaction device, in 120 DEG C of temperature
It is dehydrated 4h under degree vacuum condition, mixture moisture content≤100ppm is controlled, after being then cooled to 85 DEG C, in nitrogen protection condition
The lower diphenylmethane diisocyanate that 70g is added reacts 4h, obtains two component polyurethane bonded adhesives performed polymer.
Step 2: preparation component A: by two component polyurethane bonded adhesives performed polymer made from 562g step 1, the more methylenes of 72g
Quito phenyl isocyanate is added in reaction kettle, stirs under conditions of temperature is 45 DEG C, vacuum degree is 0.09 ± 0.005MPa
Pre-composition is made 1. in 30min；The item for being again 120 DEG C in temperature by 124g carbon black, 112g activated Calcium carbonate, 30g powdered whiting
It is dried under part, is then cooled to 45 DEG C, and be added to pre-composition is 1. middle and 2h is mixed, pre-composition is made 2.；In nitrogen
2.4g isooctyl acid bismuth, 2.4gN- phenyl-γ-aminopropyltrimethoxysilane and 2.4g is added to pre-composition is 2. middle under protective condition
Oxazole alkanes deicer discharges after continueing to mix stirring 1h under conditions of temperature is 45 DEG C, and component A is made, spare.
Step 3: preparation component B: by 48g molecular weight be 2000 polyether Glycols, 270g molecular weight be 5000 polyethers
Trihydroxylic alcohol, 72g castor oil polyhydric alcohol, 64g polyester diol, 126g carbon black, 48g activated Calcium carbonate, 122g phthalic acid two
Monooctyl ester, 14g1,4- butanediol is added in reaction unit, under conditions of temperature is 95 DEG C, vacuum degree is 0.09 ± 0.005MPa
4h is stirred, is then cooled to 45 DEG C, mixture 1 is made；2.4g isooctyl acid bismuth, 2.4g N- benzene are added under the conditions of nitrogen protection
Base-γ-aminopropyltrimethoxysilane discharges after continueing to mix stirring 1.5h under conditions of temperature is 45 DEG C, component is made
B, it is spare.
Step 4: preparation reaction thickening type two component polyurethane glass bonded adhesives: by component A and step made from step 2
Component B made from three is that 20min is mixed in 1:1 with volume ratio, then reacts thickening type two component polyurethane glass bonded adhesives.
Comparative example 2
A kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, comprising the following steps:
Step 1: prepare two component polyurethane bonded adhesives performed polymer: by 100g molecular weight be 2000 polyether Glycols,
260g molecular weight be 5000 polyether-tribasic alcohol, 110g dioctyl phthalate be added in vacuum reaction device, in temperature
To be dehydrated 4h under 120 DEG C of vacuum conditions, mixture moisture content≤100ppm is controlled, is then cooled to 85 DEG C, is protected in nitrogen
The diphenylmethane diisocyanate that 70g is added under the conditions of shield reacts 4h, and dual-component polyurethane performed polymer is made.
Step 2: preparation component A: by dual-component polyurethane performed polymer made from 548g step 1, the more benzene of 56g polymethylene
Based isocyanate is added in reaction unit, stirs under conditions of temperature is 45 DEG C, vacuum degree is 0.09 ± 0.005MPa
Pre-composition is made 1. in 30min；The item for being again 120 DEG C in temperature by 120g carbon black, 130g activated Calcium carbonate, 46g powdered whiting
It is dried under part, is then cooled to 45 DEG C, and be added to pre-composition is 1. middle and 2h is mixed, pre-composition is made 2.；In nitrogen
Under protective condition to pre-composition 2. in be added 2.4g isooctyl acid bismuth, 2.4g N- phenyl-γ-aminopropyltrimethoxysilane and
2.4g oxazole alkanes deicer discharges after continueing to mix stirring 1h under conditions of temperature is 45 DEG C, and component A is made, spare.
Step 3: preparation component B: polyether-tribasic alcohol, 72g castor oil polyhydric alcohol, 64g that 270g molecular weight is 5000 are gathered
Ester dihydric alcohol, 126g carbon black, 48g activated Calcium carbonate, 122g dioctyl phthalate, 85g tetrahydroxypropyl ethylenediamine are added anti-
It answers in device, after stirring 4h under conditions of temperature is 95 DEG C, vacuum degree is 0.09 ± 0.005MPa, is cooled to 45 DEG C, be made
Mixture 1；Under the conditions of nitrogen protection, 2.4g isooctyl acid bismuth, 2.4g N- phenyl-γ-aminopropyl three are added into mixture 1
Methoxy silane discharges after continueing to mix stirring 1.5h under conditions of temperature is 45 DEG C, and component B is made, spare.
Step 4: preparation reaction thickening type two component polyurethane glass bonded adhesives: by component A and step made from step 2
Component B made from three is that 20min is mixed in 1:1 with volume ratio, then reacts thickening type two component polyurethane glass bonded adhesives.
Will made from embodiment 1-6 and comparative example 1-2 reaction thickening type two component polyurethane glass bonded adhesives carry out viscosity,
The performance tests such as gel time, tensile shear strength, removing cementability, and following test method is used, and test result is seen below
Table:
1. reacting the viscosity test of thickening type two component polyurethane glass bonded adhesives:
Glue is filled up into flow cup, according to GB/T 2794-1995 " measurement of adhesive viscosity " tested viscosity, is tested respectively
The viscosity of 15min after component A, the respective initial viscosity of component B, mixing, and record test result.
2, the gel time test of thickening type two component polyurethane glass bonded adhesives is reacted:
After component A and component B are mixed in proportion, with standard type gel time tester, rotor rotates in glue, when out
Torque is excessive when existing gelatin phenomenon, stops working, and the record time is gel time.
3. reacting thickening type two component polyurethane glass bonded adhesives to test the removing cementability of black surround glass:
It after component A and component B are mixed in proportion, imposes on the black surround glass of wiped clean, makes a call to 3 adhesive tape, colloid is wide
About 5mm, thickness about 3mm are spent, is tested and is shelled according to HG/T 4363-2012 " automobile window glass one-component polyurethane adhesive "
From cementability, every other day observation is primary, records test result.
4. reacting the tensile shear strength test of thickening type two component polyurethane glass bonded adhesives:
After component A and component B are mixed in proportion, the shearing sample with a thickness of 4.0mm is made, according to GB/T 7124-
2008 " adhesive tensile shear strength measuring methods " test tensile shear strength, and tensile speed 20mm/min is conserved respectively
It is tested after 0.5h, 168h, and records test result.
The test result of above-mentioned performance test methods see the table below:
Table data as above it is found that embodiment 1-6 and comparative example 1-2, the initial viscosity before mixing be able to satisfy construction requirement,
Cementability is removed, and 168h shear strength is also able to satisfy the application performance requirement of glass bonded adhesives.
And wherein, the comparative example 2 of low activity crosslinking agent and high activity crosslinking agent active hydrogen ratio less than 1:0.8, component A
Increase that too fast, gel time is too short with the mixed viscosity of component B, is not able to satisfy the time requirement of glass installation；And comparative example 1
Active hydrogen ratio be greater than 1:1.2, gel time is too long, be not able to satisfy glass installation quickly require.
Thus, the present invention passes through the low activity crosslinking agent and high activity crosslinking agent active hydrogen ratio in strict control component B
Between 1:0.8-1.2, bodying speed and gel time can meet requirement.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives, it is characterised in that: by component A and component
B is that 5-20min is mixed in 1:0.8-1.2 with volume ratio, then glass bonded adhesives is made；
The component A includes the component of following mass percent:
The component B includes the component of following mass percent:
2. a kind of preparation method for reacting thickening type two component polyurethane glass bonded adhesives according to claim 1, special
Sign is: the dual-component polyurethane performed polymer is prepolymer of the NCO content in 4-15%, viscosity 8000-18000mPa
s；The NCO mass fraction of the polymethylene multi-phenenyl isocyanate is 30.5-32%, average functionality 2.5-2.7, viscosity
For 100-300mPas；The deicer is in trimethyl orthoformate, oxazole alkanes deicer and tosyl isocyanates
It is at least one；The dual-component polyurethane performed polymer includes the raw material of following mass percent:
3. a kind of reaction thickening type two component polyurethane glass bonded adhesives according to claim 2, it is characterised in that: described
Dual-component polyurethane performed polymer is made by following steps:
According to weight percent dosage, polyether Glycols, polyether-tribasic alcohol and plasticizer A are added in vacuum reaction device,
It is dehydrated 2-4h in the case where temperature is 100-120 DEG C of vacuum condition, mixture moisture content≤100ppm is controlled, is then cooled to
After 50-85 DEG C, polyisocyanates is added under conditions of nitrogen protection and reacts 1-4h, dual-component polyurethane performed polymer is made.
4. a kind of reaction thickening type two component polyurethane glass bonded adhesives according to claim 2, it is characterised in that: described
The molecular weight of polyether Glycols is 1000-4000, and the molecular weight of polyether-tribasic alcohol is 5000-6000；The polyisocyanates is
In toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate
At least one.
5. a kind of reaction thickening type two component polyurethane glass bonded adhesives according to claim 2, it is characterised in that: described
Plasticizer A and plasticizer B are dioctyl phthalate, dibutyl phthalate, dimethyl adipate and adipic acid two
At least one of butyl ester.
6. a kind of reaction thickening type two component polyurethane glass bonded adhesives according to claim 1, it is characterised in that: described
Component A is made by following steps:
Step (1): according to mass percent meter, dual-component polyurethane performed polymer, polymethylene multi-phenenyl isocyanate being mixed,
10-30min is stirred under conditions of temperature is 25-45 DEG C, vacuum degree is 0.09 ± 0.005MPa, pre-composition is made 1.；
Step (2): according to mass percent meter, reinforced filling A is dried under conditions of temperature is 105-120 DEG C, so
After be cooled to 30-50 DEG C, and be added to pre-composition made from step (1) 1. in, 1-2h is mixed, pre-composition is made 2.；
Step (3): according to mass percent meter, under the conditions of nitrogen protection, to pre-composition made from step (2), 2. middle be added is urged
Agent A, adhesion promoters A and deicer continues to mix stirring 1-1.5h under conditions of temperature is 25-45 DEG C, then discharge,
Component A is made, it is spare.
7. a kind of reaction thickening type two component polyurethane glass bonded adhesives according to claim 1, it is characterised in that: described
Reinforced filling A and reinforced filling B be carbon black, activated Calcium carbonate, powdered whiting, fumed silica, silicon powder, PVC powder,
At least one of titanium dioxide and precipitated calcium carbonate；The catalyst A and catalyst B is dibutyl tin dilaurate, octanoic acid
At least one of stannous, tin dilaurate dihexyl tin, isooctyl acid bismuth and dimorpholine triethyl group ether；The adhesion promoters A and
Adhesion promoters B be γ-methyl-prop monomethacryloxypropyl trimethyl oxysilane, N- phenyl-γ-aminopropyltrimethoxysilane,
At least one of γ-aminopropyltrimethoxysilane and γ-(2,3- glycidyl) propyl trimethoxy silicane.
8. a kind of reaction thickening type two component polyurethane glass bonded adhesives according to claim 1, it is characterised in that: described
Low activity crosslinking agent is polyether Glycols, molecular weight polyether-tribasic alcohol, hydroxyl in 4800-5200 of the molecular weight in 1800-2200
Be worth 100-105mgKOH/g polyester diol, hydroxyl value in the castor oil polyhydric alcohol of 160-170mgKOH/g at least one
Kind；The high activity crosslinking agent is in trimethylolpropane, tetrahydroxypropyl ethylenediamine, 1,4- butanediol and aspartate
It is at least one；The active hydrogen ratio of the low activity crosslinking agent and high activity crosslinking agent is 1:0.8-1.2.
9. a kind of reaction thickening type two component polyurethane glass bonded adhesives according to claim 1, it is characterised in that: described
Component B is made by following steps:
Step 1: according to mass percent meter, low activity crosslinking agent, high activity crosslinking agent, reinforced filling B and plasticizer B being mixed
It closes, stirs 2-4h under conditions of temperature is 85-95 DEG C, vacuum degree is 0.09 ± 0.005MPa, be cooled to 25-45 DEG C, be made
Mixture 1；
Step 2: according to mass percent meter, under the conditions of nitrogen protection, catalyst is added into mixture 1 made from step 1
B, adhesion promoters B continuess to mix stirring 1-1.5h under conditions of temperature is 25-45 DEG C, then discharges, and component B is made, standby
With.
10. a kind of reaction thickening type two component polyurethane glass bonded adhesives, it is characterised in that: by any one of claim 1-9 institute
The preparation method for stating reaction thickening type two component polyurethane glass bonded adhesives is made, and the initial viscosity of the component A and component B are equal
For ten thousand mPas of 15-50, the viscosity for mixing bonded adhesives after 5-20min is ten thousand mPas of 200-450, gel time 1-1.5h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647125A (en) * | 2020-06-15 | 2020-09-11 | 浙江华峰新材料有限公司 | Polyurethane composition and preparation of sponge product thereof |
| CN112552863A (en) * | 2020-12-03 | 2021-03-26 | 上海回天新材料有限公司 | Solvent-free bi-component polyurethane adhesive for structural bonding and application |
| EP3819321A1 (en) * | 2019-11-07 | 2021-05-12 | Bostik Sa | Two-component adhesive composition |
| CN113372868A (en) * | 2021-05-20 | 2021-09-10 | 武汉长盈鑫科技有限公司 | Ultraviolet activated double-component super-hydrophobic polyurethane ring winding adhesive |
| CN114133906A (en) * | 2021-12-31 | 2022-03-04 | 广州市盛邦康体场地材料有限公司 | Adhesive for bonding prefabricated rubber track |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174171A (en) * | 2011-01-12 | 2011-09-07 | 厦门誉匠复合材料有限公司 | Bubble-free yellowing resistant polyurethane electronic potting adhesive composition and preparation method thereof |
| CN102212326A (en) * | 2011-05-10 | 2011-10-12 | 东莞市普赛达密封粘胶有限公司 | Bi-component polyurethane adhesive as well as preparation method and application thereof |
| WO2018013222A1 (en) * | 2016-07-11 | 2018-01-18 | Dow Global Technologies Llc | Two-component adhesive compositions and methods of making same |
| CN108559440A (en) * | 2018-04-27 | 2018-09-21 | 上海回天新材料有限公司 | A kind of no-solvent type polyurethane laminating adhesive and its preparation method and application of high speed compound, rapid aging |
-
2019
- 2019-05-08 CN CN201910380195.XA patent/CN110093137A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174171A (en) * | 2011-01-12 | 2011-09-07 | 厦门誉匠复合材料有限公司 | Bubble-free yellowing resistant polyurethane electronic potting adhesive composition and preparation method thereof |
| CN102212326A (en) * | 2011-05-10 | 2011-10-12 | 东莞市普赛达密封粘胶有限公司 | Bi-component polyurethane adhesive as well as preparation method and application thereof |
| WO2018013222A1 (en) * | 2016-07-11 | 2018-01-18 | Dow Global Technologies Llc | Two-component adhesive compositions and methods of making same |
| CN108559440A (en) * | 2018-04-27 | 2018-09-21 | 上海回天新材料有限公司 | A kind of no-solvent type polyurethane laminating adhesive and its preparation method and application of high speed compound, rapid aging |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3819321A1 (en) * | 2019-11-07 | 2021-05-12 | Bostik Sa | Two-component adhesive composition |
| WO2021089709A1 (en) * | 2019-11-07 | 2021-05-14 | Bostik Sa | Two-component adhesive composition |
| CN114729093A (en) * | 2019-11-07 | 2022-07-08 | 波士胶公司 | Two-component adhesive composition |
| CN114729093B (en) * | 2019-11-07 | 2024-04-02 | 波士胶公司 | Two-component adhesive composition |
| CN111647125A (en) * | 2020-06-15 | 2020-09-11 | 浙江华峰新材料有限公司 | Polyurethane composition and preparation of sponge product thereof |
| CN111647125B (en) * | 2020-06-15 | 2022-04-05 | 浙江华峰新材料有限公司 | Polyurethane composition and preparation of sponge product thereof |
| CN112552863A (en) * | 2020-12-03 | 2021-03-26 | 上海回天新材料有限公司 | Solvent-free bi-component polyurethane adhesive for structural bonding and application |
| CN115232286A (en) * | 2021-04-22 | 2022-10-25 | 深圳市优妮家新材料有限公司 | Bio-based aliphatic polyurethane composition and preparation method and application thereof |
| CN115232286B (en) * | 2021-04-22 | 2023-09-26 | 深圳市优妮家新材料有限公司 | Bio-based aliphatic polyurethane composition and preparation method and application thereof |
| CN113372868A (en) * | 2021-05-20 | 2021-09-10 | 武汉长盈鑫科技有限公司 | Ultraviolet activated double-component super-hydrophobic polyurethane ring winding adhesive |
| CN114133906A (en) * | 2021-12-31 | 2022-03-04 | 广州市盛邦康体场地材料有限公司 | Adhesive for bonding prefabricated rubber track |
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