CN111234764B - Polyurethane corner-combining adhesive with high bonding strength and preparation method thereof - Google Patents
Polyurethane corner-combining adhesive with high bonding strength and preparation method thereof Download PDFInfo
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- CN111234764B CN111234764B CN202010151819.3A CN202010151819A CN111234764B CN 111234764 B CN111234764 B CN 111234764B CN 202010151819 A CN202010151819 A CN 202010151819A CN 111234764 B CN111234764 B CN 111234764B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- 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
- C08G18/40—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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- 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
- 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
Abstract
The invention provides a polyurethane corner adhesive with high bonding strength and a preparation method thereof, wherein the polyurethane corner adhesive comprises the following components in parts by weight: 60-90 parts of polyurethane prepolymer, 4-10 parts of plasticizer, 0-20 parts of filler, 0.01-1 part of catalyst, 0.5-3 parts of defoaming agent and 3-10 parts of modified hydrophilic white carbon black; the polyurethane prepolymer is prepared by reacting isocyanate, bifunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol in a mass ratio of 30-50: 3-10: 30-60; the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100. The angle glue has high bonding strength; and the stability is better. The angle glue can improve the structural bonding strength of the angle position of the wooden door and window; the bonding strength of the corner combining position of the aluminum alloy door and window can be greatly improved.
Description
Technical Field
The invention belongs to the technical field of bonding and sealing, and particularly relates to a polyurethane corner-forming adhesive with high bonding strength and a preparation method thereof.
Background
The corner-combining glue is introduced from Europe at the earliest time, and a large number of domestic corner-combining glue products are developed for the performance of standard foreign products at present. However, the market conditions of domestic and foreign doors and windows are huge, the wood door and window structure is mainly used abroad, the aluminum alloy door and window and the aluminum-plastic composite door and window are mainly used domestically, and the quantity of the wood door and window is relatively small. When the corner-combining glue product is used in Europe, the basic performance is detected according to the requirements of EN204 Classification for non-structural application thermoplastic wood adhesive, and the detection content is mainly to test the shear strength of the adhesive under various treatment conditions according to EN205 tensile shear strength test method of adhesive-non-structural application wood adhesive-lap joint. The overlapping substrate of EN205 was beech board with a thickness of 5.0mm, which was penetrated by the glue pack during the test, and therefore had a tensile shear strength of > 10 MPa. Because of the huge number of aluminum alloy doors and windows in China, the surface anodized aluminum sheet is used for tensile shear testing in the standard requirements of the corner adhesive industry, so that the requirement of the normal-temperature shear strength is only more than 3 MPa.
The change of the base material causes the data of the bonding performance of the imported single-component corner adhesive to be low, the shear strength at normal temperature after complete curing is only 3-4 MPa, and is far lower than the standard value in the wood section bar which is more than 10MPa, so that the change of the section bar can cause the applicability of the imported single-component corner adhesive to be reduced, and corresponding use risks are brought. Therefore, in order to improve the bonding strength of the corner of the aluminum door/window, a single-component corner assembly adhesive product with high bonding strength to an aluminum profile may need to be specially developed.
The gas-phase white carbon black is the most commonly used reinforcing filler for polyurethane glue, wherein the hydrophobic white carbon black has good thixotropy and better stability in a polyurethane system, so the hydrophobic white carbon black is widely applied. Compared with hydrophobic white carbon black, the hydrophilic fumed silica has larger surface area and more surface hydroxyl content, and has more obvious thixotropic and reinforcing effects in a polyurethane system, however, the hydroxyl on the surface of the hydrophilic white carbon black can react with isocyanate groups in a single-component polyurethane adhesive system, so that the polyurethane adhesive prepared by using the hydrophilic white carbon black as a raw material is higher in viscosity and unstable, and the application of the hydrophilic fumed silica in the formula of the single-component polyurethane adhesive is limited.
In order to solve the defects in the prior art, a single-component polyurethane corner adhesive system capable of applying hydrophilic fumed silica is urgently needed to be developed at present, and the bonding strength of the polyurethane corner adhesive is improved.
Disclosure of Invention
In view of the above, the invention aims to provide a polyurethane corner combining adhesive with high bonding strength and a preparation method thereof, wherein the corner combining adhesive can improve the structural bonding strength of the corner combining position of a wood door and a window; the bonding strength of the corner combining position of the aluminum alloy door and window can be greatly improved.
The invention provides a polyurethane corner adhesive with high bonding strength, which comprises the following components in parts by weight:
60-90 parts of polyurethane prepolymer, 4-10 parts of plasticizer, 0-20 parts of filler, 0.01-1 part of catalyst, 0.5-3 parts of defoaming agent and 3-10 parts of modified hydrophilic white carbon black;
the polyurethane prepolymer is prepared by reacting isocyanate, bifunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol in a mass ratio of 30-50: 3-10: 30-60;
the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100.
Preferably, the specific surface area of the hydrophilic white carbon black is 50-500 m2/g；
The type of the hydrophilic white carbon black is one or more of A380, HDKT30, HDKT40 and HDKV 15.
Preferably, the epoxy silane is selected from one or more of 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, and beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane.
Preferably, the molecular weight of the difunctional polyether polyol is 300-800 g/mol;
the molecular weight of the tetrafunctional polyether polyol is 300-800 g/mol;
the molecular weight of the trifunctional polyether polyol is 2000-6000 g/mol;
the isocyanate is selected from one or more of benzhydryl diisocyanate, toluene diisocyanate and polymethylene polyphenyl isocyanate.
Preferably, the mass ratio of isocyanate groups to hydroxyl groups of the polyol of the polyurethane prepolymer is 3.0 to 5.0.
Preferably, the plasticizer is selected from one or more of di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisobutyl phthalate, diisooctyl 4, 5-epoxy tetrahydrophthalate and Mesamoll plasticizers;
the filler is selected from one or more of nano calcium, heavy calcium, clay, talcum powder and zeolite;
the catalyst is selected from one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylenediamine, N, N-dimethylbenzylamine, bis (2, 2-morpholinoethyl) ether, dibutyltin dilaurate and dibutyltin diacetate;
the defoaming agent is selected from methyl silicone resin and/or methyl vinyl silicone resin.
The invention provides a preparation method of a polyurethane corner combining adhesive with high bonding strength, which comprises the following steps:
mixing the polyurethane prepolymer, the plasticizer, the filler, the catalyst, the defoaming agent and the modified hydrophilic white carbon black at 20-70 ℃, and stirring for 2-5 hours to obtain the high-bonding-strength polyurethane corner adhesive;
the polyurethane prepolymer is prepared by reacting isocyanate, bifunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol in a mass ratio of 30-50: 3-10: 30-60;
the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100.
Preferably, the modified hydrophilic white carbon black is prepared according to the following method:
mixing hydrophilic white carbon black with a solvent, N2Heating to 100-120 ℃ in the atmosphere, dispersing for 25-35 min, adding epoxy silane, continuously stirring and reacting for 1-4 h at 110-130 ℃, cooling, filtering and drying to obtain the modified hydrophilic white carbon black.
Preferably, the mass ratio of the hydrophilic white carbon black to the solvent is 1-3: 10;
the solvent is selected from one or more of toluene, xylene, propyl acetate and butyl acetate.
Preferably, the polyurethane prepolymer is prepared by the following method:
mixing and stirring difunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol at 80-90 ℃, drying in vacuum, cooling to 30-50 ℃, adding isocyanate, and reacting for 2-3 h at 70-80 ℃ to obtain the polyurethane prepolymer.
The invention provides a polyurethane corner adhesive with high bonding strength, which comprises the following components in parts by weight: 60-90 parts of polyurethane prepolymer, 4-10 parts of plasticizer, 0-20 parts of filler, 0.01-1 part of catalyst, 0.5-3 parts of defoaming agent and 3-10 parts of modified hydrophilic white carbon black; the polyurethane prepolymer is prepared by reacting isocyanate, bifunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol in a mass ratio of 30-50: 3-10: 30-60; the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100. According to the invention, the silane modified hydrophilic white carbon black is applied to a polyurethane adhesive system to play a multifunctional role, firstly, silane on the surface of the hydrophilic white carbon black can further react with surface groups of a substrate to improve the adhesion on the surface of an aluminum profile, and secondly, in the corner adhesive curing process, silane epoxy groups modified on the surface of the hydrophilic white carbon black and-NH generated in the polyurethane adhesive curing process2The reaction improves the strength of the fully cured corner adhesive; finally, a large number of hydroxyl groups of the hydrophilic white carbon black react with methoxyl groups in the epoxy silane, so that the influence of the hydroxyl groups on the stability of the system is reduced, and the prepared corner combining adhesive has higher stability. The angle glue can improve the structural bonding strength of the angle position of the wooden door and window; the bonding strength of the corner combining position of the aluminum alloy door and window can be greatly improved. The experimental results show that: the shearing strength of the wood section is 12.8-14.1 MPa; the shear strength of the aluminum profile is 11.8-13.8 MPa; the viscosity change rate after aging is 19-30%.
Detailed Description
The invention provides a polyurethane corner adhesive with high bonding strength, which comprises the following components in parts by weight:
60-90 parts of polyurethane prepolymer, 4-10 parts of plasticizer, 0-20 parts of filler, 0.01-1 part of catalyst, 0.5-3 parts of defoaming agent and 3-10 parts of modified hydrophilic white carbon black;
the polyurethane prepolymer is prepared by reacting isocyanate, bifunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol in a mass ratio of 30-50: 3-10: 30-60;
the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100.
According to the invention, the silane modified hydrophilic white carbon black is applied to a polyurethane adhesive system to play a multifunctional role, firstly, silane on the surface of the hydrophilic white carbon black can further react with surface groups of a substrate to improve the adhesion on the surface of an aluminum profile, and secondly, in the corner adhesive curing process, silane epoxy groups modified on the surface of the hydrophilic white carbon black and-NH generated in the polyurethane adhesive curing process2The reaction improves the strength of the fully cured corner adhesive; finally, a large number of hydroxyl groups of the hydrophilic white carbon black react with methoxyl groups in the epoxy silane, so that the influence of the hydroxyl groups on the stability of the system is reduced, and the prepared corner combining adhesive has higher stability. The angle glue can improve the structural bonding strength of the angle position of the wooden door and window; the bonding strength of the corner combining position of the aluminum alloy door and window can be greatly improved.
The polyurethane corner adhesive with high bonding strength comprises 50-90 parts by weight of polyurethane prepolymer; the polyurethane prepolymer is prepared by reacting 30-50: 3-10: 30-60 mass ratio of isocyanate, difunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol. The mass ratio of the isocyanate group of the polyurethane prepolymer to the hydroxyl group of the polyol is preferably 3.0-5.0, and more preferably 3-4.5; in particular embodiments, the isocyanate-terminated polymer has an R value of 3.42, 4.44, or 3.17.
In the invention, the molecular weight of the difunctional polyether polyol is preferably 300-800 g/mol; the molecular weight of the tetrafunctional polyether polyol is preferably 300-800 g/mol; the molecular weight of the trifunctional polyether polyol is preferably 2000-6000 g/mol. The isocyanate is selected from one or more of benzhydryl diisocyanate, toluene diisocyanate and polymethylene polyphenyl isocyanate. In particular embodiments, the molecular weight of the difunctional polyether polyol is 400g/mol or 300 g/mol; the tetrafunctional polyether polyol has a molecular weight of 400g/mol, 800g/mol, or 600 g/mol; the trifunctional polyether polyol has a molecular weight of 5000g/mol, 6000g/mol or 2400 g/mol.
The polyurethane corner adhesive with high bonding strength comprises 4-10 parts of plasticizer. The plasticizer is preferably selected from one or more of di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisobutyl phthalate, diisooctyl 4, 5-epoxy tetrahydrophthalate and Mesamoll plasticizers. In a specific embodiment, the plasticizer is one or more of 4, 5-epoxy tetrahydro-dioctyl phthalate, diisobutyl phthalate, Mesamoll plasticizer and diisodecyl phthalate.
The polyurethane corner-combining glue with high bonding strength comprises 0-20 parts of filler. In the present invention, the filler is preferably selected from one or more of nano calcium, heavy calcium, clay, talc and zeolite. In a specific embodiment, the filler is one or more of 5A zeolite, 4A zeolite, 3A zeolite and nano calcium.
The polyurethane corner-combining adhesive with high bonding strength comprises 0.01-1 part of catalyst. In the present invention, the catalyst is preferably one or more selected from the group consisting of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N' -tetramethylalkylenediamine, triethylenediamine, N-dimethylbenzylamine, bis (2, 2-morpholinoethyl) ether, dibutyltin dilaurate, dibutyltin didodecylthio and dibutyltin diacetate.
The polyurethane corner combining glue with high bonding strength comprises 0.5-3 parts of defoaming agent; the defoaming agent is preferably selected from methyl silicone resin and/or methyl vinyl silicone resin.
The high-bonding-strength polyurethane corner-forming adhesive provided by the invention comprises modified hydrophilic3-10 parts of water white carbon black; the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100. In the present invention, the epoxy silane is preferably selected from one or more of 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, γ -glycidoxypropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) -ethyltriethoxysilane and β - (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane; the preferred specific surface area of the hydrophilic white carbon black is 50-500 m2(ii) in terms of/g. In specific embodiments, the epoxy silane is gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, or 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane. The type of the hydrophilic white carbon black is one or more of A380, HDKT30, HDKT40 and HDKV 15. In a specific embodiment, the mass ratio of the epoxy silane to the hydrophilic white carbon black is 1: 10; or 1: 20; or 1: 25; or 3: 40.
The modified hydrophilic white carbon black is preferably prepared by the following method:
mixing hydrophilic white carbon black with a solvent, N2Heating to 100-120 ℃ in the atmosphere, dispersing for 25-35 min, adding epoxy silane, continuously stirring and reacting for 1-4 h at 110-130 ℃, cooling, filtering and drying to obtain the modified hydrophilic white carbon black.
In the invention, the mass ratio of the hydrophilic white carbon black to the solvent is 1-3: 10; the solvent is selected from one or more of toluene, xylene, propyl acetate and butyl acetate.
The invention provides a preparation method of a polyurethane corner combining adhesive with high bonding strength, which comprises the following steps:
mixing the polyurethane prepolymer, the plasticizer, the filler, the catalyst, the defoaming agent and the modified hydrophilic white carbon black at 20-70 ℃, and stirring for 2-5 hours to obtain the high-bonding-strength polyurethane corner adhesive;
the polyurethane prepolymer is prepared by reacting isocyanate, bifunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol in a mass ratio of 30-50: 3-10: 30-60;
the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100.
In the present invention, the types and the amounts of the polyurethane prepolymer, the plasticizer, the filler, the catalyst, the defoamer and the modified hydrophilic white carbon black are consistent with those described in the above technical solution, and are not described herein again.
The invention preferably adopts the following mode to carry out performance measurement on the corner-setting adhesive:
the shear strength detection method comprises the following steps: the method comprises the steps of preparing corner glue lap joint sample pieces with the length of 25mm, the thickness of 0.2mm and the width of 12.5mm by using aluminum sheets and beech pieces which are not polished, curing for 7 days at the temperature of 23 ℃ and the humidity of 50%, and then testing the shearing performance on an electronic universal testing machine.
The method for detecting the viscosity change rate after aging comprises the following steps: aging the prepared corner-combining glue in an oven at 70 ℃ for 2 days, and taking out; the viscosity was measured after 1 day of standing under standard conditions (23 ℃ C., 50% relative humidity).
Viscosity change rate ═ (viscosity after aging-initial viscosity)/initial viscosity ═ 100%.
In order to further illustrate the present invention, the following examples are provided to describe the polyurethane corner-forming adhesives with high adhesive strength and the preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing modified hydrophilic white carbon black:
dispersing 20g of hydrophilic white carbon black A380 in 100g of toluene solution, and stirring and dispersing for 30min at 110 ℃; then 2g of gamma-glycidoxypropyltrimethoxysilane is added, the mixture is continuously stirred and dispersed for 120min at the temperature of 110 ℃, and the silane modified hydrophilic white carbon black is obtained after cooling, filtering and drying.
Preparing the corner-combining glue:
in N2Gradually adding 800g of the isocyanate-terminated polymer, 40g of silane modified hydrophilic white carbon black, 80g of 4, 5-epoxy tetrahydro diisooctyl phthalate, 20g of methyl silicone resin, 3g of N, N-dimethyl cyclohexylamine, 2g of dibutyltin diacetate and 55g of 5A zeolite into a planetary stirrer at 25 ℃ under the atmosphere, and mixing and stirring for 2 hours to obtain the high-adhesion-strength polyurethane corner adhesive;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group corner glue with high bonding strength prepared in the example 1 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
TABLE 1 Strength of high adhesion Strength polyurethane corner-penetrating adhesive prepared in inventive examples 1 to 6 and comparative examples 1 to 2
Example 2
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing modified hydrophilic white carbon black:
dispersing 20g of hydrophilic white carbon black A380 in 100g of toluene solution, and stirring and dispersing for 30min at 110 ℃; and then adding 1g of gamma-glycidyl ether oxypropyl trimethoxy silane, continuously stirring and dispersing for 100min at 120 ℃, cooling, filtering and drying to obtain the silane modified hydrophilic white carbon black.
Preparing the corner-combining glue:
in N2Under the atmosphere, 750g of the isocyanate-terminated polymer, 35g of silane modified hydrophilic white carbon black, 90g of dioctyl phthalate, 5g of methyl vinyl silicone resin antifoaming agent, 2g of triethylene diamine and 118g of 3A zeolite are gradually added into a planetary stirrer to be mixed and stirred for 3 hours at the temperature of 30 ℃ to obtain the high-bonding-strength polyurethane corner glue;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group corner glue with high bonding strength prepared in the example 2 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Example 3
Preparation of isocyanate-terminated polymers:
adding 360g of trifunctional polyether polyol (average molecular weight of 6000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 300g/mol) and 40g of tetrafunctional polyether polyol (average molecular weight of 800g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 120g of toluene diisocyanate and 120g of diphenyl methyl diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 4.44;
preparing modified hydrophilic white carbon black:
dispersing 20g of hydrophilic white carbon black HDKV15 in 100g of toluene solution, and stirring and dispersing for 30min at 110 ℃; then 0.8g of beta- (3, 4-epoxy cyclohexyl) -ethyl trimethoxy silane is added, the mixture is continuously stirred and dispersed for 70min at the temperature of 115 ℃, and the silane modified hydrophilic white carbon black is obtained after cooling, filtering and drying.
Preparing the corner-combining glue:
in N2Under the atmosphere, gradually adding 810g of the isocyanate-terminated polymer, 90g of silane modified hydrophilic white carbon black, 82g of diisobutyl phthalate, 15g of methyl vinyl silicone resin defoaming agent and 3g of bis (2, 2-morpholinoethyl) ether into a planetary stirrer, and mixing and stirring at 30 ℃ for 1.5h to obtain the polyurethane corner glue with high bonding strength;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group corner glue with high bonding strength prepared in the example 3 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Example 4
Preparation of isocyanate-terminated polymers:
adding 360g of trifunctional polyether polyol (average molecular weight of 6000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 300g/mol) and 40g of tetrafunctional polyether polyol (average molecular weight of 800g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 120g of toluene diisocyanate and 120g of diphenyl methyl diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 4.44;
preparing modified hydrophilic white carbon black:
dispersing 20g of hydrophilic white carbon black HDKT40 in 100g of toluene solution, and stirring and dispersing for 30min at 110 ℃; then 2g of beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane is added, the mixture is continuously stirred and dispersed for 120min at 125 ℃, and the silane modified hydrophilic white carbon black is obtained after cooling, filtering and drying.
Preparing the corner-combining glue:
in N2In the atmosphere, graduallyAdding 700g of the isocyanate-terminated polymer, 100g of silane modified hydrophilic white carbon black, 100g of Mesamoll plasticizer, 25g of methyl silicone resin defoamer, 2g of dibutyltin dilaurate catalyst and 73g of 4A zeolite into a planetary stirrer, and mixing and stirring at 40 ℃ for 1.5 hours to obtain the polyurethane corner glue with high bonding strength;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group corner glue with high bonding strength prepared in the example 4 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Example 5
Adding 320g of trifunctional polyether polyol (average molecular weight of 2400g/mol), 20g of bifunctional polyether polyol (average molecular weight of 300g/mol) and 40g of tetrafunctional polyether polyol (average molecular weight of 600g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 205g of toluene diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then adding 25g of polymethylene polyphenyl polyisocyanate (the content of isocyanate is 31%), subsequently cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.17;
preparing modified hydrophilic white carbon black:
dispersing 20g of hydrophilic white carbon black HDKT30 in 100g of toluene solution, and stirring and dispersing for 30min at 110 ℃; then adding 3- (2, 3-epoxypropoxy) propyl methyl diethoxysilane 1.5g, continuing stirring and dispersing for 60min at 130 ℃, cooling, filtering and drying to obtain the silane modified hydrophilic white carbon black.
Preparing the corner-combining glue:
in N2Gradually adding 890g of the isocyanate-terminated polymer, 40g of silane modified hydrophilic white carbon black, 45g of diisodecyl phthalate, 9g of methyl silicone resin defoaming agent, 1g of bis (2-dimethylaminoethyl) ether catalyst and 15g of nano calcium into a planetary stirrer at 40 ℃ under the atmosphere, and mixing and stirring for 2 hours to obtain the polyurethane corner glue with high bonding strength;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group corner glue with high bonding strength prepared in the example 5 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Comparative example 1
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing the corner-combining glue:
in N2Gradually adding 800g of the isocyanate-terminated polymer, 40g of hydrophilic white carbon black A380, 80g of 4, 5-epoxy tetrahydro-phthalic acid diisooctyl ester, 20g of methyl silicone resin, 3g of N, N-dimethyl cyclohexylamine, 2g of dibutyltin diacetate and 55g of 5A zeolite into a planetary stirrer in an atmosphere, and mixing and stirring for 2 hours at 25 ℃ to obtain the polyurethane corner adhesive;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group angle glue prepared in the comparative example 1 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Comparative example 2
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing the corner-combining glue:
in N2Gradually adding 800g of the isocyanate-terminated polymer, 40g of hydrophobic white carbon H18, 80g of 4, 5-epoxy tetrahydro-dioctyl phthalate, 20g of methyl silicone resin, 3g of N, N-dimethyl cyclohexylamine, 2g of dibutyltin diacetate and 55g of 5A zeolite into a planetary stirrer in an atmosphere, and mixing and stirring for 2 hours at 25 ℃ to obtain the polyurethane corner adhesive;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group angle glue prepared in the comparative example 2 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Comparative example 3
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing the corner-combining glue:
in N2Gradually adding 800g of the isocyanate-terminated polymer, 36g of hydrophilic white carbon black A380, 4g of gamma-glycidoxypropyltrimethoxysilane, 80g of 4, 5-epoxy-tetrahydro-phthalic acid diisooctyl ester, 20g of methyl silicone resin, 3g of N, N-dimethyl cyclohexylamine, 2g of dibutyltin diacetate and 55g of 5A zeolite into a planetary stirrer in an atmosphere, and mixing and stirring for 2 hours at 25 ℃ to obtain the polyurethane corner glue;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane corner glue prepared in the comparative example 3 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Comparative example 4
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing the corner-combining glue:
in N2Gradually adding 800g of the isocyanate-terminated polymer, 36g of hydrophobic white carbon H18, 4g of gamma-glycidoxypropyltrimethoxysilane, 80g of 4, 5-epoxy tetrahydro diisooctyl phthalate, 20g of methyl silicone resin, 3g of N, N-dimethyl cyclohexylamine, 2g of dibutyltin diacetate and 55g of 5A zeolite into a planetary stirrer in an atmosphere, and mixing and stirring for 2 hours at 25 ℃ to obtain the polyurethane corner glue;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane corner glue prepared in the comparative example 4 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Comparative example 5
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing modified hydrophilic white carbon black:
dispersing 20g of hydrophilic white carbon black A380 in 100g of toluene solution, and stirring and dispersing for 30min at 110 ℃; and then 2g of mercaptopropyl trimethoxy silane is added, stirring and dispersing are continued for 120min at the temperature of 110 ℃, and the silane modified hydrophilic white carbon black is obtained after cooling, filtering and drying.
Preparing the corner-combining glue:
in N2Gradually adding 800g of the isocyanate-terminated polymer, 40g of silane modified hydrophilic white carbon black, 80g of 4, 5-epoxy tetrahydro diisooctyl phthalate, 20g of methyl silicone resin, 3g of N, N-dimethyl cyclohexylamine, 2g of dibutyltin diacetate and 55g of 5A zeolite into a planetary stirrer at 25 ℃ under the atmosphere, and mixing and stirring for 2 hours to obtain the polyurethane corner glue;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group angle glue prepared in the comparative example 5 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Comparative example 6
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing modified hydrophilic white carbon black:
dispersing 20g of hydrophobic white carbon black H18 in 100g of toluene solution, and stirring and dispersing for 30min at 110 ℃; then 2g of gamma-glycidoxypropyltrimethoxysilane is added, the mixture is continuously stirred and dispersed for 120min at the temperature of 110 ℃, and the silane modified hydrophobic white carbon black is obtained after cooling, filtering and drying.
Preparing the corner-combining glue:
in N2Gradually adding 800g of the isocyanate-terminated polymer, 40g of silane modified hydrophilic white carbon black, 80g of 4, 5-epoxy tetrahydro diisooctyl phthalate, 20g of methyl silicone resin, 3g of N, N-dimethyl cyclohexylamine, 2g of dibutyltin diacetate and 55g of 5A zeolite into a planetary stirrer at 25 ℃ under the atmosphere, and mixing and stirring for 2 hours to obtain the polyurethane corner glue;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group angle glue prepared in the comparative example 6 on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
Comparative example 7
Preparation of isocyanate-terminated polymers:
adding 200g of trifunctional polyether polyol (average molecular weight of 5000g/mol), 20g of bifunctional polyether polyol (average molecular weight of 400g/mol) and 20g of tetrafunctional polyether polyol (average molecular weight of 400g/mol) into a reactor with a mechanical stirring device, a vacuum device, a nitrogen protection device and a heating device, stirring at 90 ℃, and vacuum-drying for 3 hours; then cooling to 30 ℃, adding 180g of diphenylmethane diisocyanate, reacting for 2h at 70 ℃ under a vacuum condition, then cooling to less than 40 ℃, and discharging to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer is 3.42;
preparing modified hydrophilic white carbon black:
dispersing 100g of hydrophilic white carbon black A380 in 100g of toluene solution, and stirring and dispersing for 30min at 110 ℃; and then adding 0.3g of gamma-glycidoxypropyltrimethoxysilane, continuously stirring and dispersing at 110 ℃ for 120min, cooling, filtering and drying to obtain the silane modified hydrophilic white carbon black.
Preparing the corner-combining glue:
in N2Under the atmosphere, gradually adding 800g of the isocyanate-terminated polymer, 40g of silane modified hydrophilic white carbon black and 80g of 4, 5-epoxy tetrahydro dioctyl phthalate20g of methyl silicone resin, 3g of N, N-dimethylcyclohexylamine, 2g of dibutyltin diacetate and 55g of 5A zeolite are added into a planetary stirrer, mixed and stirred for 2 hours at the temperature of 25 ℃ to obtain polyurethane corner-combining glue;
according to the bonding effect test method of the technical scheme, the shear strength of the polyurethane group angle glue prepared in the comparative example on beech chips and aluminum sheets and the viscosity change rate after high-temperature aging are detected, and the test results are shown in table 1.
From the above examples, the invention provides a polyurethane corner-forming adhesive with high bonding strength, which comprises the following components in parts by weight: 50-90 parts of polyurethane prepolymer, 4-10 parts of plasticizer, 0-20 parts of filler, 0.01-1 part of catalyst, 0.5-3 parts of defoaming agent and 3-10 parts of modified hydrophilic white carbon black; the polyurethane prepolymer is prepared by reacting isocyanate, bifunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol in a mass ratio of 30-50: 3-10: 30-60; the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100. According to the invention, the silane modified hydrophilic white carbon black is applied to a polyurethane adhesive system to play a multifunctional role, firstly, silane on the surface of the hydrophilic white carbon black can further react with surface groups of a substrate to improve the adhesion on the surface of an aluminum profile, and secondly, in the corner adhesive curing process, silane epoxy groups modified on the surface of the hydrophilic white carbon black and-NH generated in the polyurethane adhesive curing process2The reaction improves the strength of the fully cured corner adhesive; finally, a large number of hydroxyl groups of the hydrophilic white carbon black react with methoxyl groups in the epoxy silane, so that the influence of the hydroxyl groups on the stability of the system is reduced, and the prepared corner combining adhesive has higher stability. The angle glue can improve the structural bonding strength of the angle position of the wooden door and window; the bonding strength of the corner combining position of the aluminum alloy door and window can be greatly improved. The experimental results show that: the shearing strength of the wood section is 12.8-14.1 MPa; the shear strength of the aluminum profile is 11.8-13.8 MPa; the viscosity change rate after aging is 19-30%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A polyurethane corner-combining adhesive with high bonding strength comprises the following components in parts by weight:
60-90 parts of polyurethane prepolymer, 4-10 parts of plasticizer, 0-20 parts of filler, 0.01-1 part of catalyst, 0.5-3 parts of defoaming agent and 3-10 parts of modified hydrophilic white carbon black;
the polyurethane prepolymer is prepared by reacting 30-50: 3-10: 30-60 mass ratio of isocyanate, difunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol;
the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100.
2. The polyurethane corner combining glue according to claim 1, wherein the specific surface area of the hydrophilic white carbon black is 50-500 m2/g；
The type of the hydrophilic white carbon black is one or more of A380, HDKT30, HDKT40 and HDKV 15.
3. The polyurethane corner cube according to claim 1, wherein the epoxy silane is selected from one or more of 3- (2, 3-glycidoxy) propylmethyldiethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, γ -glycidoxypropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, and β - (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane.
4. The polyurethane corner cube according to claim 1, wherein the difunctional polyether polyol has a molecular weight of 300-800 g/mol;
the molecular weight of the tetrafunctional polyether polyol is 300-800 g/mol;
the molecular weight of the trifunctional polyether polyol is 2000-6000 g/mol;
the isocyanate is selected from one or more of benzhydryl diisocyanate, toluene diisocyanate and polymethylene polyphenyl isocyanate.
5. The polyurethane corner cube according to claim 1, wherein the ratio of the amount of isocyanate groups to the amount of hydroxyl groups of the polyol in the polyurethane prepolymer is 3.0-5.0.
6. The polyurethane corner cube according to claim 1, wherein the plasticizer is selected from one or more of di (2-ethylhexyl) phthalate, dioctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisobutyl phthalate, diisooctyl 4, 5-epoxy tetrahydrophthalate, and Mesamoll plasticizer;
the filler is selected from one or more of nano calcium, heavy calcium, clay, talcum powder and zeolite;
the catalyst is selected from one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylenediamine, N, N-dimethylbenzylamine, bis (2, 2-morpholinoethyl) ether, dibutyltin dilaurate and dibutyltin diacetate;
the defoaming agent is selected from methyl silicone resin and/or methyl vinyl silicone resin.
7. The preparation method of the high-bonding-strength polyurethane corner-combining glue disclosed by claim 1 comprises the following steps:
mixing the polyurethane prepolymer, the plasticizer, the filler, the catalyst, the defoaming agent and the modified hydrophilic white carbon black at 20-70 ℃, and stirring for 2-5 hours to obtain the high-bonding-strength polyurethane corner adhesive;
the polyurethane prepolymer is prepared by reacting 30-50: 3-10: 30-60 mass percent of isocyanate, difunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol;
the modified hydrophilic white carbon black is prepared by reacting epoxy silane and hydrophilic white carbon black in a mass ratio of 1-10: 100.
8. The preparation method according to claim 7, wherein the modified hydrophilic white carbon black is prepared according to the following method:
mixing hydrophilic white carbon black with a solvent, N2Heating to 100-120 ℃ in the atmosphere, dispersing for 25-35 min, adding epoxy silane, continuously stirring and reacting for 1-4 h at 110-130 ℃, cooling, filtering and drying to obtain the modified hydrophilic white carbon black.
9. The preparation method according to claim 8, wherein the mass ratio of the hydrophilic white carbon black to the solvent is 1-3: 10;
the solvent is selected from one or more of toluene, xylene, propyl acetate and butyl acetate.
10. The method according to claim 7, wherein the polyurethane prepolymer is prepared by:
mixing and stirring difunctional polyether polyol, tetrafunctional polyether polyol and trifunctional polyether polyol at 80-90 ℃, drying in vacuum, cooling to 30-50 ℃, adding isocyanate, and reacting for 2-3 h at 70-80 ℃ to obtain the polyurethane prepolymer.
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| US5889068A (en) * | 1997-07-24 | 1999-03-30 | Bayer Corporation | Water blown polyurethane soling systems |
| CN109021212A (en) * | 2018-07-13 | 2018-12-18 | 杭州之江新材料有限公司 | A kind of transparent group of angle glue of mono-component polyurethane and preparation method thereof |
| CN109082260A (en) * | 2018-07-13 | 2018-12-25 | 杭州之江新材料有限公司 | Transparent group of angle glue of one pack system and preparation method thereof |
| CN109280528A (en) * | 2018-10-09 | 2019-01-29 | 杭州之江新材料有限公司 | A kind of High-strength double-component polyurethane group angle glue and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5889068A (en) * | 1997-07-24 | 1999-03-30 | Bayer Corporation | Water blown polyurethane soling systems |
| CN109021212A (en) * | 2018-07-13 | 2018-12-18 | 杭州之江新材料有限公司 | A kind of transparent group of angle glue of mono-component polyurethane and preparation method thereof |
| CN109082260A (en) * | 2018-07-13 | 2018-12-25 | 杭州之江新材料有限公司 | Transparent group of angle glue of one pack system and preparation method thereof |
| CN109280528A (en) * | 2018-10-09 | 2019-01-29 | 杭州之江新材料有限公司 | A kind of High-strength double-component polyurethane group angle glue and preparation method thereof |
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