CN112175572A - High-strength bi-component polyurethane adhesive and preparation method thereof - Google Patents
High-strength bi-component polyurethane adhesive and preparation method thereof Download PDFInfo
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 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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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K2201/00—Specific properties of additives
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a high-strength bi-component polyurethane adhesive, which comprises a component A and a component B; the component A comprises 45-55% of a polyol polymer, 35-45% of an inorganic filler, 1-3% of a cross-linking agent, 1-2% of a wetting agent, 1-3% of a dispersing agent, 1-3% of a chain extender and 3-6% of an adhesion promoter in mass ratio; the component B is isocyanate; the volume ratio of the component A to the component B is 100: 20-30. The polyol polymer in the invention is a mixture of polycaprolactone diol, vegetable oil polyol, cashew nut shell oil polyol and castor oil, and the interaction of different components ensures that the adhesive has the characteristics of high curing speed, high crosslinking density, high tensile strength and the like; the cashew nut shell oil polyalcohol has good water resistance, weather resistance and low shrinkage. In addition, the adhesive has high temperature resistance and high metal adhesion strength, and is particularly suitable for gluing aluminum plates.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a high-strength bi-component polyurethane adhesive and a preparation method thereof.
Background
With the increase of petroleum consumption, people face increasing shortage of petroleum resources and increasing of crude oil price, and the production of biological materials, chemical raw materials and fuels by using renewable resources attracts more and more attention. The vegetable oil is a renewable raw material, the polyurethane adhesive prepared by taking the vegetable oil containing hydroxyl or the hydroxylated vegetable oil as the polyalcohol completely meets the requirement of environmental protection, the main component of the fatty glyceride of the vegetable oil has hydrophobicity, and the polyurethane adhesive prepared by using the vegetable oil polyalcohol has good chemical and physical properties. Thus, vegetable oil polyols and their polyurethane adhesives have rapidly developed.
However, the polyurethane adhesive prepared from vegetable oil polyol in the market has single component, long curing time, greatly reduced bonding strength in a high-temperature environment, wider application range and no vegetable oil polyol polyurethane adhesive special for aluminum plates.
The invention aims to provide a high-strength bi-component polyurethane adhesive which has the advantages of short curing time and high bonding strength and is suitable for bonding aluminum alloy products.
Disclosure of Invention
In order to solve the above problems, the present invention provides in a first aspect a high strength two-component polyurethane adhesive comprising a component a and a component B; the component A comprises 45-55% of a polyol polymer, 35-45% of an inorganic filler, 1-3% of a cross-linking agent, 1-2% of a wetting agent, 1-3% of a dispersing agent, 1-3% of a chain extender and 3-6% of an adhesion promoter in mass ratio; the component B is isocyanate; the volume ratio of the component A to the component B is 100: 20-30.
As a preferable technical scheme, the polyol polymer is a mixture of polycaprolactone diol, vegetable oil polyol, cashew nut shell oil polyol and castor oil.
As a preferable technical scheme, the mass ratio of the polycaprolactone diol, the vegetable oil polyol, the cashew nut shell oil polyol and the castor oil is 2: 2.5-3.5: 3.5-4.5: 1.
as a preferable technical scheme, the number average molecular weight of the polycaprolactone diol is 1000-3000, and the hydroxyl value is 35-120 mgKOH/g.
As a preferable technical scheme, the average functionality of the vegetable oil polyalcohol is 3-8, and the hydroxyl value is 150-450 mgKOH/g.
As a preferable technical scheme, the viscosity of the cashew nut shell oil polyalcohol is 1000-3000cPs at 25 ℃; the hydroxyl value is 75-200 mgKOH/g.
As a preferable technical scheme, the inorganic filler is modified nano titanium dioxide.
As a preferable technical scheme, the specific surface area of the modified nano titanium dioxide is 60-90m2Per g, the particle diameter is 20-30 nm.
As a preferable technical scheme, the adhesion promoter is a mixture of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate.
As a preferable technical scheme, the mass ratio of the methacryloyloxyethyl phosphate to the ethylene glycol methacrylate phosphate is 2: 1 to 1.5.
The second aspect of the present invention provides a method for preparing the high strength two-component polyurethane adhesive, comprising the steps of:
s1, preparation of the component A: firstly, putting a polyalcohol polymer into a reaction kettle, uniformly stirring, heating to 80-100 ℃, carrying out vacuum dehydration, cooling to 50-70 ℃, sequentially adding an inorganic filler, a cross-linking agent, a wetting agent, a dispersing agent, a chain extender and an adhesion promoter, uniformly stirring, and barreling;
s2, when in use, the component A and the component B are mixed evenly according to the volume ratio to obtain the high-strength bi-component polyurethane adhesive.
Has the advantages that:
the polyol polymer in the invention is a mixture of polycaprolactone diol, vegetable oil polyol, cashew nut shell oil polyol and castor oil, and the interaction of different components ensures that the adhesive has the characteristics of high curing speed, high crosslinking density, high tensile strength and the like; the cashew nut shell oil polyalcohol has good water resistance, weather resistance and low shrinkage. In addition, the adhesive has high temperature resistance and high metal adhesion strength, and is particularly suitable for gluing aluminum plates.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
In order to solve the above problems, the present invention provides in a first aspect a high strength two-component polyurethane adhesive comprising a component a and a component B; the component A comprises 45-55% of a polyol polymer, 35-45% of an inorganic filler, 1-3% of a cross-linking agent, 1-2% of a wetting agent, 1-3% of a dispersing agent, 1-3% of a chain extender and 3-6% of an adhesion promoter in mass ratio; the component B is isocyanate; the volume ratio of the component A to the component B is 100: 20-30.
In some preferred embodiments, the polyol polymer is a mixture of polycaprolactone diol, vegetable oil polyol, cashew nut shell oil polyol, and castor oil. The polyol polymer is selected from the mixture of polycaprolactone diol, vegetable oil polyol, cashew nut shell oil polyol and castor oil, so that the tensile strength and the curing time of the polyurethane adhesive are improved; when the component only contains the vegetable oil polyalcohol, polar groups in the structure of the component are easy to react with water molecules, so that the number of the polar groups is reduced, the probability of reaction with isocyanate is reduced, the curing time is long, the crosslinking density is low, and the tensile strength is reduced. In the system, polycaprolactone diol, vegetable oil polyol, cashew nut shell oil polyol and castor oil interact with each other, so that the hydrophobic property of the polycaprolactone diol is greatly improved, and the crosslinking density is increased under the action of a crosslinking agent and a chain extender, so that the polycaprolactone diol has higher tensile strength.
In some preferred embodiments, the mass ratio of the polycaprolactone diol, the vegetable oil polyol, the cashew nut shell oil polyol and the castor oil is 2: 2.5-3.5: 3.5-4.5: 1.
in some preferred embodiments, the polycaprolactone diol has a number average molecular weight of 1000-3000 and a hydroxyl number of 35-120 mgKOH/g. The number average molecular weight of the polycaprolactone diol is 1000-3000, and the hydroxyl value is 35-120 mgKOH/g; the number average molecular weight of the adhesive is selected to be within the range of 1000-3000 because when the molecular weight of polycaprolactone diol is too small, the crosslinking density is insufficient, the adhesive shows more rigidity, and the toughness is insufficient; when the molecular weight is too large, the length of the molecular chain of the polyol is correspondingly increased, so that the viscosity of the system is high, and the curing reaction is not facilitated. The hydroxyl value is selected to be between 35 and 120mgKOH/g, because the hydroxyl value of the vegetable oil polyol in the system is 150-450mgKOH/g, and the hydroxyl value of the cashew nut shell oil polyol is 75-200mgKOH/g, through the synergistic effect of different hydroxyl value contents, on one hand, the curing time can be accelerated, and on the other hand, the adhesive force with the aluminum plate can be enhanced.
The polycaprolactone diol in the invention is purchased from Hunan Polyben chemical new materials science and technology Co., Ltd, preferably PCL-2000 series;
in some preferred embodiments, the vegetable oil polyol has an average functionality of 3 to 8 and a hydroxyl number of 150-450 mgKOH/g. The average functionality of the vegetable oil polyalcohol is 3-8, the hydroxyl value is 150-450mgKOH/g, the vegetable oil polyalcohol with higher functionality is selected, the curing speed is improved, in addition, the hydroxyl value is selected at 150-450mgKOH/g, the compatibility of the vegetable oil polyalcohol with polycaprolactone dihydric alcohol, cashew nut shell oil polyalcohol and castor oil is improved on one hand, the reaction activity of the system is improved due to the existence of a large amount of polar molecules, and the curing effect at low temperature is also better.
The vegetable oil polyol is purchased from aeronautical science and technology limited of Zhang Home, and the FH series of vegetable oil polyols is optimized;
in some preferred embodiments, the cashew nut shell oil polyol has a viscosity of 1000-; the hydroxyl value is 75-200 mgKOH/g. The viscosity 25 ℃ (cPs) of the cashew nut shell oil polyalcohol is 1000-3000 cPs; the hydroxyl value is 75-200 mgKOH/g; the viscosity 25 ℃ (cPs) of cashew nut shell oil polyalcohol is 1000-3000cPs because the number average molecular weight of polycaprolactone diol in the system is 1000-3000, the proper flowing property of the system is controlled, and the curing reaction is favorably carried out; the hydroxyl value is selected to be between 75 and 200mgKOH/g because of the synergistic effect with vegetable oil polyol with the hydroxyl value of 150-450mgKOH/g and polycaprolactone diol with the hydroxyl value of 35 to 120mgKOH/g, thereby improving the adhesive force.
The cashew nut shell oil polyol in the invention is purchased from Kadelia;
in some preferred embodiments, the inorganic filler is modified nano titanium dioxide. The inorganic filler is selected from modified nano titanium dioxide, so that the compatibility of the nano titanium dioxide and a polymer system is improved; in addition, the specific surface area of the modified nano titanium dioxide is selected to be 60-90m2/g, the particle size is selected to be 20-30nm, on one hand, the dispersibility of the modified nano titanium dioxide in a system can be improved, and on the other hand, when the modified nano titanium dioxide and the dispersing agent fumed silica act together, the high temperature resistance and the weather resistance of the adhesive can be greatly improved.
In some preferred embodiments, the specific surface area of the modified nano titanium dioxide is 60 to 90m2Per g, the particle diameter is 20-30 nm.
The modified nano titanium dioxide in the invention is selected from Hangzhou Wanjing new material company, model number: VK-T25S;
in some preferred embodiments, the crosslinking agent is a silicone-based crosslinking agent or an acrylate-based crosslinking agent.
Preferably, the organosilicon crosslinking agent comprises gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane; the acrylate crosslinking agent comprises 1, 4-butanediol diacrylate, ethylene glycol dimethacrylate and butyl acrylate.
More preferably, the silicone-based crosslinking agent is gamma-glycidoxypropyltrimethoxysilane (CAS number 2530-83-8); the acrylate crosslinking agent is ethylene glycol dimethacrylate (CAS number: 97-90-5).
In some preferred embodiments, the wetting agent is a polyoxyethylene alkylphenol ether, a polyoxyethylene fatty alcohol ether, a polyoxyethylene polyoxypropylene block copolymer.
Preferably, the wetting agent used in the embodiment of the present invention is alkylphenol ethoxylates which are available from the chemical industry ltd of yun hai, junan, model number: YH-TX-10;
in some preferred embodiments, the dispersant is fumed silica selected from the group consisting of deluxe trade ltd, model number: QS-102;
in some preferred embodiments, the chain extender is an alcoholic chain extender, specifically including 1, 4-butanediol, 1, 6-hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, neopentyl glycol, sorbitol, diethylaminoethanol, etc., preferably neopentyl glycol (CAS number: 126-30-7);
in some preferred embodiments, the adhesion promoter is a mixture of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate. The adhesion promoter is a mixture of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate, and the interaction of two polyfunctional group substances improves the adhesion of an adhesive system to an aluminum plate.
In some preferred embodiments, the mass ratio of methacryloyloxyethyl phosphate to ethylene glycol methacrylate phosphate is 2: 1 to 1.5.
The methacryloyloxyethyl phosphate and the ethylene glycol methacrylate phosphate in the invention are both from Guangzhou Fine chemical materials, Inc.;
the second aspect of the present invention provides a method for preparing the high strength two-component polyurethane adhesive, comprising the steps of:
s1, preparation of the component A: firstly, putting a polyalcohol polymer into a reaction kettle, uniformly stirring, heating to 80-100 ℃, carrying out vacuum dehydration, cooling to 50-70 ℃, sequentially adding an inorganic filler, a cross-linking agent, a wetting agent, a dispersing agent, a chain extender and an adhesion promoter, uniformly stirring, and barreling;
s2, when in use, the component A and the component B are mixed evenly according to the volume ratio to obtain the high-strength bi-component polyurethane adhesive.
The isocyanate of the component B in the invention is selected from German scientific institute (original Bayer) BAYER curing agent L75 (C).
Examples
The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples. Unless otherwise specified, all the raw materials in the present invention are commercially available.
Example 1
Example 1 provides a high strength two component polyurethane adhesive comprising a component a and a component B; the component A comprises 45% of a polyol polymer, 45% of an inorganic filler, 1% of a cross-linking agent, 1% of a wetting agent, 1% of a dispersing agent, 2% of a chain extender and 5% of an adhesion promoter in mass ratio; the component B is isocyanate; the volume ratio of the component A to the component B is 100: 20.
The polyalcohol polymer is a mixture of polycaprolactone dihydric alcohol, vegetable oil polyalcohol, cashew nut shell oil polyalcohol and castor oil.
The mass ratio of the polycaprolactone dihydric alcohol to the vegetable oil polyol to the cashew nut shell oil polyol to the castor oil is 2: 2.5: 3.5: 1.
the number average molecular weight of the polycaprolactone diol is 1000, and the hydroxyl value is 108-116mgKOH/g (which is purchased from Hunan Polyben chemical new materials science and technology Co., Ltd., model: PCL-2102).
The vegetable oil polyol has an average functionality of 3.8 and a hydroxyl value of 190-210mgKOH/g (available from air technology, Inc., Zhang Home, model: FH-4210).
The viscosity of the cashew nut shell oil polyalcohol is 1400cPs at 25 ℃; the hydroxyl value was 75mgKOH/g (available from Kadeli, type: GX-9201).
The inorganic filler is modified nano titanium dioxide, and the specific surface area of the modified nano titanium dioxide is 60-90m2(ii) particle size of 20-30nm (selected from Hangzhou Wanjing New Material Co., Ltd., model: VK-T25S).
The cross-linking agent is gamma-glycidoxypropyltrimethoxysilane or ethylene glycol dimethacrylate.
The wetting agent is alkylphenol polyoxyethylene (purchased from Jinan Yunyan chemical Co., Ltd., type YH-TX-10).
The dispersant is fumed silica (selected from Desheng trade Co., Ltd., Zhongshan City, model: QS-102);
the chain extender is neopentyl glycol;
the adhesion promoter is a mixture of methacryloyloxyethyl phosphate (from Guangzhou Fine chemical materials, Inc., model: PM1000) and ethylene glycol methacrylate phosphate (from Guangzhou fine chemical materials, Inc., model: PM1500), and the mass ratio of the two is 2: 1.
the embodiment also provides a preparation method of the high-strength two-component polyurethane adhesive, which comprises the following steps:
s1, preparation of the component A: firstly, putting the polyol polymer with the mass ratio into a reaction kettle, uniformly stirring, heating to 80 ℃, dehydrating for 2 hours in vacuum (the vacuum degree is 0.09MPa), cooling to 50 ℃, sequentially adding the inorganic filler, the cross-linking agent, the wetting agent, the dispersing agent, the chain extender and the adhesion promoter with the mass ratio, uniformly stirring, and barreling;
s2, when in use, the component A and the component B are mixed evenly according to the volume ratio to obtain the high-strength bi-component polyurethane adhesive.
The isocyanate of the component B in the invention is selected from German scientific institute (original Bayer) BAYER curing agent L75 (C).
Example 2
Embodiment 2 provides a high strength two-component polyurethane adhesive comprising a component a and a component B; the component A comprises 55% of a polyol polymer, 35% of an inorganic filler, 3% of a cross-linking agent, 2% of a wetting agent, 1% of a dispersing agent, 1% of a chain extender and 3% of an adhesion promoter in mass ratio; the component B is isocyanate; the volume ratio of the component A to the component B is 100: 30.
The polyalcohol polymer is a mixture of polycaprolactone dihydric alcohol, vegetable oil polyalcohol, cashew nut shell oil polyalcohol and castor oil.
The mass ratio of the polycaprolactone dihydric alcohol to the vegetable oil polyol to the cashew nut shell oil polyol to the castor oil is 2: 3.5: 4.5: 1.
the number average molecular weight of the polycaprolactone diol is 3000, and the hydroxyl value is 35-39mgKOH/g (the polycaprolactone diol is purchased from Hunan Polyben chemical new materials science and technology Co., Ltd., model: PCL-2302).
The vegetable oil polyol has an average functionality of 8 and a hydroxyl value of 390-450mgKOH/g (available from air technology ltd, Zhang Home, model: FH-8450).
The viscosity of the cashew nut shell oil polyalcohol is 3000cPs at 25 ℃; the hydroxyl value was 170mgKOH/g (from Kadeli, type: GX-9005).
The inorganic filler is modified nano titanium dioxide, and the specific surface area of the modified nano titanium dioxide is 60-90m2(ii) particle size of 20-30nm (selected from Hangzhou Wanjing New Material Co., Ltd., model: VK-T25S).
The cross-linking agent is gamma-glycidoxypropyltrimethoxysilane or ethylene glycol dimethacrylate.
The wetting agent is alkylphenol polyoxyethylene (purchased from Jinan Yunyan chemical Co., Ltd., type YH-TX-10).
The dispersant is fumed silica (selected from Desheng trade Co., Ltd., Zhongshan City, model: QS-102);
the chain extender is neopentyl glycol;
the adhesion promoter is a mixture of methacryloyloxyethyl phosphate (from Guangzhou Fine chemical materials, Inc., model: PM1000) and ethylene glycol methacrylate phosphate (from Guangzhou fine chemical materials, Inc., model: PM1500), and the mass ratio of the two is 2: 1 to 1.5.
The embodiment also provides a preparation method of the high-strength two-component polyurethane adhesive, which comprises the following steps:
s1, preparation of the component A: firstly, putting the polyalcohol polymer with the mass ratio into a reaction kettle, uniformly stirring, heating to 100 ℃, dehydrating for 2 hours in vacuum (the vacuum degree is 0.09MPa), cooling to 70 ℃, sequentially adding the inorganic filler, the cross-linking agent, the wetting agent, the dispersing agent, the chain extender and the adhesion promoter with the mass ratio, uniformly stirring, and barreling;
s2, when in use, the component A and the component B are mixed evenly according to the volume ratio to obtain the high-strength bi-component polyurethane adhesive.
The isocyanate of the component B in the invention is selected from German scientific institute (original Bayer) BAYER curing agent L75 (C).
Example 3
Embodiment 3 provides a high strength two component polyurethane adhesive comprising a component a and a component B; the component A comprises 50% of a polyol polymer, 40% of an inorganic filler, 1% of a cross-linking agent, 1% of a wetting agent, 1% of a dispersing agent, 2% of a chain extender and 5% of an adhesion promoter in mass ratio; the component B is isocyanate; the volume ratio of the component A to the component B is 100: 25.
The polyalcohol polymer is a mixture of polycaprolactone dihydric alcohol, vegetable oil polyalcohol, cashew nut shell oil polyalcohol and castor oil.
The mass ratio of the polycaprolactone dihydric alcohol to the vegetable oil polyol to the cashew nut shell oil polyol to the castor oil is 2: 3: 4: 1.
the number average molecular weight of the polycaprolactone diol is 2000, and the hydroxyl value is 54-58mgKOH/g (the polycaprolactone diol is purchased from Hunan Polyben chemical new materials science and technology Co., Ltd., model: PCL-2202).
The vegetable oil polyol has an average functionality of 6 and a hydroxyl value of 320-340mgKOH/g (available from air technology ltd, Zhang Home, model: FH-6330).
The viscosity of the cashew nut shell oil polyalcohol is 2000cPs at 25 ℃; a hydroxyl value of 175mgKOH/g (available from Kadeli, Inc., type: NX-9001).
The inorganic filler is modified nano titanium dioxide, and the specific surface area of the modified nano titanium dioxide is 60-90m2(ii) particle size of 20-30nm (selected from Hangzhou Wanjing New Material Co., Ltd., model: VK-T25S).
The cross-linking agent is gamma-glycidoxypropyltrimethoxysilane or ethylene glycol dimethacrylate.
The wetting agent is alkylphenol polyoxyethylene (purchased from Jinan Yunyan chemical Co., Ltd., type YH-TX-10).
The dispersant is fumed silica (selected from Desheng trade Co., Ltd., Zhongshan City, model: QS-102);
the chain extender is neopentyl glycol;
the adhesion promoter is a mixture of methacryloyloxyethyl phosphate (from Guangzhou Fine chemical materials, Inc., model: PM1000) and ethylene glycol methacrylate phosphate (from Guangzhou fine chemical materials, Inc., model: PM1500), and the mass ratio of the two is 2: 1 to 1.5.
The embodiment also provides a preparation method of the high-strength two-component polyurethane adhesive, which comprises the following steps:
s1, preparation of the component A: firstly, putting the polyalcohol polymer with the mass ratio into a reaction kettle, uniformly stirring, heating to 90 ℃, dehydrating for 2 hours in vacuum (the vacuum degree is 0.09MPa), cooling to 60 ℃, sequentially adding the inorganic filler, the cross-linking agent, the wetting agent, the dispersing agent, the chain extender and the adhesion promoter with the mass ratio, uniformly stirring, and barreling;
s2, when in use, the component A and the component B are mixed evenly according to the volume ratio to obtain the high-strength bi-component polyurethane adhesive.
The isocyanate of the component B in the invention is selected from German scientific institute (original Bayer) BAYER curing agent L75 (C).
Comparative example 1
The polyol polymer was changed to only vegetable oil polyol, as in example 3;
comparative example 2
The polyol polymer is changed into a mixture of polycaprolactone diol and vegetable oil polyol, and the mass ratio of the polycaprolactone diol to the vegetable oil polyol is 2: 3; the rest of the procedure was the same as in example 3;
comparative example 3
The number average molecular weight of polycaprolactone diol was changed to 400, and the hydroxyl value was 270-290mgKOH/g (available from Hunan Polyben chemical New Material science and technology Co., Ltd., model: PCL-2044), and the rest of the procedure was as in example 3;
comparative example 4
The average functionality of the vegetable oil polyol is 2, the hydroxyl value is 120-140mgKOH/g (purchased from air technology Co., Ltd., Zhang Home, model: FH-2130), and the rest is the same as in example 3;
comparative example 5
Mixing cashew nut shell oil polyalcohol with viscosity of 25 deg.C (cPs) of 8000 cPs; the hydroxyl value was 440mgKOH/g (from Kadeli, type: GX-9102), as in example 3;
comparative example 6
The modified nano titanium dioxide is changed into hydrophilic nano titanium dioxide with the model of VK-T25H, and the manufacturer is Hangzhou Wanjing new material company Limited; the rest of the procedure was the same as in example 3;
comparative example 7
The adhesion promoter was changed to contain only methacryloyloxyethyl phosphate as in example 3;
comparative example 8
The adhesion promoter was changed to contain only ethylene glycol methacrylate phosphate, as in example 3;
performance testing
1. Viscosity test, namely performing viscosity test on the high-strength bi-component polyurethane adhesive prepared in the embodiments 1 to 3 and the comparative examples 1 to 8, wherein the test method is to use an NDJ-7 rotational viscometer of Shanghai instruments (group) supply and sales companies to perform the test at room temperature, and the viscosity grade with the viscosity value lower than 1000cPs is set as C grade; setting the viscosity grade with the viscosity value in the range of 1000-2000cPs as B grade; the viscosity grade with the viscosity value in the range of 2000-3000cPs is set as A grade, which is shown in Table 1 specifically;
2. performing flexibility test, namely coating adhesive on an aluminum foil with the length of 10cm and the width of 2cm by a No. 25 wire rod for 2 times, drying at 60 ℃, cooling, folding at 35 ℃ respectively until white creases appear, calculating the folding times, setting 5 times for each sample, and taking the average value of the data; specific values are shown in table 1;
3. bonding strength: making a metal sheet into a standard sample sheet with the length of 100mm, the width of 25mm and the thickness of 2mm according to GB/T14732-;
4. and (3) testing weather resistance: the high-strength bi-component polyurethane adhesives prepared in the above examples 1 to 3 and comparative examples 1 to 8 were glued to an outdoor aluminum plate, and the gluing condition was observed after 3 months, as shown in table 1.
TABLE 1
Claims (10)
1. A high-strength bi-component polyurethane adhesive comprises a component A and a component B; the adhesive is characterized in that the component A comprises, by mass, 45-55% of a polyol polymer, 35-45% of an inorganic filler, 1-3% of a cross-linking agent, 1-2% of a wetting agent, 1-3% of a dispersing agent, 1-3% of a chain extender and 3-6% of an adhesion promoter; the component B is isocyanate; the volume ratio of the component A to the component B is 100: 20-30.
2. A high strength two-component polyurethane adhesive as claimed in claim 1, wherein the polyol polymer is a mixture of polycaprolactone diol, vegetable oil polyol, cashew nut shell oil polyol and castor oil.
3. The high-strength two-component polyurethane adhesive as claimed in claim 2, wherein the mass ratio of the polycaprolactone diol, the vegetable oil polyol, the cashew nut shell oil polyol and the castor oil is 2: 2.5-3.5: 3.5-4.5: 1.
4. the two-component polyurethane adhesive with high strength as claimed in claim 2 or 3, wherein the polycaprolactone diol has a number average molecular weight of 1000-3000 and a hydroxyl value of 35-120 mgKOH/g.
5. The two-component polyurethane adhesive with high strength as claimed in claim 2 or 3, wherein the vegetable oil polyol has an average functionality of 3-8 and a hydroxyl value of 150-450 mgKOH/g.
6. The high-strength two-component polyurethane adhesive as claimed in claim 2 or 3, wherein the viscosity of the cashew nut shell oil polyol is 1000-; the hydroxyl value is 75-200 mgKOH/g.
7. The high-strength two-component polyurethane adhesive as claimed in claim 1, wherein the inorganic filler is modified nano titanium dioxide.
8. The high-strength two-component polyurethane adhesive as claimed in claim 7, wherein the modified nano titanium dioxide has a specific surface area of 60-90m2Per g, the particle diameter is 20-30 nm.
9. The high-strength two-component polyurethane adhesive as claimed in claim 1, wherein the adhesion promoter is a mixture of methacryloyloxyethyl phosphate and ethylene glycol methacrylate phosphate in a mass ratio of 2: 1 to 1.5.
10. A method for preparing a high strength two-component polyurethane adhesive according to any one of claims 1 to 9, comprising the steps of:
s1, preparation of the component A: firstly, putting a polyalcohol polymer into a reaction kettle, uniformly stirring, heating to 80-100 ℃, carrying out vacuum dehydration, cooling to 50-70 ℃, sequentially adding an inorganic filler, a cross-linking agent, a wetting agent, a dispersing agent, a chain extender and an adhesion promoter, uniformly stirring, and barreling;
s2, when in use, the component A and the component B are mixed evenly according to the volume ratio to obtain the high-strength bi-component polyurethane adhesive.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812681A (en) * | 2021-02-08 | 2021-05-18 | 国网山东省电力公司济南供电公司 | Room temperature curing waterproof flame-retardant bi-component polyurethane casting resin and preparation method thereof |
| CN114763461A (en) * | 2021-12-27 | 2022-07-19 | 上海都昱新材料科技有限公司 | Heat-conducting solvent-free polyurethane lithium battery adhesive and preparation method thereof |
| CN115466588A (en) * | 2022-09-06 | 2022-12-13 | 有行鲨鱼(珠海)新材料科技有限公司 | Adhesive composition for carriage board and preparation method thereof |
| CN115820189A (en) * | 2021-12-29 | 2023-03-21 | 有行鲨鱼（上海）科技股份有限公司 | High-performance heat-sensitive polyurethane adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348469A (en) * | 2015-12-15 | 2016-02-24 | 山东北方现代化学工业有限公司 | Heat resistant waterproof high strength polyurethane adhesive and preparing method thereof |
| CN105820794A (en) * | 2016-05-30 | 2016-08-03 | 三友（天津）高分子技术有限公司 | Inorganic filler modified ultraviolet curing adhesive |
| CN108329883A (en) * | 2018-01-17 | 2018-07-27 | 上海华峰新材料研发科技有限公司 | Solvent-free class polyurethane adhesive of quick-dry type and preparation method thereof |
| CN110317564A (en) * | 2019-07-30 | 2019-10-11 | 厦门誉匠复合材料有限公司 | A kind of packaging process of polyurethane pouring sealant and its preparation method and application and nylon element |
-
2020
- 2020-10-09 CN CN202011074459.8A patent/CN112175572A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348469A (en) * | 2015-12-15 | 2016-02-24 | 山东北方现代化学工业有限公司 | Heat resistant waterproof high strength polyurethane adhesive and preparing method thereof |
| CN105820794A (en) * | 2016-05-30 | 2016-08-03 | 三友（天津）高分子技术有限公司 | Inorganic filler modified ultraviolet curing adhesive |
| CN108329883A (en) * | 2018-01-17 | 2018-07-27 | 上海华峰新材料研发科技有限公司 | Solvent-free class polyurethane adhesive of quick-dry type and preparation method thereof |
| CN110317564A (en) * | 2019-07-30 | 2019-10-11 | 厦门誉匠复合材料有限公司 | A kind of packaging process of polyurethane pouring sealant and its preparation method and application and nylon element |
Non-Patent Citations (2)
| Title |
|---|
| 刘益军: "《聚氨酯原料及助剂手册》", 30 April 2005, 化学工业出版社 * |
| 吴智勇: "《建筑装饰材料》", 31 July 2015, 北京理工大学出版 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812681A (en) * | 2021-02-08 | 2021-05-18 | 国网山东省电力公司济南供电公司 | Room temperature curing waterproof flame-retardant bi-component polyurethane casting resin and preparation method thereof |
| CN114763461A (en) * | 2021-12-27 | 2022-07-19 | 上海都昱新材料科技有限公司 | Heat-conducting solvent-free polyurethane lithium battery adhesive and preparation method thereof |
| CN114763461B (en) * | 2021-12-27 | 2024-04-12 | 上海都昱新材料科技有限公司 | Heat-conducting solvent-free polyurethane lithium battery adhesive and preparation method thereof |
| CN115820189A (en) * | 2021-12-29 | 2023-03-21 | 有行鲨鱼（上海）科技股份有限公司 | High-performance heat-sensitive polyurethane adhesive and preparation method thereof |
| CN115466588A (en) * | 2022-09-06 | 2022-12-13 | 有行鲨鱼(珠海)新材料科技有限公司 | Adhesive composition for carriage board and preparation method thereof |
| CN115466588B (en) * | 2022-09-06 | 2023-08-29 | 有行鲨鱼(珠海)新材料科技有限公司 | Bonding composition for carriage plate and preparation method thereof |
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