CN115232593B - Cold and hot shock resistant flame retardant type bi-component polyurethane structural adhesive and preparation method thereof - Google Patents
Cold and hot shock resistant flame retardant type bi-component polyurethane structural adhesive and preparation method thereof Download PDFInfo
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- CN115232593B CN115232593B CN202211069063.3A CN202211069063A CN115232593B CN 115232593 B CN115232593 B CN 115232593B CN 202211069063 A CN202211069063 A CN 202211069063A CN 115232593 B CN115232593 B CN 115232593B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4692—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing silicon
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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
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a cold-heat shock resistant flame retardant bi-component polyurethane structural adhesive and a preparation method thereof, wherein the component A comprises the following components: a polyol, an inorganic flame retardant, a silane coupling agent, a plasticizer, and a curing speed regulator; the polyatomic alcohol is compounded by polyester polyatomic alcohol and polyether polyatomic alcohol; the component B comprises: modified polyester polyol, diisocyanate and inorganic flame retardant; the modified polyester polyol is prepared by the condensation reaction of difunctional alkyl acyl chloride and difunctional hydroxyl silane. The modified polyester polyol with Si-O-Si and C-C chain segments alternately connected is produced by the reaction of the difunctional hydroxyl silane and the difunctional alkyl acyl chloride in the component B, and the cross-linked reticular polyurethane structural adhesive produced by the reaction of the modified polyester polyol and the product-terminal isocyanate prepolymer of diisocyanate and the polyol in the component A has good cold and hot impact performance, can bear larger load and has larger bonding strength.
Description
Technical Field
The invention belongs to the technical field of polyurethane adhesives, and particularly relates to a cold-heat shock resistant flame retardant type bi-component polyurethane structural adhesive and a preparation method thereof.
Background
In recent years, along with the increasing serious environmental pollution of the world and the continuous aggravation of global energy crisis, new energy automobiles gradually become the main stream of automobile industry development in China, and a power supply system is the power place of the new energy automobiles and plays a decisive role in the performance of the new energy automobiles. The power supply system is composed of more than 80% of organic chemical materials, and comprises structural bonding materials, heat conducting materials, insulating materials, heat insulating materials, sealing materials and the like, wherein the structural bonding materials are mainly used for bonding the battery core and the battery core, the battery core and foam, the battery core and a module shell and the like, and the battery core and the module are integrated, so that the requirements of vibration resistance, impact resistance, drop resistance and the like of the module are required to be met, and the performance of the power supply system is greatly influenced by the performance of the power supply system and the service life of the power supply system.
The solvent-free polyurethane structural adhesive is a structural adhesive material which can be coated and bonded without using any solvent, is a low-viscosity liquid capable of flowing when being heated to 40-90 ℃, is a viscous liquid at normal temperature, and has the characteristics of good oil resistance and elasticity, wide bonding objects and easy bonding, so that the solvent-free polyurethane structural adhesive is widely used as the structural adhesive material of a power supply system. As disclosed in patent CN202010157137.3, a two-component polyurethane structural adhesive for bonding a power battery and a preparation method thereof are disclosed, wherein the polyurethane structural adhesive comprises a component a and a component B; the component A comprises 40-65 parts of polymethylene polyphenyl isocyanate, 30-50 parts of aluminum hydroxide, 2-5 parts of hydrophobic fumed silica and 0-5 parts of plasticizer; the component B comprises 40 to 65 parts of biological polyol, 1 to 4 parts of gas-phase white carbon black, 25 to 50 parts of flame retardant, 1 to 5 parts of adhesion promoter and 0.01 to 0.5 part of catalyst; the bio-based polyol is selected from one or more of rapeseed oil modified polyol, castor oil modified polyol, soybean oil modified polyol and palm oil modified polyol; the adhesion promoter is prepared by reacting aminophenylsilane with a silane modifier. Patent CN201911299534.8 discloses a two-component polyurethane adhesive for bonding power batteries and a preparation method thereof, and the raw material formula of component a comprises: 10-40% of hydrophobic polyol; 2-10% of polyester polyol; 1 to 10 percent of molecular sieve; 40-80% of surface modified heat conducting filler; 0.1 to 5 percent of other fillers; 0.1 to 0.5 percent of catalyst; the raw material formula of the component B comprises: 10-50% of isocyanate; 2-10% of isocyanate trimer; 0.1 to 5 percent of water scavenger; 40-80% of surface modified heat conducting filler; 0.1 to 1 percent of dispersing auxiliary agent.
In recent years, new energy automobile battery explosion accidents frequently occur, and the performance of structural adhesive under the condition of accelerated aging of cold and hot impact is also more important. The technology is solvent-free polyurethane structural adhesive, which can bear larger load and provide larger bonding strength for meeting the requirements of vibration resistance, impact resistance and drop resistance, and a large amount of polar fillers and rigid molecules are used in the structural adhesive, but the attenuation of the bonding strength under the accelerated aging of cold and hot impact is overlarge, so that the risk of explosion in the battery charging process is increased.
Therefore, developing a double-component polyurethane structural adhesive which can bear larger load, provide larger bonding strength and have lower bonding strength attenuation under the condition of cold and hot impact accelerated aging has important significance for life safety of people and application and popularization of new energy automobiles.
Disclosure of Invention
In order to solve the technical problems, the invention provides a cold and hot shock resistant flame retardant type bi-component polyurethane structural adhesive and a preparation method thereof, wherein bi-functional hydroxyl silane and bi-functional alkyl acyl chloride are used as raw materials to prepare modified polyester polyol, the modified polyester polyol and diisocyanate are prepolymerized to obtain a product isocyanate-terminated prepolymer, and when the polyurethane structural adhesive is used, the A component containing the polyol and the B component containing the isocyanate-terminated prepolymer are mixed to generate the cold and hot shock resistant polyurethane structural adhesive which can bear larger load and has a cross-linked net shape with larger bonding strength.
In order to achieve the above purpose, the following specific technical scheme is adopted:
a cold-heat resistant flame-retardant bi-component polyurethane structural adhesive comprises A, B components,
the component A comprises the following raw materials: a polyol, an inorganic flame retardant, a silane coupling agent, a plasticizer, and a curing speed regulator; the polyatomic alcohol is compounded by polyester polyatomic alcohol and polyether polyatomic alcohol;
the component B comprises the following raw materials: modified polyester polyol, diisocyanate and inorganic flame retardant; the modified polyester polyol is prepared by condensation reaction of difunctional alkyl acyl chloride and difunctional hydroxyl silane.
Further, the weight ratio of the component A to the component B is 1-1.3:1, and the component A comprises the following raw materials in parts by weight: 25-60 parts of poly polyol, 20-40 parts of inorganic flame retardant, 0.1-2 parts of silane coupling agent, 1-5 parts of plasticizer and 0.01-1 part of curing speed regulator; the weight ratio of the polyester polyol to the polyether polyol is 3-5:1, preferably 2-4:1;
the component B comprises the following raw materials in parts by weight: 20-30 parts of modified polyester polyol, 25-50 parts of diisocyanate and 25-50 parts of inorganic flame retardant; the molar ratio of the difunctional hydroxyl silane to the difunctional alkyl acyl chloride is 1.12-1.25:1.
The difunctional hydroxysilane is selected from (1, 3-tetramethyl-1, 3-disiloxane diyl) dimethanol, (1, 3-tetramethyl-1, 3-disiloxane diyl) diethanol 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane, 1, 3-bis (3-hydroxyisobutyl) tetramethyldisiloxane, or a combination of two or more thereof.
The alkyl carbon number of the difunctional alkyl acyl chloride is 5-10, and the difunctional alkyl acyl chloride is one or a combination of two or more selected from glutaryl chloride, adipoyl chloride, 1, 8-dioctyl acyl chloride, 1, 7-pimeloyl chloride, nonyldiacyl chloride and sebacoyl chloride. Preferably, the difunctional alkyl acyl chloride has an alkyl carbon number of 5-8, and is specifically selected from one or a combination of two or more of glutaryl chloride, adipoyl chloride, 1, 8-dioctyl acyl chloride and 1, 7-pimeloyl chloride.
The modified polyester polyol is prepared by a process comprising the steps of:
under inert atmosphere, dissolving difunctional alkyl acyl chloride and difunctional hydroxyl silane in an organic solvent, heating and keeping constant temperature, dropwise adding an acid binding agent, reacting under stirring, dropwise adding an alkali solution to be neutral after the reaction is finished, separating an organic phase, drying, concentrating, and separating by a chromatographic column to obtain the modified polyester polyol.
The acid binding agent is a tertiary amine compound, and is selected from one or a combination of two or more of N, N-dimethyl cyclohexylamine, N-dimethyl benzylamine, triethanolamine, pyridine and N, N' -dimethyl pyridine triethylamine; the mol ratio of the acid binding agent to the difunctional alkyl acyl chloride is 2.25-2.45:1; the dropping speed of the acid binding agent is 0.5-1 drop/second; the organic solvent is selected from one or two of toluene, xylene and diphenyl ether; raising the temperature to 100-130 ℃; the reaction time is 12-36h, the alkali liquor is not particularly limited, the alkali liquor is commonly used in the field and comprises one or two of sodium hydroxide and sodium bicarbonate aqueous solution, the drying is to remove water by using a drying agent, the drying agent is not particularly limited and comprises anhydrous sodium sulfate, the eluent separated by the chromatographic column is toluene and ethyl acetate, and the volume ratio of the toluene to the ethyl acetate is 2-5:1.
The functionality of the polyester polyol is 2-3, and the hydroxyl value is 200-400mgKOH/g. The polyester polyol is one or the combination of two of aliphatic polyester polyol and aromatic polyester polyol. The polyester polyol is obtained by polycondensation reaction of a polyhydric alcohol and a polybasic acid, wherein the polyhydric alcohol comprises one or two or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, triethylene glycol and neopentyl glycol, the polybasic acid is not particularly limited, and the polybasic acid is commonly used in the field and comprises one or two or more of phthalic acid, terephthalic acid, adipic acid, sebacic acid and azelaic acid.
The functionality of the polyether polyol is 2-4, and the number average molecular weight is 500-1500; preferably, the polyether polyol has a functionality of 2.5 to 4 and a data molecular weight of 1000 to 1500. The polyether polyol is selected from one or two of polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene-ethylene glycol and ethylenediamine polyoxypropylene tetraol. The polyether polyol with larger functionality is favorable for forming polyurethane with a reticular structure, the bonding strength and the load bearing capacity of the polyurethane are improved, the larger the functionality is, the better the larger the functionality is, the more complex the reticular structure is formed, so that the hardness of the structural adhesive is increased, the elasticity is reduced, and the shock resistance and the drop resistance are deteriorated.
The inorganic flame retardant is selected from one or a combination of two or more of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, melamine polyphosphate and melamine cyanurate. Preferably, the inorganic flame retardant is a composition of aluminum hydroxide and ammonium polyphosphate in a weight ratio of 1:1-3; more preferably, the inorganic flame retardant is a composition of aluminum hydroxide and ammonium polyphosphate in a weight ratio of 1:1-1.5.
The coupling agent has the effect of improving the adhesion force, and is commonly used in the field, and comprises one or a combination of two or more of gamma-aminopropyl triethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane and isocyanic acid propyl triethoxysilane.
The plasticizer is selected from one or a combination of two or more of methyl dimethyl phosphate, ethyl diethyl phosphate, triethyl phosphate, toluene diphenyl phosphate and tricresyl phosphate.
The curing speed regulator is a component for controlling and regulating the reaction speed and the usable time, the type of the curing speed regulator is one selected from tertiary amine catalysts and organotin catalysts, and the curing speed regulator is one or a combination of two selected from dibutyl tin dilaurate, stannous octoate, triethylenediamine, triethanolamine and triethylamine.
The diisocyanate is selected from one or two of aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate. Preferably, the diisocyanate is an aromatic diisocyanate and the cycloaliphatic diisocyanate is present in a weight ratio of 1:3-4. The higher the functionality of isocyanate is, the more favorable to form a network structure, and the strength of polyurethane structural adhesive is improved, but the higher the functionality is, the more fragile the structural adhesive is, the toughness is reduced, and the fatigue resistance is reduced.
The aromatic diisocyanate is not particularly limited, and may be one or a combination of two or more selected from TDI toluene diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, and 4,4' -methylenebis (phenyl isocyanate), which are commonly used in the art.
The alicyclic diisocyanate is not particularly limited, and may be one or a combination of two or more selected from isophorone diisocyanate, 4-diisocyanate dicyclohexylmethane and 1, 4-cyclohexanedimethyl diisocyanate, which are commonly used in the art.
The component A can also comprise 0.5-2wt% of auxiliary agent, wherein the auxiliary agent is one or a combination of two or more of thickening agent, thixotropic agent, colorant and reinforcing agent.
The component B can also comprise 0.5-2wt% of auxiliary agent, wherein the auxiliary agent is selected from one or a combination of two or more of antioxidant, thixotropic agent, colorant and reinforcing agent.
The antioxidant is selected from one or a combination of two or more of antioxidant 1010, antioxidant 1098 and antioxidant 1076.
The thixotropic agent is fumed silica.
The reinforcing agent is selected from one or more of calcium carbonate, talcum powder and silicon micropowder.
The colorant is not particularly limited, and has a coloring function, and can not react with other components in the structural adhesive to affect other properties of the structural adhesive, including but not limited to one of ultramarine blue, carbon black and titanium pigment.
The invention also provides a preparation method of the cold-heat resistant flame-retardant bi-component polyurethane structural adhesive, which comprises the following steps:
t1, mixing the polyalcohol, the inorganic flame retardant, the silane coupling agent and the plasticizer, stirring to be uniform, heating, vacuumizing, cooling, adding the curing speed regulator, vacuumizing, and stirring to be uniform to obtain a component A;
t2 mixing the modified polyester polyol, diisocyanate and inorganic flame retardant, stirring to be uniform, heating and reacting at constant temperature, naturally cooling to room temperature after the reaction is finished, and vacuumizing to obtain a component B;
and T3, uniformly mixing the component A and the component B to obtain the double-component polyurethane structural adhesive.
The temperature is raised to 100-130 ℃ in the step T1, the vacuum degree of the vacuumized air after the temperature is raised is 0.01-0.1MPa, and the time is 1-3h; the temperature is reduced to the room temperature of-50 ℃, the vacuum degree of the vacuumized air after the temperature reduction is 0.01-0.1MPa, and the time is 0.5-1.5h;
the temperature is raised to 50-70 ℃ in the step T2, the reaction time is 1-3h, and the inorganic flame retardant can be added into the reaction kettle in 1-5 batches so as to be more uniformly dispersed; the vacuum degree of the vacuumizing is 0.01-0.1MPa, and the time is 0.5-1.5h.
The component B is a system with-NCO/-OH > 1, modified polyester polyol and diisocyanate react to generate isocyanate-terminated prepolymer, and A, B component A and-NCO in component B react to generate polyurethane macromolecules after being uniformly mixed.
The application of the cold-heat shock resistant flame retardant type bi-component polyurethane structural adhesive is used for cementing in the process of assembling a power supply system of a new energy automobile.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses the raw materials of the component B, namely the difunctional hydroxyl silane and the difunctional alkyl acyl chloride to react to generate the modified polyester polyol with Si-O-Si and C-C chain segments alternately connected, and the modified polyester polyol and the product of diisocyanate, namely the isocyanate prepolymer, are used for removing the crosslinking reticular polyurethane structural adhesive generated by the polyol in the component A, so that the modified polyester polyol has good cold and heat shock resistance, can bear larger load and has larger bonding strength.
The inventor finds that the modified polyester polyol has the function of improving the flame retardant property of the polyurethane structural adhesive in cooperation with the inorganic flame retardant.
The polyurethane structural adhesive prepared by the invention is suitable for cementing in the process of assembling a power supply system of a new energy automobile.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited to the disclosure. Unless otherwise specified, "parts" are parts by weight in the examples of the present invention. All reagents used are those commercially available in the art.
Aromatic polyester polyol available from Invista brand Terate 2000, functionality 2.3, hydroxyl number 295mgKOH/g;
the polyoxypropylene triol was purchased from Morda chemical (Nantong) Inc., trade name GP-310, number average molecular weight 1000, functionality 2.6.
Preparation of modified polyester polyol
Preparation example 1
Under nitrogen atmosphere, 1.25mol of (1, 3-tetramethyl-1, 3-disiloxane diyl) dimethanol and 1mol of glutaryl chloride are dissolved in 4.5mol of toluene, the temperature is raised to 110 ℃ and kept constant, 2.275mol of N, N-dimethylcyclohexylamine is dropwise added, the reaction is carried out for 24 hours under the stirring condition, saturated sodium hydroxide solution is dropwise added until the reaction is neutral after the reaction is finished, an organic phase is separated, anhydrous sodium sulfate is added for drying, rotary evaporation and concentration are carried out, and toluene-ethyl acetate eluent with the volume ratio of 4:1 is used for chromatographic column separation, thus obtaining the modified polyester polyol.
Preparation example 2
The remainder was the same as in preparation example 1 except that 1, 7-pimeloyl chloride was used instead of glutaryl chloride.
Preparation example 3
The remainder was the same as in preparation example 1 except that (1, 3-tetramethyl-1, 3-disilanediyl) dimethanol was used in an amount of 1.12mol.
Preparation example 4
The rest is the same as in preparation example 1, except that sebacoyl chloride is used instead of glutaryl chloride.
Preparation of two-component polyurethane structural adhesive
Example 1
T1 mixing 48 parts of aromatic polyester polyol terrate 2000, 12 parts of polyoxypropylene triol GP-310, 15 parts of aluminum hydroxide, 15 parts of ammonium polyphosphate, 1 part of gamma-aminopropyl triethoxysilane and 1 part of diethyl ethylphosphate, stirring uniformly, heating to 100 ℃, vacuumizing for 3 hours, reducing the vacuum degree to 0.1MPa, cooling to room temperature, adding 1 part of dibutyl tin dilaurate, vacuumizing to 0.1MPa, stirring for 1 hour uniformly to obtain a component A;
t2 mixing 20 parts of modified polyester polyol prepared in preparation example 1, 10 parts of 4,4' -methylenebis (phenyl isocyanate), 40 parts of isophorone diisocyanate, 15 parts of aluminum hydroxide and 15 parts of ammonium polyphosphate, stirring to be uniform, heating to 60 ℃ and keeping the temperature for reaction for 3 hours, naturally cooling to room temperature after the reaction is finished, vacuumizing for 1.5 hours, and obtaining a component B, wherein the vacuum degree is 0.1 MPa;
and T3, uniformly mixing A, B components according to the weight ratio of 1:1 to obtain the double-component polyurethane structural adhesive.
Examples 2 to 4
The remainder was the same as in example 1 except that the modified polyester polyols used in step T2 were prepared in accordance with preparation examples 2 to 4, respectively.
Example 5
The remainder was the same as in example 1 except that the modified polyester polyol of production example 1 was used in an amount of 30 parts.
Example 6
The rest is the same as in example 1 except that the amount of aluminum hydroxide used in step T1 is 12 parts and the amount of ammonium polyphosphate used is 18 parts; the amount of aluminum hydroxide used in the step T2 was 12 parts, and the amount of ammonium polyphosphate was 18 parts.
Comparative example 1
The remainder was the same as in example 1 except that the modified polyester polyol prepared in preparation example 1 was replaced with aromatic polyester polyol rate 2000 in step T2.
The following performance tests were performed on the preparation of the above examples and comparative examples:
combustion performance: the test was performed with reference to the standard GB/T2408-2008 horizontal and vertical methods for determining the burning properties of plastics.
Tensile shear strength: with reference to the measurement of tensile shear strength of the standard GB/T7124-2008 adhesive (rigid material to rigid material), the single lap tensile shear strength of PET film and PET film, 30003 aluminum alloy and 30003 aluminum alloy was tested, the tensile speed was 2mm/min, the number of samples was 5, the maximum load of shear failure was recorded as the failure load, the test result was expressed as the arithmetic average of the tensile shear strength, and the tensile shear strength was calculated by dividing the failure load by the shear area.
Cold and hot impact aging test: with reference to standard GB/T31467.3-2015 battery pack, system safety requirements and test methods, placing a shear sample in an alternating environment with (-40+/-2) DEG C- (85+/-2) DEG C, wherein the conversion time of two extreme temperatures is within 30min, and the shear sample is kept for 8h in each extreme environment, circulated for 5 times, and then the shear strength is tested again, and the shear strength loss rate is calculated.
TABLE 1
The polyurethane structural adhesive prepared by the invention has good cold and hot shock resistance, can bear larger load and has larger bonding strength.
It is obvious from example 1 and comparative example 1 that the modified polyester polyol prepared by the invention has the effect of improving the flame retardant property of the structural adhesive in cooperation with the inorganic flame retardant.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (15)
1. A cold-heat resistant flame-retardant bi-component polyurethane structural adhesive is characterized by comprising a A, B component,
the weight ratio of the component A to the component B is 1-1.3:1,
the component A comprises the following raw materials in parts by weight: 25-60 parts of poly polyol, 20-40 parts of inorganic flame retardant, 0.1-2 parts of silane coupling agent, 1-5 parts of plasticizer and 0.01-1 part of curing speed regulator; the polyatomic alcohol is compounded by polyester polyol and polyether polyol, and the weight ratio of the polyester polyol to the polyether polyol is 3-5:1; the curing speed regulator is selected from one of tertiary amine catalysts and organotin catalysts;
the component B comprises the following raw materials in parts by weight: 20-30 parts of modified polyester polyol, 25-50 parts of diisocyanate and 25-50 parts of inorganic flame retardant; the modified polyester polyol is prepared by condensation reaction of difunctional alkyl acyl chloride and difunctional hydroxyl silane; the molar ratio of the difunctional hydroxyl silane to the difunctional alkyl acyl chloride is 1.12-1.25:1.
2. The cold and hot shock resistant flame retardant two-component polyurethane structural adhesive of claim 1, wherein the weight ratio of the polyester polyol to the polyether polyol is 2-4:1.
3. The cold-heat shock resistant flame retardant two-component polyurethane structural adhesive of claim 1, which is characterized in that, the difunctional hydroxysilane is selected from (1, 3-tetramethyl-1, 3-disiloxane diyl) dimethanol, (1, 3-tetramethyl-1, 3-disiloxane diyl) diethanol one or two or more of 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane, 1, 3-bis (4-hydroxybutyl) tetramethyl disiloxane and 1, 3-bis (3-hydroxyisobutyl) tetramethyl disiloxane; the alkyl carbon number of the difunctional alkyl acyl chloride is 5-10, and the difunctional alkyl acyl chloride is one or a combination of two or more of glutaryl chloride, adipoyl chloride, 1, 8-dioctyl acyl chloride, 1, 7-pimeloyl chloride, nonyldichloride and sebacoyl chloride.
4. The cold and hot shock resistant flame retardant two-component polyurethane structural adhesive according to claim 1, wherein the difunctional alkyl acyl chloride is selected from one or a combination of two or more of glutaryl chloride, adipoyl chloride, 1, 8-dioctyl acyl chloride and 1, 7-heptyldichloride.
5. The cold and hot shock resistant flame retardant two-component polyurethane structural adhesive of claim 1, wherein the modified polyester polyol is prepared by a process comprising the steps of:
under inert atmosphere, dissolving difunctional alkyl acyl chloride and difunctional hydroxyl silane in an organic solvent, heating and keeping constant temperature, dropwise adding an acid binding agent, reacting under stirring, dropwise adding an alkali solution to be neutral after the reaction is finished, separating an organic phase, drying, concentrating, and separating by a chromatographic column to obtain the modified polyester polyol.
6. The cold-heat shock resistant flame retardant type two-component polyurethane structural adhesive according to claim 5, wherein the acid binding agent is a tertiary amine compound, and is selected from one or a combination of two or more of N, N-dimethylcyclohexylamine, N-dimethylbenzylamine, triethanolamine, pyridine and N, N' -dimethylpyridine triethylamine; the mol ratio of the acid binding agent to the difunctional alkyl acyl chloride is 2.25-2.45:1; the dropping speed of the acid binding agent is 0.5-1 drop/second; raising the temperature to 100-130 ℃; the reaction time is 12-36h; the eluent separated by the chromatographic column is toluene and ethyl acetate, and the volume ratio of the toluene to the ethyl acetate is 2-5:1.
7. The cold-heat shock resistant flame retardant two-component polyurethane structural adhesive of claim 1, wherein the polyester polyol has a functionality of 2-3 and a hydroxyl value of 200-400mgKOH/g; the polyester polyol is one or the combination of two of aliphatic polyester polyol and aromatic polyester polyol; the functionality of the polyether polyol is 2-4, and the number average molecular weight is 500-1500; the polyether polyol is selected from one or two of polyoxypropylene glycol, polyoxypropylene triol, polyoxypropylene-ethylene glycol and ethylenediamine polyoxypropylene tetraol.
8. The cold-heat shock resistant flame retardant two-component polyurethane structural adhesive of claim 7, wherein the polyether polyol has a functionality of 2.5-4 and a number average molecular weight of 1000-1500.
9. The cold-heat shock resistant flame retardant type two-component polyurethane structural adhesive according to claim 1, wherein the inorganic flame retardant is selected from one or a combination of two or more of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, melamine polyphosphate and melamine cyanurate.
10. The cold and hot shock resistant flame retardant type two-component polyurethane structural adhesive of claim 9, wherein the inorganic flame retardant is a composition of aluminum hydroxide and ammonium polyphosphate according to a weight ratio of 1:1-3.
11. The cold and hot shock resistant flame retardant type two-component polyurethane structural adhesive of claim 10, wherein the inorganic flame retardant is a composition of aluminum hydroxide and ammonium polyphosphate in a weight ratio of 1:1-1.5.
12. The cold-heat shock resistant flame retardant two-component polyurethane structural adhesive according to claim 1, wherein the diisocyanate is selected from one or a combination of two of aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate.
13. The cold-heat shock resistant flame retardant two-component polyurethane structural adhesive of claim 12, wherein the diisocyanate is a composition of aromatic diisocyanate and alicyclic diisocyanate in a weight ratio of 1:3-4; the aromatic diisocyanate is selected from one or a combination of two or more of toluene diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate and 4,4' -methylenebis (phenyl isocyanate); the alicyclic diisocyanate is selected from one or a combination of two or more of isophorone diisocyanate, 4-diisocyanate dicyclohexylmethane and 1, 4-cyclohexanedimethyl diisocyanate.
14. The method for preparing the cold-heat-resistant flame-retardant two-component polyurethane structural adhesive as claimed in any one of claims 1 to 13, which is characterized by comprising the following steps:
t1, mixing the polyalcohol, the inorganic flame retardant, the silane coupling agent and the plasticizer, stirring to be uniform, heating, vacuumizing, cooling, adding the curing speed regulator, vacuumizing, and stirring to be uniform to obtain a component A;
t2 mixing the modified polyester polyol, diisocyanate and inorganic flame retardant, stirring to be uniform, heating and reacting at constant temperature, naturally cooling to room temperature after the reaction is finished, and vacuumizing to obtain a component B;
and T3, uniformly mixing the component A and the component B to obtain the double-component polyurethane structural adhesive.
15. The method for preparing the cold and hot shock resistant flame retardant type two-component polyurethane structural adhesive according to claim 14, wherein the temperature rise in the step T1 is 100-130 ℃; and (3) heating to 50-70 ℃ in the step T2, wherein the reaction time is 1-3h.
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