CN115232593A - Cold-thermal shock resistant flame-retardant bi-component polyurethane structural adhesive and preparation method thereof - Google Patents
Cold-thermal shock resistant flame-retardant bi-component polyurethane structural adhesive and preparation method thereof Download PDFInfo
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- CN115232593A CN115232593A CN202211069063.3A CN202211069063A CN115232593A CN 115232593 A CN115232593 A CN 115232593A CN 202211069063 A CN202211069063 A CN 202211069063A CN 115232593 A CN115232593 A CN 115232593A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a thermal shock resistant flame retardant type bi-component polyurethane structural adhesive and a preparation method thereof, wherein the component A comprises the following components: the curing agent comprises polyhydric alcohol, inorganic flame retardant, silane coupling agent, plasticizer and curing speed regulator; the polyester polyol is compounded by polyester polyol and polyether polyol; the component B comprises: modified polyester polyol, diisocyanate and an inorganic flame retardant; the modified polyester polyol is prepared by condensation reaction of difunctional alkyl acyl chloride and difunctional hydroxyl silane. The difunctional hydroxyl silane and the difunctional alkyl acyl chloride in the component B react to generate modified polyester polyol with alternately connected Si-O-Si and C-C chain segments, and the modified polyester polyol and a product of diisocyanate, namely an isocyanate-terminated prepolymer are further reacted with the polymeric polyol in the component A to generate the cross-linked reticular polyurethane structural adhesive which 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 thermal shock resistant flame-retardant bi-component polyurethane structural adhesive and a preparation method thereof.
Background
In recent years, with the increasing severity of world ecological environment pollution and the increasing of global energy crisis, new energy automobiles gradually become the mainstream of automobile industry development in China, and a power supply system is the power of the new energy automobiles and plays a decisive role in the performance of the new energy automobiles. More than 80% of the power supply system is made of organic chemical materials, and the power supply system comprises structural bonding materials, heat conduction materials, insulating materials, heat insulating materials, sealing materials and the like, wherein the structural bonding materials are mainly used for bonding an electric core and an electric core, the electric core and foam, the electric core and a module shell and the like, so that the electric core and the module are integrated, the requirements of the module on vibration resistance, impact resistance, falling resistance and the like are met, and the performance of the power supply system is 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 heated to 40-90 ℃, is a viscous liquid at normal temperature, and is widely used as a structural adhesive material of a power supply system due to the characteristics of good oil resistance and elasticity, wide bonding objects and easiness in bonding of polyurethane. For example, patent CN202010157137.3 discloses a two-component polyurethane structural adhesive for bonding power batteries and a preparation method thereof, 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 portions of bio-based polyol, 1 to 4 portions of fumed silica, 25 to 50 portions of flame retardant, 1 to 5 portions of adhesion promoter and 0.01 to 0.5 portion 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 aminobenzene silane with a silane modifier. Patent CN201911299534.8 discloses a two-component polyurethane adhesive for bonding power batteries and a preparation method thereof, wherein the raw material formula of component A comprises: 10-40% of hydrophobic polyol; 2 to 10 percent 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 to 50 percent of isocyanate; 2 to 10 percent of isocyanate tripolymer; 0.1 to 5 percent of water removing agent; 40-80% of surface modified heat-conducting filler; 0.1 to 1 percent of dispersing auxiliary agent.
In recent years, explosion accidents of new energy automobile batteries occur frequently, and more attention is paid to the performance of the structural adhesive under the condition of cold and hot shock accelerated aging. The solvent-free polyurethane structural adhesive is used for meeting the requirements of vibration resistance, impact resistance and drop resistance, bearing larger load and providing larger bonding strength, a large amount of polar fillers and rigid molecules are used in the structural adhesive, but the bonding strength is too attenuated under the condition of accelerated aging of cold and hot impact, and the risk of explosion in the charging process of the battery is increased.
Therefore, the development of the two-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 shock 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 thermal shock resistant flame retardant type two-component polyurethane structural adhesive and a preparation method thereof.
In order to realize the purpose, the following specific technical scheme is adopted:
a thermal shock resistant flame retardant type bi-component polyurethane structural adhesive comprises A, B components,
the component A comprises the following raw materials: the curing agent comprises a polyhydric alcohol, an inorganic flame retardant, a silane coupling agent, a plasticizer and a curing speed regulator; the polyester polyol is compounded by polyester polyol and polyether polyol;
the component B comprises the following raw materials: modified polyester polyol, diisocyanate and an 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, and the component A comprises the following raw materials in parts by weight: 25-60 parts of 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 difunctional hydroxysilane to difunctional alkyl acid chloride is from 1.12 to 1.25.
The difunctional hydroxyl silane is selected from one or the combination of two or more of (1,1,3,3-tetramethyl-1,3-disiloxanediyl) dimethanol, (1,1,3,3-tetramethyl-1,3-disiloxanediyl) diethanol, 1,3-bis (3-hydroxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-hydroxybutyl) tetramethyldisiloxane and 1,3-bis (3-hydroxyisobutyl) tetramethyldisiloxane.
The alkyl carbon atom number of the difunctional alkyl acyl chloride is 5-10, and the difunctional alkyl acyl chloride is specifically selected from one or a combination of two or more of glutaryl chloride, adipoyl chloride, 1,8-dioctanoyl chloride, 1,7-pimeloyl chloride, azelaioyl chloride and sebacoyl chloride. Preferably, the alkyl carbon number of the difunctional alkyl acyl chloride is 5-8, and the difunctional alkyl acyl chloride is specifically selected from one or a combination of two or more of glutaryl chloride, adipoyl chloride, 1,8-dioctanoyl chloride and 1,7-pimeloyl chloride.
The modified polyester polyol is prepared by a method comprising the following steps:
under the inert atmosphere, dissolving bifunctional alkyl acyl chloride and bifunctional hydroxyl silane in an organic solvent, heating and keeping the temperature constant, dropwise adding an acid-binding agent, reacting under the stirring condition, dropwise adding alkali liquor 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 the combination of two or more of N, N-dimethylcyclohexylamine, N-dimethylbenzylamine, triethanolamine, pyridine and N, N' -dimethylpyridine triethylamine; the molar ratio of the acid-binding agent to the bifunctional alkyl acyl chloride is 2.25-2.45; the dropping speed of the acid-binding agent is 0.5-1 drop/second; the organic solvent is selected from one or a combination of two of toluene, xylene and diphenyl ether; the temperature is increased to 100-130 ℃; the reaction time is 12-36h, the alkali liquor is not particularly limited, and the reaction time is common in the field and can be one or a combination of two of sodium hydroxide and sodium bicarbonate aqueous solution, the drying is to remove moisture by using a drying agent, the drying agent is not particularly limited and comprises anhydrous sodium sulfate, and the eluent separated by the chromatographic column is toluene to 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 selected from one or a combination of two of aliphatic polyester polyol and aromatic polyester polyol. The polyester polyol is obtained by polycondensation reaction of polyhydric alcohol and polybasic acid, wherein the polyhydric alcohol comprises one or a combination of two or more of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol and neopentyl glycol, and the polybasic acid is not particularly limited, and can be commonly used in the field, and comprises but not limited to one or a combination of 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 diol, polyoxypropylene triol, polyoxypropylene-ethylene oxide diol and ethylenediamine polyoxypropylene tetraol. The polyether glycol with larger functionality is beneficial to forming the polyurethane with a reticular structure, the bonding strength and the load bearing capacity of the polyurethane are improved, the higher the functionality is, the better the functionality is, and the too large the formed reticular structure is too complex, so that the hardness of the structural adhesive is increased, the elasticity is reduced, and the vibration and falling resistance performance is deteriorated.
The inorganic flame retardant is selected from one or the 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 function of improving the binding power, and is commonly used in the field, and comprises one or the combination of two or more of gamma-aminopropyltriethoxysilane, gamma- (2,3-epoxypropoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and isocyanic propyltriethoxysilane.
The plasticizer is selected from one or the combination of two or more of dimethyl methyl phosphate, diethyl ethyl phosphate, triethyl phosphate, cresyldiphenyl phosphate and tricresyl phosphate.
The curing speed regulator is a component which has the functions of controlling and regulating reaction speed and using time, and the type of the curing speed regulator is selected from one of tertiary amine catalysts and organic tin catalysts, and is specifically selected from one or a combination of two of dibutyltin dilaurate, stannous octoate, triethylene diamine, triethanolamine and triethylamine.
The diisocyanate is selected from one or two of aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate. The diisocyanate is preferably a composition of aromatic diisocyanate and alicyclic diisocyanate in a weight ratio of 1:3-4. The higher the functionality of the isocyanate is, the better the network structure is formed and the strength of the polyurethane structural adhesive is improved, but the structural adhesive is more brittle and has reduced toughness and reduced fatigue resistance, and the diisocyanate is selected and used in the invention.
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, 4,4' -methylene bis (phenyl isocyanate), which is 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, 4,4-diisocyanate dicyclohexylmethane, 1,4-cyclohexane dimethyldiisocyanate, which are commonly used in the art.
The component A can also comprise 0.5-2wt% of an auxiliary agent, wherein the auxiliary agent is selected from one or a combination of two or more of a thickening agent, a thixotropic agent, a coloring agent and a reinforcing agent.
The component B can also comprise 0.5-2wt% of an auxiliary agent, wherein the auxiliary agent is selected from one or a combination of two or more of an antioxidant, a thixotropic agent, a coloring agent and a reinforcing agent.
The antioxidant is selected from one or a combination of two or more of an antioxidant 1010, an antioxidant 1098 and an antioxidant 1076.
The thixotropic agent is fumed silica.
The reinforcing agent is one or the combination of two or more of calcium carbonate, talcum powder and silicon micropowder.
The colorant is not particularly limited, has a coloring function, does not react with other components in the structural adhesive to influence other properties of the structural adhesive, and comprises but is not limited to one of ultramarine blue, carbon black and titanium dioxide.
The invention also provides a preparation method of the thermal shock resistant flame retardant bi-component polyurethane structural adhesive, which comprises the following steps:
t1, mixing the polyhydric alcohol, the inorganic flame retardant, the silane coupling agent and the plasticizer, stirring uniformly, heating, vacuumizing, cooling, adding the curing speed regulator, vacuumizing, and stirring uniformly to obtain a component A;
t2, mixing the modified polyester polyol, diisocyanate and inorganic flame retardant, stirring uniformly, 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.
In the step T1, the temperature is increased to 100-130 ℃, the vacuum degree of vacuumizing after temperature increase is 0.01-0.1MPa, and the time is 1-3h; the temperature is reduced to room temperature of 50 ℃ below zero, the vacuum degree of the vacuumization after the temperature reduction is 0.01 MPa to 0.1MPa, and the time is 0.5 h to 1.5h;
in the step T2, the temperature is raised to 50-70 ℃, 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 dispersed more uniformly; the vacuum degree of the vacuum pumping 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 a prepolymer with end isocyanate groups, and-OH in the component A and-NCO in the component B react to generate polyurethane macromolecules after the component A, B is uniformly mixed.
An application of a thermal shock resistant flame retardant bi-component polyurethane structural adhesive is used for gluing in the assembling process of a new energy automobile power supply system.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the raw material difunctional hydroxyl silane in the component B and the difunctional alkyl acyl chloride react to generate the modified polyester polyol alternately connected with the chain segments of Si-O-Si and C-C, and the modified polyester polyol and the product of diisocyanate, namely the isocyanate-terminated prepolymer are then mixed with the polymeric polyol in the component A to generate the cross-linked reticular polyurethane structural adhesive which 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 by cooperating with the inorganic flame retardant.
The polyurethane structural adhesive prepared by the invention is suitable for bonding in the assembling process of a new energy automobile power supply system.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are parts by weight. All reagents used are commercially available in the art.
Aromatic polyester polyol available from Invista brand Terate 2000, functionality 2.3, hydroxyl number 295mgKOH/g;
polyoxypropylene triol was purchased from Santana chemical (Nantong) Inc. under the designation GP-310, number average molecular weight 1000, functionality 2.6.
Preparation of modified polyester polyol
Preparation example 1
Dissolving 1.25mol (1,1,3,3-tetramethyl-1,3-disiloxane diyl) dimethanol and 1mol of glutaryl chloride in 4.5mol of toluene under the nitrogen atmosphere, heating to 110 ℃, keeping the temperature, dropwise adding 2.275molN and N-dimethylcyclohexylamine at the dropping speed of 0.5 drop/second, reacting for 24 hours under the stirring condition, dropwise adding a saturated sodium hydroxide solution to neutrality after the reaction is finished, separating an organic phase, adding anhydrous sodium sulfate for drying, carrying out rotary evaporation and concentration, and carrying out chromatographic column separation by using a toluene and ethyl acetate eluent with the volume ratio of 4:1 to obtain the modified polyester polyol.
Preparation example 2
The procedure was as in preparation example 1, except that the glutaryl chloride was replaced with 1,7-pimeloyl chloride.
Preparation example 3
The procedure was as in preparation example 1 except that (1,1,3,3-tetramethyl-1,3-disiloxanediyl) dimethanol was used in an amount of 1.12mol.
Preparation example 4
The procedure of preparation example 1 was repeated, except that glutaryl chloride was replaced with sebacoyl chloride.
Preparation of two-component polyurethane structural adhesive
Example 1
T1, mixing 48 parts of aromatic polyester polyol Terate 2000, 12 parts of polyoxypropylene triol GP-310, 15 parts of aluminum hydroxide, 15 parts of ammonium polyphosphate, 1 part of gamma-aminopropyltriethoxysilane and 1 part of diethyl ethylphosphate, stirring uniformly, heating to 100 ℃, vacuumizing for 3 hours with the vacuum degree of 0.1MPa, cooling to room temperature, adding 1 part of dibutyltin dilaurate, vacuumizing to 0.1MPa, and stirring uniformly for 1 hour 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 uniformly, heating to 60 ℃, reacting for 3 hours at constant temperature, 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 in a weight ratio of 1:1 to obtain the double-component polyurethane structural adhesive.
Examples 2 to 4
The same as in example 1 except that the modified polyester polyol used in step T2 was prepared in accordance with preparation examples 2 to 4, respectively.
Example 5
The same as in example 1 except that the modified polyester polyol of preparation example 1 was used in an amount of 30 parts.
Example 6
The rest of the process is the same as the example 1, except that the amount of the aluminum hydroxide used in the step T1 is 12 parts, and the amount of the ammonium polyphosphate used in the step T1 is 18 parts; in the step T2, the amount of the aluminum hydroxide is 12 parts, and the amount of the ammonium polyphosphate is 18 parts.
Comparative example 1
The same as in example 1 except that the modified polyester polyol prepared in production example 1 was replaced with an aromatic polyester polyol Terate 2000 in step T2.
The above examples and comparative examples were prepared to be subjected to the following performance tests:
combustion performance: and the test is carried out according to the horizontal method and the vertical method for measuring the combustion performance of the plastic in the standard GB/T2408-2008.
Tensile shear strength: the single lap tensile shear strength of PET film to PET film, 30003 aluminum alloy to 30003 aluminum alloy, was tested with reference to the determination of the standard GB/T7124-2008 adhesive tensile shear strength (rigid material versus rigid material), with a tensile speed of 2mm/min, number of specimens 5, and the maximum shear failure load was recorded as the failure load, and the test results were expressed as the arithmetic mean of the tensile shear strength calculated by dividing the failure load by the shear area.
Cold and hot impact aging test: according to a standard GB/T31467.3-2015 battery pack, system safety requirements and a test method, a shear sample is placed in an alternating environment of (-40 +/-2) DEG C to- (85 +/-2) DEG C, the conversion time of two extreme temperatures is within 30min, the shear sample is kept for 8h in an extreme environment, circulation is carried out for 5 times, the shear strength is tested again, and the shear strength loss rate is calculated.
TABLE 1
The table shows that the polyurethane structural adhesive prepared by the invention has good cold and heat impact resistance, can bear larger load and has larger bonding strength.
It is apparent from example 1 and comparative example 1 that the modified polyester polyol prepared by the invention has the function of improving the flame retardant property of the structural adhesive in cooperation with the inorganic flame retardant.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
1. A thermal shock resistant flame retardant type bi-component polyurethane structural adhesive is characterized by comprising A, B components,
the component A comprises the following raw materials: the curing agent comprises a polyhydric alcohol, an inorganic flame retardant, a silane coupling agent, a plasticizer and a curing speed regulator; the polyester polyol is compounded by polyester polyol and polyether polyol;
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.
2. The cold-thermal shock resistant flame retardant two-component polyurethane structural adhesive according to claim 1, wherein the weight ratio of the component A to the component B is 1-1.3,
the component A comprises the following raw materials in parts by weight: 25-60 parts of 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 difunctional hydroxyl silane to difunctional alkyl acid chloride is from 1.12 to 1.25.
3. The structural cold-and hot-shock-resistant, flame-retardant, two-component polyurethane adhesive of claim 1, wherein the difunctional hydroxysilane is selected from the group consisting of (1,1,3,3-tetramethyl-1,3-disiloxane diyl) dimethanol, (1,1,3,3-tetramethyl-1,3-disiloxane diyl) diethanol, 1,3-bis (3-hydroxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-hydroxybutyl) tetramethyldisiloxane, 1,3-bis (3-hydroxyisobutyl) tetramethyldisiloxane; the alkyl carbon atom number of the difunctional alkyl acyl chloride is 5-10, and the difunctional alkyl acyl chloride is selected from one or the combination of two or more of glutaryl chloride, adipoyl chloride, 1,8-dioctanoyl chloride, 1,7-pimeloyl chloride, azelaioyl chloride and sebacoyl chloride; preferably, the alkyl carbon atom number of the difunctional alkyl acyl chloride is 5-8, and the difunctional alkyl acyl chloride is selected from one or the combination of two or more of glutaryl chloride, adipoyl chloride, 1,8-dioctanoyl chloride and 1,7-pimeloyl chloride.
4. The structural cold-thermal shock resistant flame retardant two-component polyurethane adhesive of claim 1, wherein the modified polyester polyol is prepared by a process comprising the steps of:
under the inert atmosphere, dissolving bifunctional alkyl acyl chloride and bifunctional hydroxyl silane in an organic solvent, heating and keeping the temperature constant, dropwise adding an acid-binding agent, reacting under the stirring condition, dropwise adding alkali liquor 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.
5. The structural adhesive according to claim 1, wherein the acid-binding agent is a tertiary amine compound selected from one or a combination of two or more of N, N-dimethylcyclohexylamine, N-dimethylbenzylamine, triethanolamine, pyridine, and N, N' -dimethylpyridine triethylamine; the molar ratio of the acid-binding agent to the bifunctional alkyl acyl chloride is 2.25-2.45; the dropping speed of the acid-binding agent is 0.5-1 drop/second; the temperature is increased 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.
6. The structural cold-thermal shock resistant and flame retardant two-component polyurethane adhesive of claim 1, wherein the polyester polyol has a functionality of 2 to 3 and a hydroxyl value of 200 to 400mgKOH/g; the polyester polyol is selected from one or a 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; 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 diol, polyoxypropylene triol, polyoxypropylene-ethylene oxide diol and ethylenediamine polyoxypropylene tetraol.
7. The thermal shock resistant flame retardant 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; 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.
8. The structural cold-heat shock resistant and flame retardant two-component polyurethane adhesive according to claim 1, wherein the diisocyanate is one or a combination of two of aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate; preferably, 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 the combination of two or more of toluene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate and 4,4' -methylene bis (phenyl isocyanate); the alicyclic diisocyanate is selected from one or the combination of two or more of isophorone diisocyanate, 4,4-diisocyanate dicyclohexylmethane and 1,4-cyclohexane dimethyl diisocyanate.
9. The preparation method of the cold-heat shock resistant and flame retardant two-component polyurethane structural adhesive according to any one of claims 1 to 8, which is characterized by comprising the following steps:
t1, mixing the polyhydric alcohol, the inorganic flame retardant, the silane coupling agent and the plasticizer, stirring uniformly, heating, vacuumizing, cooling, adding the curing speed regulator, vacuumizing, and stirring uniformly to obtain a component A;
t2, mixing the modified polyester polyol, diisocyanate and inorganic flame retardant, stirring uniformly, 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.
10. The method for preparing the thermal shock resistant flame retardant two-component polyurethane structural adhesive according to claim 9, wherein the temperature rise in the step T1 is increased to 100 to 130 ℃; in the step T2, the temperature is raised to 50-70 ℃, and the reaction time is 1-3h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117447958A (en) * | 2023-12-21 | 2024-01-26 | 山东一诺威聚氨酯股份有限公司 | High-temperature-resistant aging-resistant heat-conducting polyurethane structural adhesive and preparation method thereof |
| CN117447958B (en) * | 2023-12-21 | 2024-04-19 | 山东一诺威聚氨酯股份有限公司 | High-temperature-resistant aging-resistant heat-conducting polyurethane structural adhesive and preparation method thereof |
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| CN111040418A (en) * | 2019-12-26 | 2020-04-21 | 刘大刚 | Color-homogenizing high-toughness plastic film and preparation process thereof |
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| CN117447958B (en) * | 2023-12-21 | 2024-04-19 | 山东一诺威聚氨酯股份有限公司 | High-temperature-resistant aging-resistant heat-conducting polyurethane structural adhesive and preparation method thereof |
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