CN116265558B - Polyurethane structural adhesive with low specific gravity and high heat conduction and preparation method thereof - Google Patents

Polyurethane structural adhesive with low specific gravity and high heat conduction and preparation method thereof Download PDF

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Publication number
CN116265558B
CN116265558B CN202310136216.XA CN202310136216A CN116265558B CN 116265558 B CN116265558 B CN 116265558B CN 202310136216 A CN202310136216 A CN 202310136216A CN 116265558 B CN116265558 B CN 116265558B
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parts
component
structural adhesive
polyester polyol
polyol
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CN116265558A (en
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何志球
方珍英
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Youxing Shark Zhuhai New Material Technology Co ltd
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Youxing Shark Zhuhai New Material Technology Co ltd
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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
    • 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
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/4266—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
    • 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
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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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
    • 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
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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 relates to the technical field of C09J175/00, in particular to a polyurethane structural adhesive with low specific gravity and high heat conduction and a preparation method thereof, wherein the polyurethane structural adhesive comprises a component A and a component B, and the mass ratio of the component A to the component B is 100: (90-110); the preparation raw materials of the component A at least comprise the following components in parts by weight: 30-50 parts of polyol prepolymer, 1-5 parts of chain extender micromolecular dihydric alcohol, 0.01-1 part of initiator, 40-60 parts of heat conducting filler A, 1-5 parts of flame retardant A, 1-5 parts of fumed silica A and 0.001-1 part of catalyst; the preparation raw materials of the component B at least comprise the following components in parts by weight: 30-50 parts of modified isocyanate-terminated prepolymer, 40-60 parts of heat conducting filler B, 1-5 parts of flame retardant B and 1-5 parts of fumed silica B, so that high bonding strength and heat conductivity coefficient under the condition of low specific gravity are realized, and meanwhile, the attenuation of bonding strength under the condition of environmental aging is avoided.

Description

Polyurethane structural adhesive with low specific gravity and high heat conduction and preparation method thereof
Technical Field
The invention relates to the technical field of C09J175/00, in particular to polyurethane structural adhesive with low specific gravity and high heat conduction and a preparation method thereof.
Background
The double-component polyurethane adhesive is widely applied to occasions such as food packaging, paper-plastic composite, civil construction and structural bonding, ultralow-temperature bonding and the like due to excellent impact resistance, durability, low-temperature resistance, fatigue resistance and good construction performance. In recent years, along with the rapid development of the new energy automobile industry, the two-component polyurethane adhesive is gradually applied as a structural adhesive to the bonding integration among the electric cores and between the electric cores, foam and a module shell in a power supply system of a new energy automobile, so that the performance quality and the service life of the power supply system are directly influenced.
However, the two-component polyurethane structural adhesive has a certain gap in terms of bonding strength compared with the epoxy resin structural adhesive and the second-generation acrylic resin structural adhesive. Accordingly, the prior art is directed to the development of high bond strength two-component polyurethane structural adhesives. For example, chinese application publication No. CN104449538B discloses a normal temperature coated two-component solvent-free polyurethane structural adhesive, and a preparation method and an application method thereof, specifically, a diisocyanate component a containing a difunctional polyol and a component B containing a polyol and a solid powder filler are adopted, when in use, the component a and the component B are coated with the adhesive to achieve bonding, but the adhesive strength of the structural adhesive is excessively attenuated under the environmental aging condition, and the thermal conductivity coefficient of the structural adhesive needs to be further improved. Chinese patent (issued publication No. CN 111303820B) discloses a double-component polyurethane structural adhesive for bonding a power battery and a preparation method thereof, and specifically adopts an isocyanate component A and a bio-based polyol component B to prepare the double-component polyurethane structural adhesive, but a large amount of solid powder filler is used in the structural adhesive, so that the weight of a power battery module is increased, and the requirement of a new energy automobile on the low-specific gravity structural adhesive cannot be met. Chinese patent application (application number CN 114316880A) discloses a polyurethane structural adhesive with low density and high thermal conductivity, which realizes the thermal conductivity of the structural adhesive by introducing high content of thermal conductive filler aluminum hydroxide and aluminum oxide, and simultaneously introduces low density filler to reduce the overall density, but the thermal conductivity (0.82-0.92) of the structural adhesive is still to be further improved.
Disclosure of Invention
In order to solve the problems, the invention provides the polyurethane structural adhesive with low specific gravity and high heat conductivity and the preparation method thereof, so that the prepared polyurethane structural adhesive realizes high bonding strength and heat conductivity coefficient under the condition of low specific gravity, avoids the attenuation of bonding strength under the condition of environmental aging, and meets the application requirements of the structural adhesive of the power battery module.
The invention provides polyurethane structural adhesive with low specific gravity and high heat conductivity, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 100: (90-110); the preparation raw materials of the component A at least comprise the following components in parts by weight: 30-50 parts of polyol prepolymer, 1-5 parts of chain extender micromolecular dihydric alcohol, 0.01-1 part of initiator, 40-60 parts of heat conducting filler A, 1-5 parts of flame retardant A, 1-5 parts of fumed silica A and 0.001-1 part of catalyst; the preparation raw materials of the component B at least comprise the following components in parts by weight: 30-50 parts of modified isocyanate-terminated prepolymer, 40-60 parts of heat conducting filler B, 1-5 parts of flame retardant B and 1-5 parts of fumed silica.
As a preferred technical scheme, the preparation raw materials of the polyol prepolymer at least comprise the following raw materials in parts by weight: 80-120 parts of polyester polyol A, 20-40 parts of polyether polyol, 1-5 parts of small molecular alcohol A and 5-20 parts of diisocyanate.
As a preferable embodiment, the polyester polyol a is at least one of an adipic acid polyester polyol, a caprolactone polyester polyol and a polycarbonate polyol. Preferably, the polyester polyol A is a combination of adipic acid polyester polyol, caprolactone polyester polyol and polycarbonate polyol; the mass ratio of the adipic acid polyester polyol to the caprolactone polyester polyol to the polycarbonate polyol is (3-5): (1-3): 1.
as a preferable technical scheme, the hydroxyl value of the adipic acid polyester polyol is 30-60mgKOH/g, and the molecular weight is 2000-3000g/moL.
Preferably, the adipic acid-based polyester polyol is at least one of poly (ethylene glycol-1, 4-butylene glycol adipate), poly (neopentyl glycol adipate) and poly (1, 6-hexanediol adipate). Preferably, the adipic acid-based polyester polyol is a combination of poly (ethylene glycol-1, 4-butylene glycol adipate) and poly (neopentyl glycol adipate); the mass ratio of the poly (ethylene glycol-1, 4-butanediol adipate) to the poly (neopentyl glycol adipate) is 1: (0.5-2). The hydroxyl value of the poly (adipic acid-ethylene glycol-1, 4-butanediol ester) is 53-59mgKOH/g, the molecular weight is 2000+/-150 g/moL, the model is PE-1320, and the poly (adipic acid-ethylene glycol-1, 4-butanediol ester) is derived from a formative group; the hydroxyl value of the poly (adipic acid-neopentyl glycol) ester is 53-59mgKOH/g, the molecular weight is 2000+/-150 g/moL, the model is PE-5556, and the poly (adipic acid-neopentyl glycol) ester is derived from a Huafeng group.
As a preferable technical scheme, the caprolactone-based polyester polyol is polycaprolactone diol, and the molecular weight of the polycaprolactone diol is 1000-2000g/moL.
As a preferred embodiment, the polycarbonate polyol is a polycarbonate diol having a molecular weight of 1000 to 2000g/moL.
The polyurethane structural adhesive provided by the invention is prepared by respectively preparing a polyol prepolymer and a modified isocyanate-terminated prepolymer, and matching with a heat conducting filler and other raw materials. The inventor finds that the polyurethane structural adhesive prepared by adopting the polyester polyol A and the polyether polyol and the micromolecular alcohol to be introduced, especially when the polyester polyol A is the combination of adipic acid polyester polyol, caprolactone polyester polyol and polycarbonate polyol, has excellent bonding strength and thermal stability. Further, by controlling the molecular weight of the polyester polyol A in the system to be in the range of 1000-3000g/moL, the toughness and the tensile strength of the polyurethane structural adhesive are balanced, and the reduction of the tensile strength and the hardness of the structural adhesive caused by longer molecular chains is avoided.
As a preferable technical scheme, the polyether polyol is at least one of polytetrahydrofuran glycol, polyoxypropylene glycol and castor oil modified polyether polyol. Preferably, the polyether polyol is polyoxypropylene diol; the molecular weight of the polyoxypropylene diol is 1000-2000g/moL, preferably 2000g/moL.
As a preferable technical scheme, the small molecular alcohol A is at least one of ethylene glycol, diethylene glycol, 1, 4-butanediol, hexanediol, trimethylolpropane, glycerol and triethanolamine; preferably, the small molecule alcohol A is diethylene glycol.
As a preferred technical scheme, the diisocyanate is one of PAPI, MDI, TDI, HDI biuret, TDI-TMP adduct and HDI trimer. Preferably, the diisocyanate is an HDI trimer, model Wannate HT-600, from the fly courser.
As a preferable technical scheme, the preparation raw materials of the modified isocyanate-terminated prepolymer at least comprise, by weight, 80-120 parts of isocyanate, 60-80 parts of hydroxyl modified polybutadiene, 10-30 parts of polyester polyol B and 0.01-1 part of small molecular alcohol B;
as a preferred technical scheme, the isocyanate is one of PAPI, MDI, TDI, HDI biuret, TDI-TMP adduct and HDI trimer. Preferably, the isocyanate is PAPI (polymethylene polyphenyl polyisocyanate).
As a preferred embodiment, the molecular weight of the hydroxy-modified polybutadiene is 2000-3000g/moL and the 1, 2-vinyl content is 20-30%. Preferably, the hydroxy-modified polybutadiene has a molecular weight of 2900g/moL, a1, 2-vinyl content of 22% and a type number ofHT, derived from Evonik.
As a preferable embodiment, the polyester polyol B is at least one of an adipic acid polyester polyol, a caprolactone polyester polyol and a polycarbonate polyol; preferably, the polyester polyol B is poly (1, 4-butanediol adipate), preferably, the hydroxyl value of the poly (1, 4-butanediol adipate) is 36-40mgKOH/g, and the molecular weight is 2800-3200g/moL; preferably, the hydroxyl value of the poly (1, 4-butanediol adipate) is 36-40mgKOH/g, the molecular weight is 3000g/moL, and the model is PE-2708 or PE-2811, and the poly (1-butanediol adipate) is derived from the Huafeng group.
Preferably, the small molecular alcohol B is at least one of ethylene glycol, diethylene glycol, 1, 4-butanediol, hexanediol, trimethylolpropane, glycerol and triethanolamine; preferably, the small molecule alcohol B is ethylene glycol.
The polyurethane structural adhesive provided by the invention is prepared by reacting polymethylene polyphenyl polyisocyanate with hydroxyl modified polybutadiene, poly (1, 4-butylene adipate) and ethylene glycol, and is particularly prepared by pre-polymerizing and modifying polymethylene polyphenyl polyisocyanate by using hydroxyl modified polybutadiene with the molecular weight of 2000-3000g/moL and the 1, 2-vinyl content of 20-30% together with poly (1, 4-butylene adipate) and ethylene glycol, so that on one hand, the dispersion and compatibility of a heat conducting filler, a flame retardant and gas phase silicon dioxide in a component B system are facilitated, and on the other hand, the overall reactivity of the polyurethane structural adhesive system mixed with the component A is in a proper level, and the coating construction performance and the curing performance of the polyurethane structural adhesive are balanced, and meanwhile, the high adhesive strength and the adhesive strength retention performance under high-temperature high-humidity conditions of the polyurethane structural adhesive are ensured.
As a preferable technical scheme, the chain extender small molecular dihydric alcohol is at least one of ethylene glycol, butanediol, hexanediol, neopentyl glycol and ethylbutyl propylene glycol. Preferably, the chain extender small-molecule dihydric alcohol is ethylene glycol.
As a preferred technical scheme, the initiator is a peroxide initiator; preferably, the peroxide initiator is dicumyl peroxide.
As a preferred technical scheme, the catalyst is an organotin catalyst; preferably, the organotin catalyst is dibutyltin dilaurate.
As a preferable technical scheme, the flame retardant A and the flame retardant B are at least one of aluminum hydroxide, magnesium hydroxide and antimony trioxide. The flame retardant A and the flame retardant B are aluminum hydroxide (superfine) and are derived from Shanghai Yuan Jiang chemical industry Co.
As a preferred embodiment, the fumed silica A and the fumed silica B have BET specific surface areas of 170-330m 2 And/g. Preferably, the BET specific surface area of the fumed silica A and the fumed silica B is 300+ -30 m 2 And/g, model YJ2#, which is from Shanghai Yuan Jiang chemical Co., ltd.
As a preferable technical scheme, the heat conducting filler a and the heat conducting filler B are at least one of alumina, boron nitride, one-dimensional Boron Nitride Nanotubes (BNNTs) and two-dimensional Boron Nitride Nanoplatelets (BNNSs).
As a preferable technical scheme, the heat-conducting filler A and the heat-conducting filler B are subjected to surface treatment by amino siloxane coupling agents.
Preferably, the amino siloxane coupling agent is one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, benzyl triethoxysilane, benzyl trimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane and N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane; preferably, the amino-type siloxane coupling agent is N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane.
Based on the polyurethane structural adhesive system provided by the invention, after the component A containing the polyol prepolymer is mixed with the component B containing the hydroxylated polybutadiene modified isocyanate end-capped prepolymer, an interpenetrating polyurethane-polybutadiene network system is formed under the action of dicumyl peroxide and dibutyltin dilaurate, and the polyurethane structural adhesive has a bicontinuous percolation structure, and the two systems of the polyurethane system and the polybutadiene system are linked by ester group chemical bonds, so that the polyurethane structural adhesive has excellent overall strength and reliability. Further, the heat-conducting filler A, B subjected to surface treatment by the amino siloxane coupling agent is introduced into the system, and the heat-conducting filler A, B is intensively dispersed in the polyurethane continuous phase, so that the continuous conduction effect under the condition of low heat-conducting filler addition is realized, and the heat-conducting composite material with the double continuous percolation structure and low specific gravity and high heat conduction is prepared. The inventors analyzed the cause may be: after the heat conducting filler is subjected to surface treatment by adopting an amino siloxane coupling agent, under a bicontinuous structure formed by polyurethane and polybutadiene, the heat conducting filler is uniformly dispersed in one polymer phase, and the heat conducting filler is lapped to form a heat conducting passage, so that when the heat conducting filler is added with lower content, the heat conducting filler is enough to form a heat conducting network, the consumption of the heat conducting filler is greatly reduced, the cost is reduced, and the heat conductivity of the prepared heat conducting composite material is better.
The invention also provides a preparation method of the polyurethane structural adhesive with low specific gravity and high heat conduction, which at least comprises the following steps:
(1) Mixing the prepared polyol prepolymer with chain extender micromolecular dihydric alcohol, an initiator, a heat-conducting filler A, a flame retardant A, fumed silica A and a catalyst according to parts by weight to obtain a component A;
(2) Mixing the prepared modified isocyanate-terminated prepolymer with a heat-conducting filler B, a flame retardant B and fumed silica B according to parts by weight to obtain a component B;
(3) When in use, the component A and the component B are uniformly mixed according to the mass ratio and cured to obtain the composite material.
Advantageous effects
1. The invention provides a polyurethane structural adhesive with low specific gravity and high heat conductivity and a preparation method thereof, so that the prepared polyurethane structural adhesive realizes high bonding strength and heat conductivity coefficient under the condition of low specific gravity, avoids the attenuation of bonding strength under the condition of environmental aging, and meets the application requirement of the structural adhesive of a power battery module.
2. Based on the system, the prepared polyurethane structural adhesive has excellent bonding strength and thermal stability by adopting the polyester polyol A and the introduction of polyether polyol and micromolecular alcohol, especially when the polyester polyol A is the combination of adipic acid polyester polyol, caprolactone polyester polyol and polycarbonate polyol.
3. Based on the polyurethane structural adhesive system provided by the invention, after the component A containing the polyol prepolymer is mixed with the component B containing the hydroxylated polybutadiene modified isocyanate end-capped prepolymer, an interpenetrating polyurethane-polybutadiene network system is formed under the action of dicumyl peroxide and dibutyltin dilaurate, and the polyurethane structural adhesive has a bicontinuous percolation structure, and the two systems of the polyurethane system and the polybutadiene system are linked by ester group chemical bonds, so that the polyurethane structural adhesive has excellent overall strength and reliability.
4. Based on the system, the heat-conducting filler A, B subjected to surface treatment by the amino siloxane coupling agent is introduced, the heat-conducting filler A, B is intensively dispersed in the polyurethane continuous phase, the continuous conduction effect under the condition of low heat-conducting filler addition is realized, and the heat-conducting composite material with the double continuous percolation structure and low specific gravity and high heat conduction is prepared.
Detailed Description
Example 1
In one aspect, embodiment 1 of the present invention provides a polyurethane structural adhesive with low specific gravity and high thermal conductivity, which comprises a component a and a component B, wherein the mass ratio of the component a to the component B is 100:100; the preparation raw materials of the component A comprise the following components in parts by weight: 40 parts of polyol prepolymer, 3 parts of chain extender micromolecular dihydric alcohol, 0.2 part of initiator, 50 parts of heat conducting filler A, 3 parts of flame retardant A, 3 parts of fumed silica A and 0.05 part of catalyst; the preparation raw materials of the component B comprise the following components in parts by weight: 40 parts of modified isocyanate-terminated prepolymer, 50 parts of heat conducting filler B, 3 parts of flame retardant B and 3 parts of fumed silica.
The preparation raw materials of the polyol prepolymer comprise the following raw materials in parts by weight: 100 parts of polyester polyol A, 30 parts of polyether polyol, 3 parts of small molecular alcohol A and 10 parts of diisocyanate.
The preparation method of the polyol prepolymer comprises the step of mixing polyester polyol A, polyether polyol, micromolecular alcohol A and diisocyanate according to the formula amount.
The polyester polyol A is a combination of adipic acid polyester polyol, caprolactone polyester polyol and polycarbonate polyol; the mass ratio of the adipic acid polyester polyol to the caprolactone polyester polyol to the polycarbonate polyol is 4:2:1.
the adipic acid polyester polyol is a combination of poly (ethylene glycol-1, 4-butanediol adipate) and poly (neopentyl glycol adipate); the mass ratio of the poly (ethylene glycol-1, 4-butanediol adipate) to the poly (neopentyl glycol adipate) is 1:1. the hydroxyl value of the poly (adipic acid-ethylene glycol-1, 4-butanediol ester) is 53-59mgKOH/g, the molecular weight is 2000+/-150 g/moL, the model is PE-1320, and the poly (adipic acid-ethylene glycol-1, 4-butanediol ester) is derived from a formative group; the hydroxyl value of the poly (adipic acid-neopentyl glycol) ester is 53-59mgKOH/g, the molecular weight is 2000+/-150 g/moL, the model is PE-5556, and the poly (adipic acid-neopentyl glycol) ester is derived from a Huafeng group.
The caprolactone-based polyester polyol is polycaprolactone diol, and the molecular weight of the polycaprolactone diol is 2000g/moL.
The polycarbonate polyol is a polycarbonate diol having a molecular weight of 2000g/moL.
The polyether polyol is polyoxypropylene glycol; the molecular weight of the polyoxypropylene diol was 2000g/moL.
The small molecular alcohol A is diethylene glycol.
The diisocyanate is HDI trimer, the model is Wannate HT-600, and the diisocyanate is derived from the flying courser.
The preparation raw materials of the modified isocyanate-terminated prepolymer comprise 100 parts of isocyanate, 70 parts of hydroxyl modified polybutadiene, 20 parts of polyester polyol B and 0.5 part of micromolecular alcohol B in parts by weight;
the preparation raw materials of the modified isocyanate-terminated prepolymer are obtained by mixing isocyanate, hydroxyl modified polybutadiene, polyester polyol B and micromolecular alcohol B according to the formula amount.
The isocyanate is PAPI (polymethylene polyphenyl polyisocyanate).
The molecular weight of the hydroxyl modified polybutadiene is 2900g/moL, the 1, 2-vinyl content is 22%, and the model isHT, derived from Evonik.
The polyester polyol B is poly (1, 4-butanediol adipate), the hydroxyl value of the poly (1, 4-butanediol adipate) is 36-40mgKOH/g, the molecular weight is 3000g/moL, the model is PE-2708, and the poly (1, 4-butanediol adipate) is derived from a Huafeng group.
The small molecular alcohol B is ethylene glycol.
The chain extender small molecular dihydric alcohol is ethylene glycol.
The initiator is a peroxide initiator; the peroxide initiator is dicumyl peroxide.
The catalyst is an organotin catalyst; the organotin catalyst is dibutyl tin dilaurate.
The flame retardant A and the flame retardant B are aluminum hydroxide (superfine) and are derived from Shanghai Yuan Jiang chemical industry Co.
The BET specific surface areas of the fumed silica A and the fumed silica B are 300+/-30 m 2 And/g, model YJ2#, which is from Shanghai Yuan Jiang chemical Co., ltd.
The heat conducting filler A and the heat conducting filler B are hexagonal boron nitride (Shanghai high-View technology Co., ltd.).
The heat conducting filler A and the heat conducting filler B are subjected to surface treatment by amino siloxane coupling agents, the amino siloxane coupling agents and ethanol are mixed to prepare dilute solutions with solute concentration of 1wt%, the heat conducting filler A and the heat conducting filler B are respectively placed into a solid stirrer, the dilute solutions are sprayed on the heat conducting filler A or the heat conducting filler B, wherein the spraying amount of the dilute solutions is 10 times of the mass of the heat conducting filler A or the heat conducting filler B, and the heat conducting filler A or the heat conducting filler B is dried for 2 hours at 120 ℃ after stirring and dispersing for 30 minutes.
The amino-type siloxane coupling agent is N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane.
The embodiment 1 of the invention provides a preparation method of polyurethane structural adhesive with low specific gravity and high heat conductivity, which comprises the following steps:
(1) Mixing the prepared polyol prepolymer with chain extender micromolecular dihydric alcohol, an initiator, a heat-conducting filler A, a flame retardant A, fumed silica A and a catalyst according to parts by weight to obtain a component A;
(2) Mixing the prepared modified isocyanate-terminated prepolymer with a heat-conducting filler B, a flame retardant B and fumed silica B according to parts by weight to obtain a component B;
(3) When in use, the component A and the component B are uniformly mixed according to the mass ratio and cured to obtain the composite material.
Example 2
Example 2 of the present invention provides a polyurethane structural adhesive with low specific gravity and high heat conductivity and a preparation method thereof, and a specific embodiment thereof is the same as example 1, except that hydroxy modified polybutadiene is replaced with winning polyester polyol 7380.
Example 3
The embodiment 3 of the invention provides a polyurethane structural adhesive with low specific gravity and high heat conductivity and a preparation method thereof, and the specific implementation mode of the polyurethane structural adhesive is the same as the embodiment 1, wherein the heat-conducting filler A and the heat-conducting filler B do not adopt amino siloxane coupling agents for surface treatment.
Example 4
The embodiment 4 of the invention provides a polyurethane structural adhesive with low specific gravity and high heat conductivity and a preparation method thereof, and the specific implementation mode of the polyurethane structural adhesive is the same as that of the embodiment 1, and the amino-type siloxane coupling agent is replaced by a silane coupling agent KH-570.
Example 5
The embodiment 5 of the invention provides a polyurethane structural adhesive with low specific gravity and high heat conductivity, which is different from the embodiment 1 in that the polyester polyol A is poly (1, 4-butylene adipate).
Performance test method
(1) The components A and B prepared in the examples 1-5 of the invention are uniformly mixed according to the mass ratio and then coated on the surface of a polytetrafluoroethylene plate, the thickness of a polyurethane structural adhesive layer formed after curing for 7 days at 25 ℃ is 200 mu m, and the specific gravity and the heat conductivity coefficient of the polyurethane structural adhesive layer are measured, and the results are shown in Table 1.
(2) a, uniformly mixing the components A and B prepared in the examples 1-5 according to the mass ratio, bonding 3 series aluminum sheets (aluminum manganese alloy aluminum sheets, thickness of 2 mm), curing at 25 ℃ for 7 days to form a polyurethane structural adhesive layer with thickness of 200 mu m, measuring the shearing strength of the polyurethane structural adhesive according to the national standard GB 7124, marking as S0, and obtaining the result shown in the table 1;
b. the components A and B prepared in the examples 1-5 of the invention are uniformly mixed according to the mass ratio and then are used for bonding between a 3-series aluminum sheet (upper layer), a PET (middle layer) and a 3-series aluminum sheet (lower layer) to obtain a sandwich structure, the thickness of a polyurethane structural adhesive layer formed after curing for 7 days at 25 ℃ is 200 mu m, the shear strength of the polyurethane structural adhesive is measured by referring to the national standard GB 7124 and recorded as S1, and the result is shown in the table 1.
(3) Ageing resistance: the components A and B prepared in the examples 1-5 are uniformly mixed according to the mass ratio and then used for bonding (namely, sandwich structure) among 3 aluminum sheets (upper layer), PET (middle layer) and 3 aluminum sheets (lower layer), the thickness of a polyurethane structural adhesive layer formed after curing is 200 mu m, the whole is placed at 85 ℃ and 85% RH for 1000 hours, the shearing strength of the polyurethane structural adhesive is measured by referring to national standard GB 7124 and recorded as S2, and the shearing strength attenuation rate R1= (S1-S2) multiplied by 100%/S1 is calculated through a formula, and the result is shown in Table 1.
(4) The components A and B prepared in the examples 1-5 are uniformly mixed according to the mass ratio and then used for bonding (namely, sandwich structure) among 3 aluminum sheets (upper layer), PET (middle layer) and 3 aluminum sheets (lower layer), the thickness of a polyurethane structural adhesive layer formed after curing for 7 days at 25 ℃ is 200 mu m, the whole is subjected to cold and hot impact test (-40-85 ℃ for 500 cycles and 1000 hours), the shearing strength of the polyurethane structural adhesive is measured by referring to the national standard GB 7124 and recorded as S3, and the shearing strength attenuation rate R2= (S1-S3)/S1×100% is calculated by a formula, wherein the result is shown in the table 1.
TABLE 1,

Claims (5)

1. The polyurethane structural adhesive with low specific gravity and high heat conductivity is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 100: (90-110); the preparation raw materials of the component A at least comprise the following components in parts by weight: 30-50 parts of polyol prepolymer, 1-5 parts of chain extender micromolecular dihydric alcohol, 0.01-1 part of initiator, 40-60 parts of heat conducting filler A, 1-5 parts of flame retardant A, 1-5 parts of fumed silica A and 0.001-1 part of catalyst; the preparation raw materials of the component B at least comprise the following components in parts by weight: 30-50 parts of modified isocyanate-terminated prepolymer, 40-60 parts of heat conducting filler B, 1-5 parts of flame retardant B and 1-5 parts of fumed silica;
the preparation raw materials of the polyol prepolymer at least comprise the following raw materials in parts by weight: 80-120 parts of polyester polyol A, 20-40 parts of polyether polyol, 1-5 parts of small molecular alcohol A and 5-20 parts of diisocyanate;
the polyester polyol A is a combination of adipic acid polyester polyol, caprolactone polyester polyol and polycarbonate polyol; the mass ratio of the adipic acid polyester polyol to the caprolactone polyester polyol to the polycarbonate polyol is (3-5): (1-3): 1, a step of;
the small molecular alcohol A is at least one of ethylene glycol, diethylene glycol, 1, 4-butanediol, hexanediol, trimethylolpropane, glycerol and triethanolamine;
the preparation raw materials of the modified isocyanate-terminated prepolymer at least comprise, by weight, 80-120 parts of isocyanate, 60-80 parts of hydroxyl modified polybutadiene, 10-30 parts of polyester polyol B and 0.01-1 part of small molecular alcohol B;
the polyester polyol B is at least one of adipic acid polyester polyol, caprolactone polyester polyol and polycarbonate polyol;
the small molecular alcohol B is at least one of ethylene glycol, diethylene glycol, 1, 4-butanediol, hexanediol, trimethylolpropane, glycerol and triethanolamine
The heat conducting filler A and the heat conducting filler B are at least one of aluminum oxide, boron nitride, one-dimensional boron nitride nanotubes and two-dimensional boron nitride nanosheets; the heat conducting filler A and the heat conducting filler B are subjected to surface treatment by amino siloxane coupling agents;
the flame retardant A and the flame retardant B are at least one of aluminum hydroxide, magnesium hydroxide and antimony trioxide;
the BET specific surface area of the fumed silica A and the fumed silica B is 170-330m 2 /g。
2. The polyurethane structural adhesive with low specific gravity and high heat conductivity according to claim 1, wherein the adipic acid polyester polyol is at least one of poly (ethylene glycol-1, 4-butylene glycol) adipate, poly (neopentyl glycol) adipate and poly (1, 6-hexanediol) adipate.
3. The polyurethane structural adhesive with low specific gravity and high heat conductivity according to claim 2, wherein the molecular weight of the hydroxyl modified polybutadiene is 2000-3000g/moL, and the content of 1, 2-vinyl is 20-30%.
4. The polyurethane structural adhesive with low specific gravity and high heat conductivity according to claim 3, wherein the amino-siloxane coupling agent is one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane and N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane.
5. A method for preparing the polyurethane structural adhesive with low specific gravity and high heat conductivity according to any one of claims 1 to 4, which comprises at least the following steps:
(1) Mixing the prepared polyol prepolymer with chain extender micromolecular dihydric alcohol, an initiator, a heat-conducting filler A, a flame retardant A, fumed silica A and a catalyst according to parts by weight to obtain a component A;
(2) Mixing the prepared modified isocyanate-terminated prepolymer with a heat-conducting filler B, a flame retardant B and fumed silica B according to parts by weight to obtain a component B;
(3) When in use, the component A and the component B are uniformly mixed according to the mass ratio and cured to obtain the composite material.
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