CN113480968A - Heat-insulating structural adhesive for new energy power battery and manufacturing method thereof - Google Patents
Heat-insulating structural adhesive for new energy power battery and manufacturing method thereof Download PDFInfo
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- CN113480968A CN113480968A CN202110765839.4A CN202110765839A CN113480968A CN 113480968 A CN113480968 A CN 113480968A CN 202110765839 A CN202110765839 A CN 202110765839A CN 113480968 A CN113480968 A CN 113480968A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- 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
- C08G18/692—Polymers of conjugated dienes containing carboxylic acid groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8125—Unsaturated isocyanates or isothiocyanates having two or more isocyanate or isothiocyanate groups
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- 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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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
- H01M10/625—Vehicles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- 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
- C08K2003/2255—Oxides; Hydroxides of metals of molybdenum
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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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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 discloses a heat-insulating structural adhesive for a new energy power battery and a manufacturing method thereof, wherein a composition A comprises 16-31% of a block polymerization telechelic carboxyl compound, 0-1.5% of a telechelic amino compound, 0-2.5% of a coupling agent and a modifier, 0-2.5% of a curing accelerator, 44-62% of heat-insulating powder and 15-26% of a flame-retardant component; b composition containing block polymerized telechelic isocyanate compound16-31% of telechelic epoxy compound, 0-1.5% of coupling agent and modifier, 0-2.5% of curing accelerator, 44-62% of heat insulation powder and 15-26% of flame retardant component; uniformly mixing 1 part of the composition A and 0.25-2 parts of the composition B in a volume ratio, and curing; the density is less than 0.6g/cm3The thermal conductivity coefficient is less than 0.08W/(m.K), the tensile strength is more than or equal to 5MPa, the elongation at break is more than or equal to 23 percent, the shear bonding strength is more than or equal to 4MPa, the breakdown strength is more than or equal to 12.4kV/mm, and the volume resistivity is more than or equal to 2.4 multiplied by 1013Flame retardancy of V0Extinguishing when the fire leaves; the requirements of heat insulation and structural strength of the front edge CTP battery pack in the service period can be met.
Description
Technical Field
The invention belongs to the design and manufacture of the intersection field of polymer-based composite high polymer materials, high-strength bonding structural materials and heat-insulating functional materials, and particularly relates to heat-insulating structural adhesive for a new energy power battery and a manufacturing method thereof.
Background
The global new energy automobile technology is developing at an accelerated speed, and the development trend of the technology is difficult to change in the visible future. The core technology of the new energy automobile is that the energy density and the total electric energy index of the power battery are higher and higher, and the storage and conversion functions of electric quantity exist in the same space. One of the new problems faced is that the heating density in unit volume or unit area is higher and higher, and the problems of safety, reliability and environmental adaptability during the service period and even the whole life cycle of the power battery pack are correspondingly outstanding, if the battery cells are in fault, overcharge and overdischarge, especially under the conditions of accidental short circuit, collision and other terminals, the thermal runaway of individual battery cells easily causes the chain temperature rise reaction of adjacent battery cells, so that the probability of rapid ignition and deflagration of the whole power battery pack is obviously higher than the control target of 6 sigma. Therefore, thermal insulation protection needs to be arranged between the battery cell monomers, between the modules and between the battery pack and the passenger cabin body, so that the purpose of delaying thermal runaway is achieved, and the time of the escape window is prolonged.
In recent years, although progress has been made in the research and application of thermal insulation technology for power battery packs, the overall distance from the design requirement target is not satisfactory. For example, US 7820319B 2 by Tesla discloses a thermal barrier between battery cells, in which one or more layers of insulating and expanding material are applied to the outer or double or inner shell of the cell to absorb heat, expand or coke, thereby preventing heat diffusion; the expansion material selected in the patent comprises graphite expansion material, thermoplastic elastomer, ceramic-based intumescent material, vermiculite/mineral fiber-based intumescent material and ammonium polyphosphate-based intumescent material.
The above patent seems to achieve thermal runaway barrier by the design of the thermal barrier material and structure, but after careful DFMEA analysis, the defects are found to be non-negligible:
1) in a normal service period, the thermal conductivity of the thermal insulation layer is still above 0.25W/(m.K), and only when the temperature of a local battery core is above 245 ℃, the thermal insulation layer can generate a remarkable expansion effect to reduce the thermal conductivity to below 0.20W/(m.K), namely, the thermal insulation function of the battery pack is awakened only when a fire occurs, and is later;
2) the graphite expansion type material is mixed in a thermal insulation layer formed by a thermoplastic elastomer, a ceramic-based intumescent material, a vermiculite/mineral fiber-based intumescent material and an ammonium polyphosphate-based intumescent material, has the obvious defect of low shear bonding strength, is not enough to achieve the structural strength required by a CTP battery pack, and is reduced in safety.
Therefore, the front problem is to invent a better heat insulation structural adhesive for the new energy power battery, and the heat conductivity coefficient is less than 0.20W/W/(m.K), the shear strength is more than or equal to 4MPa, the flame retardance is V-0, and the density is less than 0.6g/cm3The aim is to meet the requirements of heat insulation and structural strength required by the leading-edge CTP battery pack during normal service and even in the whole life cycle.
Disclosure of Invention
The invention aims to provide a heat-insulating structural adhesive for a new energy power battery and a manufacturing method thereof, wherein the heat conductivity coefficient is less than 0.20W/(m.K), the shear bonding strength is more than or equal to 4MPa, the flame retardance is V-0, and the density is less than 0.6g/cm3The method aims to solve the problem of thermal runaway of the new energy power battery to the maximum extent so as to meet the requirements of heat insulation and structural strength required by the CTP battery pack during normal service and even in a full life cycle.
In order to achieve one of the above purposes, the heat insulation structural adhesive for the new energy power battery comprises the following components in percentage by mass: the composition A contains (16-31)% of at least one of a block-polymerized telechelic carboxyl compound and/or a block-polymerized telechelic amino compound, 0-1.5)% of a coupling agent and/or a modifying agent, 0-2.5)% of a curing accelerator, 44-62)% of a heat-insulating powder, and 15-26)% of a flame-retardant component; the composition B contains 16-31% of at least one of a block-polymerized telechelic isocyanate-based compound and/or a block-polymerized telechelic epoxy-based compound, 0-1.5% of a coupling agent and/or a modifying agent, 0-2.5% of a curing accelerator, 44-62% of a heat-insulating powder and 15-26% of a flame-retardant component; when in use, 1 part of the composition A and 0.25-2 parts of the composition B are uniformly mixed according to the volume ratio or the mass ratio and are cured into the heat-insulating structural adhesive or the bonding material for end use.
To achieve the second purpose, the invention provides a method for manufacturing a heat insulation structural adhesive for a new energy power battery, comprising the following steps: the method comprises the following steps of (A) a block polymerization method of a telechelic carboxyl compound and/or telechelic amino compound base material, and a block polymerization method of a telechelic isocyanate compound and/or telechelic epoxy compound base material, wherein the head-head connection or head-tail connection orientation of molecular chains is random during block polymerization, and the atom arrangement orientation of cis-form or trans-form molecular chain segments is random; controlling a mixing method for the shearing strength of the liquid material and the powder material; step three, controlling a positive pressure or negative pressure reaction; step four, heating and cooling; at least two of the four steps or combining step (one) and step (two) into one step.
Further, in the a composition, the block polymerized telechelic carboxyl compound further comprises: at least one of telechelic carboxyl polybutadiene with a chemical structural formula (1), a product of reacting isocyanate with telechelic carboxyl polybutadiene according to a chemical structural formula (2) and removing carbon dioxide, a product of reacting epoxy resin with telechelic carboxyl polybutadiene according to a chemical structural formula (3), and a product of reacting epoxy polyalkylsiloxane with telechelic carboxyl polybutadiene according to a chemical structural formula (4);
wherein the chemical structural formula (1) —
And in the chemical formula (1), x is 1, y is 0 to 1.0, z is a number average degree of polymerization of 9 to 27, the number average functionality of carboxyl is 2.1 to 2.2, R is a ratio of moles to x8Is vinyl or cyano;
wherein the chemical structural formula (2) — is
And in the chemical formula (2), isocyanate OCN-R1Isocyanate number average functionality of-NCO of 2.0, R1Is at least one of an alkylene, phenylene or substituted phenylene, arylcyclopropene or substituted arylcyclopropene, heterocyclylene or heterocyclylene, said alkylene being a group which cleaves at a carbon-hydrogen bond in one molecule of an organic compound to remove two hydrogen atoms (hereinafter "alkylene" is in accordance with this definition);
wherein the chemical structural formula (3) — is
And in the chemical structural formula (3), the epoxy compound conforms to the definition of the chemical structural formula (17);
wherein the chemical structural formula (4) — is
And in the chemical structural formula (4), the epoxy compound conforms to the definition of the chemical structural formula (21).
Further, in the a composition, the block polymerized telechelic amino compound further comprises: at least one of telechelic amino polypropylene oxide having chemical structural formula (5), amino polyalkylsiloxane having chemical structural formula (6), a product of reaction of isocyanate and telechelic amino polypropylene oxide according to chemical structural formula (7), a product of reaction of isocyanate and amino polyalkylsiloxane according to chemical structural formula (8), a product of reaction of epoxy resin and telechelic amino polypropylene oxide according to chemical structural formula (9), a product of reaction of epoxy resin and amino polyalkylsiloxane according to chemical structural formula (10), a product of reaction of epoxy polyalkylsiloxane and telechelic amino polypropylene oxide according to chemical structural formula (11), and a product of reaction of epoxy polyalkylsiloxane and amino polyalkylsiloxane according to chemical structural formula (12);
wherein the chemical structural formula (5) — is
In the chemical structural formula (5), k is the number average degree of polymerization of 25-50, and the number average functionality of amino is 2.0-2.3;
wherein the chemical structural formula (6) — is
And in the chemical structural formula (6), the number average polymerization degree is m ═ 0-1, n ═ 8-22, the number average functionality of amido is 2.9-3.3, R2Is alkylene having 2 to 5 carbon atoms, R3、R4、R5And R6Is at least one of alkyl, phenyl or substituted phenyl, aromatic ring group or substituted aromatic ring group, heterocyclic group or heterocyclic group;
wherein the chemical structural formula (7) — is
Wherein the chemical structural formula (8) — is
Wherein the chemical structural formula (9) — is
Wherein the chemical structural formula (10) — is
Wherein the chemical structural formula (11) — is
Wherein the chemical structural formula (12) — is
Further, in the B composition, the block polymerized telechelic isocyanate based compound further comprises: at least one of isocyanate having a chemical structural formula (13), a product of reacting isocyanate with telechelic carboxyl polybutadiene according to a chemical structural formula (14) and removing carbon dioxide, a product of reacting isocyanate with telechelic amino polypropylene oxide according to a chemical structural formula (15), and a product of reacting isocyanate with amino polyalkylsiloxane according to a chemical structural formula (16);
wherein the chemical structural formula (13) — is
OCN-R1-NCO (13)
And in the chemical formula (13), the isocyanate group has a number average functionality of 2.0, R1Is at least one of alkylene, phenylene or substituted phenylene, aromatic cyclopropene or substituted aromatic cyclopropene, heterocyclic ring or heterocyclic ring support;
wherein the chemical structural formula (14) —
Wherein the chemical structural formula (15) — is
Wherein the chemical structural formula (16) — is
Further, in the B composition, the block polymerized telechelic epoxy compound further comprises: at least one of an epoxy resin having a chemical structural formula (17), a product of a reaction of an epoxy resin and telechelic carboxy polybutadiene according to chemical structural formula (18), a product of a reaction of an epoxy resin and telechelic amino polypropylene oxide according to chemical structural formula (19), a product of a reaction of an epoxy resin and amino polyalkylsiloxane according to chemical structural formula (20), an epoxy polyalkylsiloxane having a chemical structural formula (21), a product of a reaction of an epoxy polyalkylsiloxane and telechelic carboxy polybutadiene according to chemical structural formula (22), a product of a reaction of an epoxy polyalkylsiloxane and telechelic amino polypropylene oxide according to chemical structural formula (23), and a product of a reaction of an epoxy polyalkylsiloxane and amino polyalkylsiloxane according to chemical structural formula (24);
wherein the chemical structural formula (17) —
And in the chemical structural formula (17), the number average functionality of the epoxy group is 2.0 or 3.0, further comprising: r7Is at least one of alkylene, phenylene or substituted phenylene, aromatic or substituted aromatic, heterocyclic or heterocyclic ring support according to the chemical structural formula (25) or the chemical structural formula (26);
wherein the chemical structural formula (18) — is
Wherein the chemical structural formula (19) — is
Wherein the chemical structural formula (20) — is
Wherein the chemical structural formula (21) — is
In the chemical structural formula (21), the number average polymerization degree of the alkyl siloxane is more than or equal to 0, n is 5-50, the number average functionality of the epoxy group is 2.8-3.0, R2Is alkylene having 2 to 5 carbon atoms, R3、R4、R5And R6Is at least one of alkyl, phenyl or substituted phenyl, aromatic ring group or substituted aromatic ring group, heterocyclic group or heterocyclic group;
wherein the chemical structural formula (22) — is
Wherein the chemical structural formula (23) —
Wherein the chemical structural formula (24) — is
Wherein the chemical structural formula (25) — is
And in the chemical structural formula (25), the number average polymerization degree is q 1-2, the number average functionality of the epoxy group is 2.0 or 3.0, R9At least one of alkyl with 1-5 hydrogen atoms and carbon atoms, phenyl or substituted phenyl, aromatic or substituted aromatic ring, heterocyclic radical or heterocyclic radical;
wherein the chemical structural formula (26) — is
And in the chemical structural formula (26), the number average polymerization degree is q 1-2, the number average functionality of the epoxy group is 2.0 or 3.0, R9Is at least one of an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, a phenyl group or a substituted phenyl group, an aromatic ring group or a substituted aromatic ring group, a heterocyclic group or a heterocyclic group.
Further, the coupling agent and/or modifying agent includes: hexadecyl trimethoxysilane [ CAS: 16415-12-6], hexadecyltriethoxysilane [ CAS: 16415-13-7], gamma- (2, 3-glycidoxy) propyltrimethoxysilane [ CAS: 2530-83-8], gamma- (2, 3-epoxypropoxy) propyltriethoxysilane [ CAS: 2602-34-8], gamma-aminopropyltrimethoxysilane [ CAS: 13822-56-5], gamma-aminopropyltriethoxysilane [ CAS: 919-30-2), n- (β -aminoethyl) - γ -aminopropyltrimethoxysilane [ CAS: 1760-24-3), n- (β -aminoethyl) - γ -aminopropyltriethoxysilane [ CAS: 5089-72-5], gamma- (methacryloyloxy) propyltrimethoxysilane [ CAS: 2530-85-0], gamma- (methacryloyloxy) propyltriethoxysilane [ CAS: 21142-29-0], gamma-diethylenetriaminepropylmethyldimethoxysilane [ CAS: 99740-64-4 ]; or isopropyldioleacyloxy (dioctylphosphatoxy) titanate [ CAS: 61417-49-0], isopropyltris (dioctylphosphonoxy) titanate [ CAS: 65345-34-8], isopropyl triisostearate [ CAS: 61417-49-0], bis (dioctyloxypyrophosphate) ethylene titanate [ CAS: 65467-75-6], tetraisopropylbis (dioctylphosphatoxy) titanate [ CAS: 65460-52-8 ]; or oleic acid [ CAS: 112-80-1), lauric acid [ CAS: 143-07-7), caprylic acid [ CAS: 124-07-2), ricinoleic acid [ CAS: 141-22-0], abietic acid [ CAS: 514-10-3], salicylic acid [ CAS: 69-72-7), benzoic acid [ CAS: 65-85-0], dodecylbenzenesulfonic acid [ CAS: 27176-87-0), benzotriazole [ CAS: 95-14-7, and at least one of tolyltriazole [ CAS number 29385-43-1 ].
Further, the curing accelerator includes: phenol [ CAS: 108-95-2), 2, 4, 6-tris (dimethylaminomethyl) phenol [ CAS: 90-72-2), triphenylphosphine [ CAS: 603-35-0], imidazole [ CAS: 288-32-4 ].
Further, the heat-insulating powder material comprises: at least one of hollow glass microspheres, nano hollow fibers and fumed silica; average particle diameter D of single particles and agglomerated particles of heat-insulating powder50Is between (10 to 65) mu m.
Further, the flame retardant component comprises: aluminum hydroxide [ Al (OH)3]Magnesium hydroxide [ Mg (OH) ]2]Melamine cyanurate [ CAS: 37640-57-6]Ammonium polyphosphate (APP), aluminum hypophosphite [ Al (H)2PO2)3]Tricresyl phosphate [ CAS: 1330-78-5]Diethyl ethylphosphate [ CAS: 682-30-4]At least one of; wherein the average particle diameter D of the powder flame-retardant component single particles and agglomerated particles50Is between 0.45 and 90 μm.
Further, said step (a) of block polymerization process of telechelic carboxyl compound and/or telechelic amino compound base, block polymerization process of telechelic isocyanate compound and/or telechelic epoxy compound base, the orientation of "head-to-head" or "head-to-tail" linkage of the molecular chains during block polymerization is random, and the orientation of atomic arrangement of cis or trans molecular chain segments is also random, comprising:
in the composition A, a block polymerization process of the telechelic carboxyl compound base
Adding 1 mol of any one of isocyanate, epoxy resin or epoxy polyalkylsiloxane and 1.8-5 mol of telechelic carboxyl polybutadiene into a reactor A, starting a stirring device to uniformly mix materials consisting of the isocyanate, the epoxy resin or the epoxy polyalkylsiloxane and the telechelic carboxyl polybutadiene, controlling the temperature of the materials to be between (normal temperature and 175) DEG C, and keeping the temperature for 0.5-6 h, wherein the higher the temperature of the materials is between (normal temperature and 175) DEG C, the shorter the temperature keeping time is, and the lower the temperature of the materials is, the longer the temperature keeping time is; if the added materials are isocyanate and telechelic carboxyl polybutadiene, the reaction product is obtained according to the chemical structural formula (2), if the added materials are epoxy resin and telechelic carboxyl polybutadiene, the reaction product is obtained according to the chemical structural formula (3), and if the added materials are epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene, the reaction product is obtained according to the chemical structural formula (4); if the ratio of the mass of the telechelic carboxyl polybutadiene to the molar number of the added mass of the isocyanate or epoxy resin is more than 2 and the ratio of the mass of the telechelic carboxyl polybutadiene to the molar number of the added mass of the epoxy polyalkylsiloxane is more than 2, the unreacted telechelic carboxyl polybutadiene is excessive;
in the A composition, a block polymerization process of the telechelic amino compound base
Adding any one of isocyanate or epoxy resin with the mass ratio of 1 mol and telechelic amino polypropylene oxide or amino polyalkylsiloxane with the mass ratio of (1.8-5) mol into a reactor A; or adding epoxy polyalkylsiloxane with the mass ratio of 1 mol and telechelic amino polypropylene oxide or amino polyalkylsiloxane with the mass ratio of (2.8-8) mol into the reactor A for the other time; starting a stirring device to uniformly mix materials consisting of isocyanate or epoxy resin or epoxy polyalkylsiloxane and telechelic amino polypropylene oxide or amino polyalkylsiloxane, controlling the temperature of the materials to be between (normal temperature and 175) DEG C, and keeping the temperature for 0.5 to 6 hours, wherein correspondingly, the higher the temperature of the materials is between (normal temperature and 175) DEG C, the shorter the temperature keeping time is, and the lower the temperature of the materials is, the longer the temperature keeping time is; if the added materials are isocyanate and telechelic amino polypropylene oxide, the reaction product is obtained according to the chemical structural formula (7), if the added materials are isocyanate and amino polyalkylsiloxane, the reaction product is obtained according to the chemical structural formula (8), if the added materials are epoxy resin and telechelic amino polypropylene oxide, the reaction product is obtained according to the chemical structural formula (9), if the added materials are epoxy resin and amino polyalkylsiloxane, the reaction product is obtained according to the chemical structural formula (10), if the added materials are epoxy polyalkylsiloxane and telechelic amino polypropylene oxide, the reaction product is obtained according to the chemical structural formula (11), and if the added materials are epoxy polyalkylsiloxane and amino polyalkylsiloxane, the reaction product is obtained according to the chemical structural formula (12); in the chemical structural formulae (7) to (10), if the ratio of the molar amount of the charged telechelic amino polypropylene oxide or amino polyalkylsiloxane to the charged amount of the isocyanate or epoxy resin is more than 2, the unreacted telechelic amino polypropylene oxide or amino polyalkylsiloxane becomes excessive; in the chemical structural formulae (11) to (12), if the molar ratio of the mass of telechelic amino polypropylene oxide or amino polyalkylsiloxane to the mass of epoxy polyalkylsiloxane added is more than 3, there will be an excess of unreacted telechelic amino polypropylene oxide or amino polyalkylsiloxane;
in the composition B, a method for block polymerization of the telechelic isocyanate-based compound
Adding 1.8-5 mol of isocyanate and 1 mol of telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide into a reactor B, starting a stirring device to uniformly mix the isocyanate and the materials consisting of the telechelic carboxyl polybutadiene and/or the telechelic amino polypropylene oxide, controlling the temperature of the materials to be between (normal temperature and 175) DEG C, and keeping the temperature for 0.5-6 h, wherein the higher the temperature of the materials is between (normal temperature and 175) DEG C, the shorter the temperature keeping time is, and the lower the temperature of the materials is, the longer the temperature keeping time is;
adding 2.8-8 mol of isocyanate and 1 mol of amino polyalkylsiloxane into the other reactor B, starting a stirring device to uniformly mix materials consisting of the isocyanate and the amino polyalkylsiloxane, controlling the temperature of the materials to be between (normal temperature and 175) DEG C, and keeping the temperature for 0.5-6 h, wherein the higher the temperature of the materials is between (normal temperature and 175) DEG C, the shorter the temperature is, and the lower the temperature is, the longer the temperature is; if the added materials are isocyanate and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide, the reaction product is obtained according to the chemical structural formula (14) and/or the chemical structural formula (15), and if the added materials are isocyanate and amino polyalkylsiloxane, the reaction product is obtained according to the chemical structural formula (16); in the chemical structural formulae (14) to (15), if the ratio of the mass of the isocyanate to the molar number of the added mass of the telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide is more than 2, the unreacted isocyanate will be in excess; in the chemical formula (16), if the ratio of the mass of the isocyanate to the number of moles of the added mass of the aminoalkylsiloxane is more than 3, the unreacted isocyanate may be excessive;
in the composition B, a process for block polymerization of the telechelic epoxy compound base
Adding epoxy resin and/or epoxy polyalkylsiloxane with the mass ratio of 1.8-5 mol and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide with the mass ratio of 1 mol into a reactor B; adding 2.8-8 mol of epoxy resin and/or epoxy polyalkylsiloxane and 1 mol of amino polyalkylsiloxane into the other secondary reactor B; starting a stirring device to uniformly mix materials consisting of epoxy resin and/or epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide, uniformly mix materials consisting of epoxy resin and/or epoxy polyalkylsiloxane and amino polyalkylsiloxane, control the temperature of the materials to be between (normal temperature and 175 ℃) DEG C, and keep the temperature for 0.5 to 6 hours, wherein correspondingly, the higher the temperature of the materials (normal temperature to 175 ℃) is, the shorter the heat preservation time is, and the lower the temperature of the materials is, the longer the heat preservation time is; if the materials added are epoxy resin and/or epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide, the reaction product comprises the product obtained according to the chemical structural formula (18) and/or the formula (19) and/or (22) and/or (23); if the added materials are epoxy resin and/or epoxy polyalkyl siloxane and amino polyalkyl siloxane, the reaction product is obtained according to the chemical structural formula (20) and/or (24); in the chemical formulae (18), (19), (22), (23), if the ratio of the mass of the epoxy resin and/or epoxy polyalkylsiloxane to the molar number of the mass of telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide added is more than 2, there will be an excess of unreacted epoxy resin and/or epoxy polyalkylsiloxane; in the chemical structures (20), (24), if the ratio of the charged mass of the epoxy resin and/or the epoxy polyalkylsiloxane to the molar number of the added mass of the amino polyalkylsiloxane is more than 3, there is an excess of the unreacted epoxy resin and/or the epoxy polyalkylsiloxane.
Further, the method for controlling and mixing the shear strength of the liquid material and the powder material in the step (II) comprises the following steps:
firstly adding powder of at least one (16-31)% of telechelic carboxyl compound and/or telechelic amino compound base stock, coupling agent and/or modifier (0-1.5)%, curing accelerator (0-2.5)%, heat insulation powder (44-62)% and flame retardant component (15-26)% into a reactor A with a high-speed stirring and/or high-shearing dispersing device;
firstly adding at least one (9-35)% of telechelic isocyanate-based compound and/or telechelic epoxy-based compound base material, 0-1.5)% of coupling agent and/or modifying agent, 0-2.5)% of curing accelerator, 44-62% of heat-insulating powder and 15-26% of flame-retardant component into a reactor B with a high-speed stirring and/or high-shear dispersing device;
respectively in the reactor A and the reactor B according to the average particle diameter D of the powder50The specification is divided into three or more batches of thin → medium → thick, and the finest D is added first50Powder of size → submicron D50Powder of size → intermediate D50Powder of size → coarse D50The powder with the specification is analogized until the coarsest D50Powder with specification; each time adding one D50Powder of a specification, replacementControlling the diameter or rotating speed of the stator and rotor of the high-shear dispersing device to control the shear strength to (1200-233000) s-1Controlling the temperature of the slurry within the range of (0-175) DEG C and maintaining the temperature for (0.1-4) hours; the shear strength is calculated according to equation (27),
in the formula (27), the reaction mixture is,
Ssshear strength, unified or converted units of "1/second" or s-1，
V-the rotational linear velocity of the outer diameter of the rotor, or the relative rotational linear velocity of the outer diameter of an adjacent pair of rotors, is unified or converted into units of "m/s" or m/s,
delta-the minimum gap between adjacent stators and rotors, or between adjacent rotors and rotors, in unity or in scaled units of "meters" or m;
when the powder D is in the heat-insulating powder and the flame-retardant component50When the specification is more than 1.0 mu m, the high-shear bulk device can be defaulted, the heat-insulating powder and the powder in the flame-retardant component can be added at one time, the mixture is uniformly mixed by a high-speed stirring device, and the rotating speed of the high-speed stirring device is controlled to be 100-1000 r/min.
Further, the positive pressure or negative pressure reaction control method of step (iii) includes:
the pressure is gauge pressure; the positive pressure is to maintain the pressure (0.0-0.1) MPa in the reactor; the negative pressure is to maintain the pressure in the reactor to be (-0.01 to-0.1) MPa so as to remove air, carbon dioxide, moisture and low molecular substances hidden in the raw materials; the reaction further comprises at least one of the subsequent chemical reactions according to chemical structural formulas (2) to (4), (7) to (12) in the composition A, and at least one of the subsequent chemical reactions according to chemical structural formulas (14) to (16), chemical structural formulas (18) to (20), and chemical structural formulas (22) to (24) in the composition B; and (5) starting a vacuum pump at the same time of the step (II) or at the later stage, and slowly reducing the pressure to-0.1 MPa.
Further, the step (iv) heating and cooling method includes:
filling a heat transfer medium into a jacket of the reactor while performing the step (I), the step (II) and the step (III), and driving heating and cooling by using fluid circulation equipment; the heat transfer medium comprises any one of heat transfer oil, water or cooling liquid; the circulating equipment comprises any one of a mould temperature machine, a magnetic force driving pump, a reciprocating plunger pump, a peristaltic pump and a centrifugal pump.
The invention relates to a heat insulation structural adhesive for a new energy power battery and a manufacturing method thereof, and the heat insulation structural adhesive has the beneficial technical effects that:
firstly, a block synthesis method is adopted, the proportion of a hard segment and a soft segment of a molecular chain is adjusted, and the bonding strength, the tensile strength and the secant modulus of a terminal curing product in a wider range can be flexibly obtained;
secondly, the reaction condition is mild, and the reaction can be realized at the temperature range of (normal temperature to 175) DEG C and the pressure range of (-0.1 to 0.1) MPa;
thirdly, the heat conductivity coefficient is less than 0.08W/(m.K), the shear bonding strength is more than 4MPa, the flame retardance is V-0, and the density is less than 0.6g/cm3The requirements of heat insulation and structural strength required by the CTP battery pack during normal service period and even in the whole life cycle can be met.
Drawings
FIG. 1 shows the results of shear bond strength tests of the combinations of example 7 and example 19 of the present invention, wherein the combinations are mixed and cured at a volume ratio of 1: 0.25-2.0 (Va: Vb).
Detailed Description
In order to explain the technical content, the achieved objects and the effects of the heat insulation structural adhesive for the new energy power battery and the manufacturing method thereof in detail, the following is further described with reference to the embodiments.
1) Examples of Material formulations
The invention discloses a material formula embodiment of a heat insulation structural adhesive for a new energy power battery, which comprises forty-six examples, wherein:
a) twelve examples of typical formulations of composition a, see table 1;
b) twelve examples of typical formulations of the composition B are shown in Table 2;
c) twelve physical and chemical electrical performance test results of the composition A and the composition B after mixed curing are shown in Table 3, wherein the volume ratio of the composition A to the composition B is 1: 1;
d) the shear bond strength test results of example 7 and example 19 combined at a volume ratio of 1: Vb (0.25-2.0) were ten examples of the shear bond strength test results after mixing and curing, and are shown in table 4 and fig. 1.
From tables 1 to 4, forty-six examples of formulations of materials can be seen as typical formulations within the bounds of the present invention.
2) Examples of the manufacturing method
The embodiment of the method for manufacturing the heat-insulating structural adhesive for the new energy power battery is carried out by matching with forty-six material formula embodiments, and can be regarded as a typical process within the boundary of the invention.
Step (one), example 47:
a composition, block polymerization process of telechelic carboxyl compound base material-
Adding any one of isocyanate, epoxy resin or epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene into a reactor A according to the mass ratio shown in the table 1, and starting a stirring device to uniformly mix materials consisting of the isocyanate, the epoxy resin or the epoxy polyalkylsiloxane and the telechelic carboxyl polybutadiene; when the materials are isocyanate and telechelic carboxyl polybutadiene, controlling the temperature of the materials to be between 25 and 45 ℃, and keeping the temperature for 6 hours to obtain a reaction product according to a chemical structural formula (2); when the materials are epoxy resin and telechelic carboxyl polybutadiene, controlling the temperature of the materials to be 75-135 ℃, and keeping the temperature for 4.0h to obtain a reaction product according to a chemical structural formula (3); when the materials are epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene, controlling the temperature of the materials to be 75-135 ℃, and keeping the temperature for 3.5h to obtain a reaction product according to a chemical structural formula (4); because the ratio of the mass of the telechelic carboxyl polybutadiene to the molar number of the added mass of the isocyanate or the epoxy resin is close to 2, and the ratio of the mass of the telechelic carboxyl polybutadiene to the molar number of the added mass of the epoxy polyalkylsiloxane is close to 3, the excess amount of the unreacted telechelic carboxyl polybutadiene can be ignored;
a composition, block polymerization process of telechelic amino compound base material-
In the reactor A, according to the mass ratio of the isocyanate or the epoxy resin, telechelic amino polypropylene oxide or amino polyalkylsiloxane is added according to the table 1; in another reactor A, adding epoxy polyalkylsiloxane, telechelic amino polypropylene oxide or amino polyalkylsiloxane according to the mass ratio in the following table 1; starting a stirring device to uniformly mix materials consisting of isocyanate, epoxy resin or epoxy polyalkylsiloxane and telechelic amino polypropylene oxide or amino polyalkylsiloxane; when the added materials are isocyanate and telechelic amino polypropylene oxide, controlling the temperature of the materials to be between 60 and 85 ℃, and keeping the temperature for 1.5 hours to obtain a reaction product according to a chemical structural formula (7); when the added materials are isocyanate and amino polyalkylsiloxane, controlling the temperature of the materials to be between 60 and 85 ℃, and keeping the temperature for 2 hours, wherein the reaction product is obtained according to a chemical structural formula (8); when the added materials are epoxy resin and telechelic amino polypropylene oxide, controlling the temperature of the materials to be between 65 and 90 ℃, and keeping the temperature for 1.5h to obtain a reaction product according to a chemical structural formula (9); when the materials are epoxy resin and amino polyalkylsiloxane, controlling the temperature of the materials to be between 65 and 90 ℃, and keeping the temperature for 2.0 hours, wherein the reaction product is obtained according to a chemical structural formula (10); when the materials are epoxy polyalkylsiloxane and telechelic amino polypropylene oxide, controlling the temperature of the materials to be between 55 and 75 ℃, and keeping the temperature for 3.5 hours, wherein the reaction product is obtained according to a chemical structural formula (11); when the added materials are epoxy polyalkylsiloxane and amino polyalkylsiloxane, controlling the temperature of the materials to be 50-70 ℃, and keeping the temperature for 5.5 hours, wherein the reaction product is obtained according to a chemical structural formula (12); because the ratio of the mass of the telechelic amino polypropylene oxide or amino polyalkylsiloxane to the molar number of the added mass of the isocyanate or epoxy resin is close to 2, the excess amount of unreacted telechelic amino polypropylene oxide or amino polyalkylsiloxane can be ignored; because the ratio of the mass of the telechelic amino polypropylene oxide or amino polyalkylsiloxane to the molar number of the added mass of the epoxy polyalkylsiloxane is close to 3, the excess amount of unreacted telechelic amino polypropylene oxide or amino polyalkylsiloxane can be ignored;
composition B, Process for the Block polymerization of a telechelic isocyanato Compound
Adding isocyanate, telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide in a mass ratio into a reactor B according to the table 2, and starting a stirring device to uniformly mix materials consisting of the isocyanate, the telechelic carboxyl polybutadiene and/or the telechelic amino polypropylene oxide; adding isocyanate and amino polyalkylsiloxane in the mass ratio according to the table 2 into the other reactor B, and starting a stirring device to uniformly mix materials consisting of the isocyanate and the amino polyalkylsiloxane; when the added materials are isocyanate and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide, controlling the temperature of the materials to be between 25 and 45 ℃, keeping the temperature for 5.5 hours, and obtaining a reaction product according to a chemical structural formula (14) and/or a chemical structural formula (15); when the added materials are isocyanate and amino polyalkylsiloxane, controlling the temperature of the materials to be 60-85 ℃, and keeping the temperature for 1.0h to obtain a reaction product according to a chemical structural formula (16); because the ratio of the added mass of the isocyanate to the mole number of the added mass of the telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide is close to 2, the excess amount of the unreacted isocyanate can be ignored; because the ratio of the added mass of the isocyanate to the added mass of the amino polyalkylsiloxane is close to 3, the excess amount of unreacted isocyanate can be ignored;
b composition, block polymerization process of telechelic epoxy compound base material-
In the reactor B, adding epoxy resin and/or epoxy polyalkylsiloxane, telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide according to the mass ratio in the table 2; in another B reactor, adding epoxy resin and/or epoxy polyalkylsiloxane and amino polyalkylsiloxane according to the mass ratio in the following table 2; starting a stirring device to uniformly mix materials consisting of the epoxy resin and/or the epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide and uniformly mix materials consisting of the epoxy resin and/or the epoxy polyalkylsiloxane and amino polyalkylsiloxane; when the added materials are epoxy resin and/or epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide, controlling the temperature of the materials to be between 55 and 75 ℃, and keeping the temperature for 3.5 hours, wherein the reaction product comprises a product obtained according to a chemical structural formula (18) and/or a formula (19) and/or a formula (22) and/or a formula (23); when the added materials are epoxy resin and/or epoxy polyalkyl siloxane and amino polyalkyl siloxane, controlling the temperature of the materials to be (45-65) DEG C, and preserving the temperature for 4.5h, wherein the reaction product is obtained according to the chemical structural formula (20) and/or (24); since the ratio of the mass of the epoxy resin and/or the epoxypolyalkylsiloxane to the number of moles of the added mass of the telechelic carboxylated polybutadiene and/or telechelic aminopolypropylene oxide is close to 2, the excess of unreacted epoxy resin and/or epoxypolyalkylsiloxane is negligible; since the ratio of the mass of the epoxy resin and/or the epoxy polyalkylsiloxane to the number of moles of the added mass of the amino polyalkylsiloxane is close to 3, the excess amount of unreacted epoxy resin and/or epoxy polyalkylsiloxane is negligible.
Step (two), example 48:
firstly, adding at least one of telechelic carboxyl compound and/or telechelic amino compound base stock, a coupling agent and/or a modifier, a curing accelerator, heat-insulating powder and flame-retardant components according to the step (I) into a reactor A with a high-speed stirring and high-shear dispersing device according to the table 1;
in a reactor B with a high-speed stirring and high-shear dispersing device, firstly adding at least one of telechelic isocyanate-based compound and/or telechelic epoxy-based compound base material, a coupling agent and/or a modifier, a curing accelerator, heat-insulating powder and flame-retardant components according to the step (I) in the following table 2;
respectively in the reactor A and the reactor B according to the average particle diameter D of the powder50The specification is divided into three batches of thin → medium → thick, and the finest D is added first50Powder of size → submicron D50Powder of size → coarse D50Powder with specification; each time adding one D50Powder of specified size, replacing high shear dispersing deviceThe diameters of the stator and the rotor or the rotating speed are adjusted, and the shearing strength is controlled to be (1200-5000) s-1Controlling the temperature of the slurry within the range of (5-155) DEG C and maintaining for 0.25 h; the shear strength is calculated according to equation (27); the rotating speed of the high-speed stirring device is controlled to be 100-1000 r/min.
Step (iii), example 49:
and (5) starting a vacuum pump at the same time or at the later stage of the step (II), slowly reducing the pressure in the reactor to-0.1 MPa, and maintaining the pressure of-0.1 MPa for accumulation for 0.25-1.5 hours.
Step (iv), example 50:
filling a heat transfer medium into a jacket of the reactor while performing the step (I), the step (II) and the step (III), and driving heating and cooling by using fluid circulation equipment; the heat transfer medium is heat transfer oil to control the temperature of the materials in the reactor; the circulating equipment adopts a mold temperature controller.
By adopting forty-six examples and fifty examples of the material formula, the heat-insulating structural adhesive for the new energy power battery and the manufacturing method thereof can be seen, and the beneficial technical effects of the heat-insulating structural adhesive are achieved:
firstly, a block synthesis method is adopted, the proportion of a hard segment and a soft segment of a molecular chain can be flexibly adjusted, and the physicochemical electrical property of a terminal curing product in a wider range is obtained:
when the volume ratio of the composition A to the composition B is 1: 1,
when the volume ratio of the composition A to the composition B is 1 to (0.25-2),
the shear bonding strength (0.3-13.8) MPa is continuously adjustable and controllable;
the requirements of heat insulation and structural strength required by the CTP battery pack during normal service and even in the whole life cycle can be met.
TABLE 4 test results for shear bond strengths at different volume ratios
Claims (12)
1. The heat-insulating structural adhesive for the new energy power battery is characterized by comprising the following components in percentage by mass: the composition A contains (16-31)% of at least one of a block-polymerized telechelic carboxyl compound and/or a block-polymerized telechelic amino compound, 0-1.5)% of a coupling agent and/or a modifying agent, 0-2.5)% of a curing accelerator, 44-62)% of a heat-insulating powder, and 15-26)% of a flame-retardant component; the composition B contains 16-31% of at least one of a block-polymerized telechelic isocyanate-based compound and/or a block-polymerized telechelic epoxy-based compound, 0-1.5% of a coupling agent and/or a modifying agent, 0-2.5% of a curing accelerator, 44-62% of a heat-insulating powder and 15-26% of a flame-retardant component; when in use, 1 part of the composition A and 0.25-2 parts of the composition B are uniformly mixed according to the volume ratio or the mass ratio and are cured into the heat-insulating structural adhesive or the bonding material for end use.
2. A method for manufacturing a heat insulation structural adhesive for a new energy power battery is characterized by comprising the following steps: the method comprises the following steps of (A) a block polymerization method of a telechelic carboxyl compound and/or telechelic amino compound base material, and a block polymerization method of a telechelic isocyanate compound and/or telechelic epoxy compound base material, wherein the head-head connection or head-tail connection orientation of molecular chains is random during block polymerization, and the atom arrangement orientation of cis-form or trans-form molecular chain segments is random; and (II) controlling and mixing the shearing strength of the liquid material and the powder material.
3. The structural insulating adhesive according to claim 1, wherein the block-polymerized telechelic carboxyl compound in the composition a further comprises: at least one of telechelic carboxyl polybutadiene with a chemical structural formula (1), a product of reacting isocyanate with telechelic carboxyl polybutadiene according to a chemical structural formula (2) and removing carbon dioxide, a product of reacting epoxy resin with telechelic carboxyl polybutadiene according to a chemical structural formula (3), and a product of reacting epoxy polyalkylsiloxane with telechelic carboxyl polybutadiene according to a chemical structural formula (4);
wherein the chemical structural formula (1) —
And in the chemical formula (1), x is 1, y is 0 to 1.0, z is a number average degree of polymerization of 9 to 27, the number average functionality of carboxyl is 2.1 to 2.2, R is a ratio of moles to x8Is vinyl or cyano;
wherein the chemical structural formula (2) — is
And in the chemical formula (2), isocyanate OCN-R1Isocyanate number average functionality of-NCO of 2.0, R1Is at least one of an alkylene, phenylene or substituted phenylene, arylcyclopropene or substituted arylcyclopropene, heterocyclylene or heterocyclylene, said alkylene being a group which cleaves at a carbon-hydrogen bond in one molecule of an organic compound to remove two hydrogen atoms (hereinafter "alkylene" is in accordance with this definition);
wherein the chemical structural formula (3) — is
And in the chemical structural formula (3), the epoxy compound conforms to the definition of the chemical structural formula (17);
wherein the chemical structural formula (4) — is
And in the chemical structural formula (4), the epoxy compound conforms to the definition of the chemical structural formula (21).
4. The structural insulating adhesive according to claim 1, wherein the block-polymerized telechelic amino compound in the composition a further comprises: at least one of telechelic amino polypropylene oxide having chemical structural formula (5), amino polyalkylsiloxane having chemical structural formula (6), a product of reaction of isocyanate and telechelic amino polypropylene oxide according to chemical structural formula (7), a product of reaction of isocyanate and amino polyalkylsiloxane according to chemical structural formula (8), a product of reaction of epoxy resin and telechelic amino polypropylene oxide according to chemical structural formula (9), a product of reaction of epoxy resin and amino polyalkylsiloxane according to chemical structural formula (10), a product of reaction of epoxy polyalkylsiloxane and telechelic amino polypropylene oxide according to chemical structural formula (11), and a product of reaction of epoxy polyalkylsiloxane and amino polyalkylsiloxane according to chemical structural formula (12);
wherein the chemical structural formula (5) — is
In the chemical structural formula (5), k is the number average degree of polymerization of 25-50, and the number average functionality of amino is 2.0-2.3;
wherein the chemical structural formula (6) — is
And in the chemical structural formula (6), the number average polymerization degree is m ═ 0-1, n ═ 8-22, the number average functionality of amido is 2.9-3.3, R2Is alkylene having 2 to 5 carbon atoms, R3、R4、R5And R6Is at least one of alkyl, phenyl or substituted phenyl, aromatic ring group or substituted aromatic ring group, heterocyclic group or heterocyclic group;
wherein the chemical structural formula (7) — is
Wherein the chemical structural formula (8) — is
Wherein the chemical structural formula (9) — is
Wherein the chemical structural formula (10) — is
Wherein the chemical structural formula (11) — is
Wherein the chemical structural formula (12) — is
5. The structural insulating adhesive of claim 1, wherein in said composition B, said block-polymerized telechelic isocyanate-based compound further comprises: at least one of isocyanate having a chemical structural formula (13), a product of reacting isocyanate with telechelic carboxyl polybutadiene according to a chemical structural formula (14) and removing carbon dioxide, a product of reacting isocyanate with telechelic amino polypropylene oxide according to a chemical structural formula (15), and a product of reacting isocyanate with amino polyalkylsiloxane according to a chemical structural formula (16);
wherein the chemical structural formula (13) — is
OCN-R1-NCO (13)
In the chemical structural formula (13), the number average functionality of the isocyanate group is 2.0, and R1 is at least one of alkylene, phenylene or substituted phenylene, aromatic cyclopropene or substituted aromatic cyclopropene, heterocyclic ring or heterocyclic ring-taking support;
wherein the chemical structural formula (14) —
Wherein the chemical structural formula (15) — is
Wherein the chemical structural formula (16) — is
6. The structural insulating adhesive according to claim 1, wherein the block-polymerized telechelic epoxy-based compound in the composition B further comprises: at least one of an epoxy resin having a chemical structural formula (17), a product of a reaction of an epoxy resin and telechelic carboxy polybutadiene according to chemical structural formula (18), a product of a reaction of an epoxy resin and telechelic amino polypropylene oxide according to chemical structural formula (19), a product of a reaction of an epoxy resin and amino polyalkylsiloxane according to chemical structural formula (20), an epoxy polyalkylsiloxane having a chemical structural formula (21), a product of a reaction of an epoxy polyalkylsiloxane and telechelic carboxy polybutadiene according to chemical structural formula (22), a product of a reaction of an epoxy polyalkylsiloxane and telechelic amino polypropylene oxide according to chemical structural formula (23), and a product of a reaction of an epoxy polyalkylsiloxane and amino polyalkylsiloxane according to chemical structural formula (24);
wherein the chemical structural formula (17) —
And in the chemical structural formula (17), the number average functionality of the epoxy group is 2.0 or 3.0, further comprising: r7Is at least one of alkylene, phenylene or substituted phenylene, aromatic or substituted aromatic, heterocyclic or heterocyclic ring support according to the chemical structural formula (25) or the chemical structural formula (26);
wherein the chemical structural formula (18) — is
Wherein the chemical structural formula (19) — is
Wherein the chemical structural formula (20) — is
Wherein the chemical structural formula (21) — is
In the chemical structural formula (21), the number average polymerization degree of the alkyl siloxane is more than or equal to 0, n is 5-50, the number average functionality of the epoxy group is 2.8-3.0, R2Is alkylene having 2 to 5 carbon atoms, R3、R4、R5And R6Is at least one of alkyl, phenyl or substituted phenyl, aromatic ring group or substituted aromatic ring group, heterocyclic group or heterocyclic group;
wherein the chemical structural formula (22) — is
Wherein the chemical structural formula (23) —
Wherein the chemical structural formula (24) — is
Wherein the chemical structural formula (25) — is
And in the chemical structural formula (25), the number average polymerization degree is q 1-2, the number average functionality of the epoxy group is 2.0 or 3.0, R9At least one of alkyl with 1-5 hydrogen atoms and carbon atoms, phenyl or substituted phenyl, aromatic or substituted aromatic ring, heterocyclic radical or heterocyclic radical;
wherein the chemical structural formula (26) — is
And in the chemical structural formula (26), the number average polymerization degree is q 1-2, the number average functionality of the epoxy group is 2.0 or 3.0, R9Is at least one of an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, a phenyl group or a substituted phenyl group, an aromatic ring group or a substituted aromatic ring group, a heterocyclic group or a heterocyclic group.
7. The structural insulating adhesive according to claim 1, wherein the coupling agent and/or the modifying agent comprises: hexadecyl trimethoxysilane [ CAS: 16415-12-6], hexadecyltriethoxysilane [ CAS: 16415-13-7], gamma- (2, 3-glycidoxy) propyltrimethoxysilane [ CAS: 2530-83-8], gamma- (2, 3-epoxypropoxy) propyltriethoxysilane [ CAS: 2602-34-8], gamma-aminopropyltrimethoxysilane [ CAS: 13822-56-5], gamma-aminopropyltriethoxysilane [ CAS: 919-30-2), n- (β -aminoethyl) - γ -aminopropyltrimethoxysilane [ CAS: 1760-24-3), n- (β -aminoethyl) - γ -aminopropyltriethoxysilane [ CAS: 5089-72-5], gamma- (methacryloyloxy) propyltrimethoxysilane [ CAS: 2530-85-0], gamma- (methacryloyloxy) propyltriethoxysilane [ CAS: 21142-29-0], gamma-diethylenetriaminepropylmethyldimethoxysilane [ CAS: 99740-64-4 ]; or isopropyldioleacyloxy (dioctylphosphatoxy) titanate [ CAS: 61417-49-0], isopropyltris (dioctylphosphonoxy) titanate [ CAS: 65345-34-8], isopropyl triisostearate [ CAS: 61417-49-0], bis (dioctyloxypyrophosphate) ethylene titanate [ CAS: 65467-75-6], tetraisopropylbis (dioctylphosphatoxy) titanate [ CAS: 65460-52-8 ]; or oleic acid [ CAS: 112-80-1), lauric acid [ CAS: 143-07-7), caprylic acid [ CAS: 124-07-2), ricinoleic acid [ CAS: 141-22-0], abietic acid [ CAS: 514-10-3], salicylic acid [ CAS: 69-72-7), benzoic acid [ CAS: 65-85-0], dodecylbenzenesulfonic acid [ CAS: 27176-87-0), benzotriazole [ CAS: 95-14-7, and at least one of tolyltriazole [ CAS number 29385-43-1 ].
8. The structural insulating adhesive according to claim 1, wherein the curing accelerator comprises: phenol [ CAS: 108-95-2), 2, 4, 6-tris (dimethylaminomethyl) phenol [ CAS: 90-72-2), triphenylphosphine [ CAS: 603-35-0], imidazole [ CAS: 288-32-4 ].
9. The structural insulating adhesive according to claim 1, wherein the insulating powder comprises: at least one of hollow glass microspheres, nano hollow fibers and fumed silica; average particle diameter D of single particles and agglomerated particles of heat-insulating powder50Is between (10 to 65) mu m.
10. The structural insulating adhesive according to claim 1, wherein the flame retardant component comprises: aluminum hydroxide [ Al (OH)3]Magnesium hydroxide [ Mg (OH) ]2]Melamine cyanurate [ CAS: 37640-57-6]Ammonium polyphosphate (APP), aluminum hypophosphite [ Al (H)2PO2)3]Tricresyl phosphate [ CAS: 1330-78-5]Diethyl ethylphosphate [ CAS: 682-30-4]At least one of; wherein the average particle diameter D of the powder flame-retardant component single particles and agglomerated particles50Is between 0.45 and 90 μm.
11. The structural insulating adhesive according to claim 2, wherein the step (a) of block polymerization of telechelic carboxyl compound and/or telechelic amino compound binder, and block polymerization of telechelic isocyanate compound and/or telechelic epoxy compound binder is carried out in such a manner that the orientation of "head-to-head" or "head-to-tail" of the molecular chains is random and the orientation of the atomic arrangement of the cis or trans molecular chain segments is random, comprises:
in the composition A, a block polymerization process of the telechelic carboxyl compound base
Adding 1 mol of any one of isocyanate, epoxy resin or epoxy polyalkylsiloxane and 1.8-5 mol of telechelic carboxyl polybutadiene into a reactor A, starting a stirring device to uniformly mix materials consisting of the isocyanate, the epoxy resin or the epoxy polyalkylsiloxane and the telechelic carboxyl polybutadiene, controlling the temperature of the materials to be between (normal temperature and 175) DEG C, and keeping the temperature for 0.5-6 h, wherein the higher the temperature of the materials is between (normal temperature and 175) DEG C, the shorter the temperature keeping time is, and the lower the temperature of the materials is, the longer the temperature keeping time is; if the added materials are isocyanate and telechelic carboxyl polybutadiene, the reaction product is obtained according to the chemical structural formula (2), if the added materials are epoxy resin and telechelic carboxyl polybutadiene, the reaction product is obtained according to the chemical structural formula (3), and if the added materials are epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene, the reaction product is obtained according to the chemical structural formula (4); if the ratio of the mass of the telechelic carboxyl polybutadiene to the molar number of the added mass of the isocyanate or epoxy resin is more than 2 and the ratio of the mass of the telechelic carboxyl polybutadiene to the molar number of the added mass of the epoxy polyalkylsiloxane is more than 2, the unreacted telechelic carboxyl polybutadiene is excessive;
in the A composition, a block polymerization process of the telechelic amino compound base
Adding any one of isocyanate or epoxy resin with the mass ratio of 1 mol and telechelic amino polypropylene oxide or amino polyalkylsiloxane with the mass ratio of (1.8-5) mol into a reactor A; or adding epoxy polyalkylsiloxane with the mass ratio of 1 mol and telechelic amino polypropylene oxide or amino polyalkylsiloxane with the mass ratio of (2.8-8) mol into the reactor A for the other time; starting a stirring device to uniformly mix materials consisting of isocyanate or epoxy resin or epoxy polyalkylsiloxane and telechelic amino polypropylene oxide or amino polyalkylsiloxane, controlling the temperature of the materials to be between (normal temperature and 175) DEG C, and keeping the temperature for 0.5 to 6 hours, wherein correspondingly, the higher the temperature of the materials is between (normal temperature and 175) DEG C, the shorter the temperature keeping time is, and the lower the temperature of the materials is, the longer the temperature keeping time is; if the added materials are isocyanate and telechelic amino polypropylene oxide, the reaction product is obtained according to the chemical structural formula (7), if the added materials are isocyanate and amino polyalkylsiloxane, the reaction product is obtained according to the chemical structural formula (8), if the added materials are epoxy resin and telechelic amino polypropylene oxide, the reaction product is obtained according to the chemical structural formula (9), if the added materials are epoxy resin and amino polyalkylsiloxane, the reaction product is obtained according to the chemical structural formula (10), if the added materials are epoxy polyalkylsiloxane and telechelic amino polypropylene oxide, the reaction product is obtained according to the chemical structural formula (11), and if the added materials are epoxy polyalkylsiloxane and amino polyalkylsiloxane, the reaction product is obtained according to the chemical structural formula (12); in the chemical structural formulae (7) to (10), if the ratio of the molar amount of the charged telechelic amino polypropylene oxide or amino polyalkylsiloxane to the charged amount of the isocyanate or epoxy resin is more than 2, the unreacted telechelic amino polypropylene oxide or amino polyalkylsiloxane becomes excessive; in the chemical structural formulae (11) to (12), if the molar ratio of the mass of telechelic amino polypropylene oxide or amino polyalkylsiloxane to the mass of epoxy polyalkylsiloxane added is more than 3, there will be an excess of unreacted telechelic amino polypropylene oxide or amino polyalkylsiloxane;
in the composition B, a method for block polymerization of the telechelic isocyanate-based compound
Adding 1.8-5 mol of isocyanate and 1 mol of telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide into a reactor B, starting a stirring device to uniformly mix the isocyanate and the materials consisting of the telechelic carboxyl polybutadiene and/or the telechelic amino polypropylene oxide, controlling the temperature of the materials to be between (normal temperature and 175) DEG C, and keeping the temperature for 0.5-6 h, wherein the higher the temperature of the materials is between (normal temperature and 175) DEG C, the shorter the temperature keeping time is, and the lower the temperature of the materials is, the longer the temperature keeping time is;
adding 2.8-8 mol of isocyanate and 1 mol of amino polyalkylsiloxane into the other reactor B, starting a stirring device to uniformly mix materials consisting of the isocyanate and the amino polyalkylsiloxane, controlling the temperature of the materials to be between (normal temperature and 175) DEG C, and keeping the temperature for 0.5-6 h, wherein the higher the temperature of the materials is between (normal temperature and 175) DEG C, the shorter the temperature is, and the lower the temperature is, the longer the temperature is; if the added materials are isocyanate and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide, the reaction product is obtained according to the chemical structural formula (14) and/or the chemical structural formula (15), and if the added materials are isocyanate and amino polyalkylsiloxane, the reaction product is obtained according to the chemical structural formula (16); in the chemical structural formulae (14) to (15), if the ratio of the mass of the isocyanate to the molar number of the added mass of the telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide is more than 2, the unreacted isocyanate will be in excess; in the chemical formula (16), if the ratio of the mass of the isocyanate to the number of moles of the added mass of the aminoalkylsiloxane is more than 3, the unreacted isocyanate may be excessive;
in the composition B, a process for block polymerization of the telechelic epoxy compound base
Adding epoxy resin and/or epoxy polyalkylsiloxane with the mass ratio of 1.8-5 mol and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide with the mass ratio of 1 mol into a reactor B; adding 2.8-8 mol of epoxy resin and/or epoxy polyalkylsiloxane and 1 mol of amino polyalkylsiloxane into the other secondary reactor B; starting a stirring device to uniformly mix materials consisting of epoxy resin and/or epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide, uniformly mix materials consisting of epoxy resin and/or epoxy polyalkylsiloxane and amino polyalkylsiloxane, control the temperature of the materials to be between (normal temperature and 175 ℃) DEG C, and keep the temperature for 0.5 to 6 hours, wherein correspondingly, the higher the temperature of the materials (normal temperature to 175 ℃) is, the shorter the heat preservation time is, and the lower the temperature of the materials is, the longer the heat preservation time is; if the materials added are epoxy resin and/or epoxy polyalkylsiloxane and telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide, the reaction product comprises the product obtained according to the chemical structural formula (18) and/or the formula (19) and/or (22) and/or (23); if the added materials are epoxy resin and/or epoxy polyalkyl siloxane and amino polyalkyl siloxane, the reaction product is obtained according to the chemical structural formula (20) and/or (24); in the chemical formulae (18), (19), (22), (23), if the ratio of the mass of the epoxy resin and/or epoxy polyalkylsiloxane to the molar number of the mass of telechelic carboxyl polybutadiene and/or telechelic amino polypropylene oxide added is more than 2, there will be an excess of unreacted epoxy resin and/or epoxy polyalkylsiloxane; in the chemical structures (20), (24), if the ratio of the charged mass of the epoxy resin and/or the epoxy polyalkylsiloxane to the molar number of the added mass of the amino polyalkylsiloxane is more than 3, there is an excess of the unreacted epoxy resin and/or the epoxy polyalkylsiloxane.
12. The structural insulating adhesive according to claim 2, wherein the step (two) of mixing the liquid material and the powder material with controlled shear strength comprises:
firstly adding powder of at least one (16-31)% of telechelic carboxyl compound and/or telechelic amino compound base stock, coupling agent and/or modifier (0-1.5)%, curing accelerator (0-2.5)%, heat insulation powder (44-62)% and flame retardant component (15-26)% into a reactor A with a high-speed stirring and/or high-shearing dispersing device;
firstly adding at least one (9-35)% of telechelic isocyanate-based compound and/or telechelic epoxy-based compound base material, 0-1.5)% of coupling agent and/or modifying agent, 0-2.5)% of curing accelerator, 44-62% of heat-insulating powder and 15-26% of flame-retardant component into a reactor B with a high-speed stirring and/or high-shear dispersing device;
respectively in the reactor A and the reactor B according to the average particle diameter D of the powder50The specification is divided into three or more batches of thin → medium- → thick, and the finest D is added in sequence50Powder of size → submicron D50Powder of size → intermediate D50Powder of size → coarse D50The powder with the specification is analogized until the coarsest D50Powder with specification; each time adding one D50Changing the diameter or adjusting the rotating speed of the stator and the rotor of the high-shear dispersing device to control the shear strength to (1200-233000) s-1Controlling the temperature of the slurry within the range of (0-175) DEG C and maintaining the temperature for (0.1-4) hours; the shear strength is calculated according to equation (27),
in the formula (27), the reaction mixture is,
Ssshear strength, unified or converted units of "1/second" or s-1，
V-the rotational linear velocity of the outer diameter of the rotor, or the relative rotational linear velocity of the outer diameter of an adjacent pair of rotors, is unified or converted into units of "m/s" or m/s,
delta-the minimum clearance between adjacent stators and rotors, or between adjacent rotors and rotors, either in unity or scaled units of "meters" or m.
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