CN115305039B - All-water foaming type damping fireproof adhesive and application thereof - Google Patents

All-water foaming type damping fireproof adhesive and application thereof Download PDF

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Publication number
CN115305039B
CN115305039B CN202210925418.8A CN202210925418A CN115305039B CN 115305039 B CN115305039 B CN 115305039B CN 202210925418 A CN202210925418 A CN 202210925418A CN 115305039 B CN115305039 B CN 115305039B
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source
parts
weight
trinity
type damping
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CN115305039A (en
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张武军
王书传
邬宵宵
陈鸿栅
何镕海
王诗榕
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XINHE NEW MATERIAL CO Ltd
Xinhe New Material Suzhou Co ltd
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XINHE NEW MATERIAL CO Ltd
Xinhe New Material Suzhou 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
    • C09J175/02—Polyureas
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/52—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/14—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors
    • H01M50/141—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors for protecting against humidity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/14—Primary casings, jackets or wrappings of a single cell or a single battery for protecting against damage caused by external factors
    • H01M50/143—Fireproof; Explosion-proof
    • 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
    • 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
    • C08K2003/387—Borates

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention discloses an all-water foaming type damping and fireproof adhesive and application thereof. The raw materials of the all-water foaming type damping and fireproof adhesive comprise matrix resin, a trinity flame retardant, water and the like. The trinity fire retardant is formed by at least three reactions of a C source, an N source, a P source, a B source and a Si source. The matrix resin includes a polyurea resin. The fireproof glue does not contain a physical foaming agent harmful to the atmosphere, can be coated on the surface of a new energy battery pack or the surface and/or the inside of a new energy vehicle body and forms a flame-retardant heat-insulation protective structure, has damping, shock absorption and sound insulation functions under normal environment, can provide a more comfortable riding environment, can be heated and expanded to form a carbon layer with functions of fire prevention, heat insulation and the like under the condition of fire, and can more effectively ensure the safety of passengers of the vehicle.

Description

All-water foaming type damping fireproof adhesive and application thereof
Technical Field
The invention relates to the field of damping fireproof glue, in particular to full-water foaming type damping fireproof glue containing a trinity fire retardant, a preparation method thereof and application thereof to the surfaces of new energy battery packs and new energy vehicles.
Background
In recent years, the new energy vehicle industry has been rapidly developed, and the safety problem of the new energy battery pack therein has been receiving more and more attention. In general, a new energy vehicle employs a lithium ion battery pack, which is susceptible to fire hazard when being pressed by external force and thermally out of control. These fires may spread throughout the vehicle, putting the driver and passengers at risk. The accident of ignition of the electric car due to thermal runaway of the battery pack indicates that effective protection for the battery cell, the battery pack and the vehicle is required to give safety guarantee to passengers. However, the existing new energy battery and new energy vehicle fireproof schemes have more or less defects, such as unsatisfactory flame retardant performance, high cost, large occupied space, single function and the like. Therefore, how to develop a fireproof material with low cost, strong flame retardant property, small occupied space and multiple functions has become a problem to be solved in the field.
Disclosure of Invention
The invention mainly aims to provide an all-water foaming type damping and fireproof adhesive and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the invention provides an all-water foaming type damping and fireproof adhesive, which comprises the following raw materials in parts by weight: 50-70 parts of matrix resin, 20-30 parts of trinity fire retardant and 1-3 parts of water;
wherein the trinity fire retardant is formed by at least three reactions among a C source, an N source, a P source, a B source and a Si source.
In one embodiment, the method for preparing the trinity fire retardant comprises the following steps: uniformly mixing 0-40 parts by weight of a C source, 0-40 parts by weight of an N source, 0-40 parts by weight of a P source, 0-40 parts by weight of a B source and 0-40 parts by weight of a Si source at room temperature, wherein the dosage of at least three of the C source, the N source, the P source, the B source and the Si source is more than 0, and then kneading the mixture at 120-150 ℃ for 2-4 hours.
Illustratively, the trinity fire retardant is formed by reacting 20-40 parts by weight of a C source, 20-40 parts by weight of an N source, and 30-40 parts by weight of a P source.
Illustratively, the trinity fire retardant is formed by reacting 20-40 parts by weight of a B source, 20-40 parts by weight of an N source, and 30-40 parts by weight of a Si source.
Illustratively, the trinity fire retardant is formed by reacting 20-40 parts by weight of a C source, 20-40 parts by weight of an N source, and 20-40 parts by weight of a B source.
Illustratively, the trinity fire retardant is formed by reacting 20-40 parts by weight of N source, 30-40 parts by weight of P source and 20-40 parts by weight of Si source.
The carbon residue rate of the two trinity flame retardants consisting of the Si sources is superior to that of the two trinity flame retardants consisting of the other two non-Si sources.
The above trinity flame retardant composed of different sources shows no obvious difference in fireproof flame retardant performance.
The C source, the N source, the P source, the B source, the Si source and the like are reacted to form the trinity flame retardant, so that the respective flame retardant and heat insulation performances can be comprehensively exerted, the molecular weight is increased, the compatibility with film-forming high polymers is greatly improved, the expansion flame retardant cooperativity is better when a fire is received, the pore diameter of a carbon layer is uniform, the pore is compact, and the fireproof and heat insulation performances are superior to those of non-trinity flame retardants; and the decay rate of the fireproof performance is lower after the environment is aged.
In one embodiment, the C source includes any one or a combination of pentaerythritol, dipentaerythritol, neopentyl glycol, trimethylolpropane, and is not limited thereto.
In one embodiment, the N source includes any one or more of melamine, dicyandiamide, ammonium polyphosphate, ammonium pentaborate, and is not limited thereto.
In one embodiment, the P source includes, but is not limited to, phosphorus pentoxide, phosphorus trioxide, ammonium polyphosphate, hydroxylated phosphate esters.
In one embodiment, the Si source includes, but is not limited to, ethyl silicate and its polymer, 3-aminopropyl triethoxysilane, (aminoethyl) aminopropyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-isocyanatopropyl triethoxysilane, 3- (acryloyloxy) propyl trimethoxysilane.
In one embodiment, the B source includes any one or more of boric acid, ammonium pentaborate, boron trioxide, borax pentahydrate, and is not limited thereto.
In one embodiment, the matrix resin comprises a polyurea resin formed primarily from the reaction of an isocyanate and an amine in a molar ratio of 3-6:4-7.
In one embodiment, the amine includes any one or more of diethyl toluenediamine, dimethyl thiotoluenediamine, 4' -methylene-bis (3-chloro-2, 6-diethylaniline), polyaspartic acid ester, and is not limited thereto.
In one embodiment, the isocyanate includes, but is not limited to, a TDI-polythiol prepolymer or a TDI-PCL prepolymer, wherein the weight average molecular weight of the polythiol or PCL is 1500-2000 and the NCO content of the TDI-polythiol prepolymer or TDI-PCL prepolymer is 6-10wt%.
In one embodiment, the method of preparing the isocyanate comprises: adding 1 to 1.5 weight parts of polythiol or PCL into a reaction kettle, heating to 80 to 85 ℃ in a protective atmosphere, adding 3 to 4 weight parts of TDI, reacting for 2 to 3 hours, adding a chain extender to adjust the NCO content, reacting for 30 minutes, and cooling and discharging to obtain the isocyanate.
Further, the chain extender includes N, N' -diethyl-1, 3-propanediamine (depa), and is not limited thereto.
In one embodiment, the raw materials of the all-water foaming type damping and fireproof glue comprise a component A and a component B; the component A comprises amine, a trinity flame retardant, water, reinforcing fibers which can be optionally added or not added and fillers which can be optionally added or not added; the B component comprises isocyanate.
In one embodiment, the raw materials of the flame retardant glue further comprise 1-3 parts by weight of reinforcing fibers and 10-15 parts by weight of filler.
Further, the reinforcing fiber includes at least one of mineral fiber and carbon fiber, and is not limited thereto.
Further, the filler includes any one or a combination of more of talc powder, quartz powder, titanium white, and expandable graphite, and is not limited thereto.
In another aspect, the invention provides the use of the all-water foaming type damping and fireproof adhesive, such as the use in preparing a new energy battery pack or a protective structure of a new energy vehicle. Specifically, the all-water foaming type damping and fireproof adhesive can be coated on a substrate to form a protective structure. The protective structure can be a protective layer on the surface of a new energy battery pack, a protective layer on the surface of an instrument panel, a decoration part and the like in the new energy vehicle, and the like, and can also be other protective structures which have multiple functions, for example, CO formed by the reaction of water and isocyanate in the all-water foaming type damping and fireproof adhesive 2 The foaming agent enables the colloid to expand to form a pore damping structure, has damping, shock absorption and sound insulation functions under normal environment, provides more comfortable riding environment, and under the condition of fire, the colloid continues to expand by heating, so that a protective structure with a carbon-containing layer with fireproof and heat insulation functions is formed, and the personal safety of passengers of a vehicle can be effectively protected.
Compared with the prior art, the all-water foaming type damping and fireproof adhesive provided by the invention adopts polyurea resin as matrix resin, and is added with trinity fire retardant and water, and utilizes CO formed by the reaction of water and isocyanate 2 The foaming agent expands the colloid to formThe pore damping structure is safe and environment-friendly, has damping, shock absorption and sound insulation functions in normal environment, has better resin component compatibility and better thermal expansion flame retardant cooperativity by utilizing the trinity flame retardant than the expansion flame retardant system such as ammonium polyphosphate-pentaerythritol-melamine, can enable colloid to be heated and expanded continuously under the condition of fire, forms a carbon layer for fire prevention and heat insulation, avoids the phenomenon of non-uniform pores of the carbon layer, and further avoids the defects of easy moisture absorption, poor water resistance and the like of the expansion flame retardant system such as ammonium polyphosphate-pentaerythritol-melamine, has low attenuation rate of environmental ageing and fireproof performance, and can more effectively protect the safety of passengers of vehicles.
Particularly, the polyurea resin formed by the TDI-polythiol prepolymer and the TDI-PCL prepolymer is better in fireproof flame retardance and superior in damp-heat cycle material strength and damping property compared with hydroxyl polyol-PAPI type foaming polyurethane and the like, can fully meet the external burning requirements of battery packs of GB38031-2020 and the like, can greatly prolong or inhibit or even prevent the spread of fire under the condition of thermal runaway of the battery packs, and provides more abundant rescue time.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Illustratively, the raw materials used in the following examples are as follows: the reinforcing fiber is Lapinus company product, the model is MS610, and is an aminosilane surface treatment mineral fiber; titanium white is a product of brocade titanium company, the model is CR506, and is titanium white prepared by treating silicon aluminum and special organic surfaces; the expandable graphite is an 80 mesh product of Qingdao Jin Tao graphite Co.
Embodiment 1 this embodiment provides a full water foaming type damping and fireproof adhesive, which comprises the following raw materials:
the component A is formed by uniformly mixing 80g of dimethyl thiotoluene diamine, 90g of C-N-P-containing trinity fire retardant, 9g of reinforcing fiber, 45g of filler and 6g of water at high speed and then filling;
component B, comprising 70g of TDI-polythiol prepolymer.
And during construction, mixing the component A and the component B to obtain the all-water foaming type damping and fireproof adhesive.
Wherein, the raw materials of the C-N-P-containing trinity fire retardant comprise dipentaerythritol, ammonium polyphosphate and melamine, and the specific preparation method is as follows:
10 parts (weight parts are as follows except the specific description) of dipentaerythritol, 20 parts of ammonium polyphosphate and 10 parts of melamine are uniformly mixed in a mixer at 25 ℃, the mixed materials are kneaded in a steel kneader at 125 ℃ for 2 hours, crushed and sieved to obtain the C-N-P-containing trinity flame retardant.
The preparation method of the TDI-polythiol prepolymer comprises the following steps: 100g of polythiol (Mw=1500) is added into a reaction kettle, nitrogen is introduced for protection, the temperature is heated to 80 ℃, 300g of TDI is added dropwise for reaction for 2 hours, DEPDA is added for regulating the NCO content to about 6wt% of the requirement, the reaction is carried out for 30 minutes, and the TDI-polythiol prepolymer is obtained after cooling and discharging.
Comparative example 1 this comparative example provides an all-water foaming type damping and flame-retardant adhesive having substantially the same raw materials as in example 1 except that: the C-N-P-containing trinity flame retardant is replaced by a mixture (the total weight is 90 g) of dipentaerythritol, ammonium polyphosphate and melamine with the mass ratio of 1:2:1.
Comparative example 2 this comparative example provides a foamed flame retardant adhesive having substantially the same raw materials as in example 1 except that: 150g of a hydroxyl polyol-PAPI type foaming polyurethane was used instead of the dimethyl thiotoluene diamine in the A component, and the B component was omitted.
Embodiment 2 this embodiment provides a full water foaming type damping and fireproof adhesive, which comprises the following raw materials:
the component A is formed by uniformly mixing 80g of dimethyl thiotoluene diamine, 40g of C-N-B-containing trinity fire retardant, 4g of reinforcing fiber, 20g of filler and 6g of water at a high speed and then filling;
component B, comprising 60g TDI-PCL prepolymer.
And during construction, mixing the component A and the component B to obtain the all-water foaming type damping and fireproof adhesive.
Wherein, the raw materials of the C-N-B-containing trinity fire retardant comprise trimethylolpropane, ammonium pentaborate and dicyandiamide, and the specific preparation method is as follows:
uniformly mixing 10 parts of trimethylolpropane, 20 parts of ammonium pentaborate and 10 parts of dicyandiamide in a mixer at 25 ℃; and then kneading the mixed materials on a steel kneader at 150 ℃ for 3 hours, and crushing and sieving to obtain the C-N-B-containing trinity flame retardant.
The preparation method of the TDI-PCL prepolymer comprises the following steps: 150g of PCL (Mw=2000) is added into a reaction kettle, nitrogen is introduced for protection, the temperature is heated to 80 ℃, 300g of TDI is added dropwise for reaction for 2 hours, DEPDA is added for regulating the NCO content to about 8wt% of the requirement, the reaction is carried out for 30 minutes, and the TDI-PCL prepolymer is obtained after cooling and discharging.
Comparative example 3 this comparative example provides an all-water foaming type damping and flame-retardant adhesive having substantially the same raw materials as in example 2 except that: the tri-functional flame retardant containing C-N-B is replaced by a mixture (total weight is 90 g) of trimethylolpropane, ammonium pentaborate and dicyandiamide in the mass ratio of 1:2:1.
Embodiment 3 this embodiment provides an all-water foaming type damping and fireproof adhesive, which comprises the following raw materials:
the component A is formed by uniformly mixing 70g of polyaspartic acid ester, 50g of N-P-Si-containing trinity flame retardant, 2g of reinforcing fiber, 20g of filler and 2g of water at a high speed and then filling;
component B, comprising 50g TDI-PCL prepolymer.
And during construction, mixing the component A and the component B to obtain the all-water foaming type damping and fireproof adhesive.
Wherein, the raw materials of the N-P-Si-containing trinity flame retardant comprise gamma-glycidyl ether oxypropyl trimethoxy silane, ammonium polyphosphate and melamine, and the specific preparation method is as follows:
uniformly mixing 10 parts of ammonium polyphosphate, 5 parts of melamine and 3 parts of gamma-glycidyl ether oxypropyl trimethoxy silane in a mixer at 25 ℃; and then kneading the mixed materials on a steel kneader at 120 ℃ for 4 hours, and crushing and sieving to obtain the N-P-Si-containing trinity flame retardant.
Wherein the TDI-PCL prepolymer was prepared in the same manner as in example 2.
Comparative example 4 this comparative example provides an all-water foaming type damping and flame-retardant adhesive having substantially the same raw materials as in example 3 except that: the N-P-Si-containing trinity flame retardant is replaced by a mixture (the total weight is 90 g) of ammonium polyphosphate, melamine and gamma-glycidol ether oxygen propyl trimethoxy silane with the mass ratio of 10:5:3.
Embodiment 4 this embodiment provides an all-water foaming type damping and fireproof adhesive, which comprises the following raw materials:
the component A is formed by uniformly mixing 80g of 4,4' -methylene-bis (3-chloro-2, 6-diethylaniline), 90g of B-N-Si-containing trinity fire retardant, 9g of reinforcing fiber, 45g of filler and 6g of water at high speed and then filling;
component B, comprising 70g TDI-PCL prepolymer.
And during construction, mixing the component A and the component B to obtain the all-water foaming type damping and fireproof adhesive.
Wherein, the raw materials of the B-N-Si-containing trinity flame retardant comprise boric acid, (aminoethyl) aminopropyl trimethoxysilane and melamine, and the specific preparation method is as follows:
uniformly mixing 10 parts of boric acid, 5 parts of melamine and 3 parts of (aminoethyl) aminopropyl trimethoxysilane at room temperature in a mixer; and then kneading the mixed materials on a steel kneader at 140 ℃ for 2 hours, and crushing and sieving to obtain the B-N-Si-containing trinity flame retardant.
The preparation method of the TDI-PCL prepolymer comprises the following steps: 100g of PCL (Mw=2000) is added into a reaction kettle, nitrogen is introduced for protection, the temperature is raised to 85 ℃, 400g of TDI is added dropwise for reaction for 2 hours, DEPDA is added for regulating the NCO content to about 10wt% of the requirement, the reaction is carried out for 30 minutes, and the TDI-PCL prepolymer is obtained after cooling and discharging.
Comparative example 5 this comparative example provides an all-water foaming type damping and flame-retardant adhesive having substantially the same raw materials as in example 4 except that: the B-N-Si-containing trinity flame retardant is replaced by a mixture (the total weight is 90 g) of boric acid, (aminoethyl) aminopropyl trimethoxysilane and melamine with the mass ratio of 10:5:3.
The fireproof glue obtained in the invention examples 1 to 4 and the fireproof glue obtained in the invention comparative examples 1 to 5 were subjected to fireproof performance and damping performance tests, and the test results are shown in table 1. Wherein, the fire resistance test is carried out according to GB38031-2020, the damping performance test is carried out according to GB/T18258, the high and low temperature resistant cycle alternating test is carried out according to Q/CR546.3, the water resistance test is carried out according to GB/T1733-1993, the adhesive force test is carried out according to GB/T5210-2006, and the carbon residue is measured according to GB17144 petroleum product carbon residue (trace method).
TABLE 1 results of the fire protection glue Performance test of examples 1-4 and comparative examples 1-5
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (3)

1. The all-water foaming type damping and fireproof adhesive is characterized in that the raw materials of the all-water foaming type damping and fireproof adhesive comprise a component A and a component B; the component A comprises amine, a trinity flame retardant, water, reinforcing fibers which can be optionally added or not added and fillers which can be optionally added or not added; the component B comprises isocyanate; wherein, by the mole ratio of 3-6: 4-7 parts of isocyanate and amine react to form polyurea resin which is taken as matrix resin, wherein the matrix resin is 50-70 parts by weight, the trinity fire retardant is 20-30 parts by weight, and the water is 1-3 parts by weight;
wherein the amine is selected from any one or a combination of a plurality of diethyl toluenediamine, dimethyl thiotoluenediamine, 4' -methylene-bis (3-chloro-2, 6-diethyl aniline) and polyaspartic acid ester;
the isocyanate is selected from TDI-polythiol prepolymer or TDI-PCL prepolymer, wherein the weight average molecular weight of polythiol or PCL is 1500-2000, and the NCO content of the TDI-polythiol prepolymer or TDI-PCL prepolymer is 6-10wt%, and the preparation method of the isocyanate comprises the following steps: adding 1-1.5 parts by weight of polythiol or PCL into a reaction kettle, heating to 80-85 ℃ in a protective atmosphere, adding 3-4 parts by weight of TDI, reacting for 2-3 hours, adding a chain extender to adjust NCO content, reacting for 30 minutes, and cooling and discharging, wherein the chain extender is N, N' -diethyl-1, 3-propylene diamine;
the preparation method of the trinity fire retardant comprises the following steps:
uniformly mixing 20-40 parts by weight of a B source, 20-40 parts by weight of an N source and 30-40 parts by weight of a Si source at room temperature, and then kneading at 120-150 ℃ for 2-4 hours;
or uniformly mixing 20-40 parts by weight of a C source, 20-40 parts by weight of an N source and 30-40 parts by weight of a P source at room temperature, and then kneading at 120-150 ℃ for 2-4 hours;
or uniformly mixing 20-40 parts by weight of a C source, 20-40 parts by weight of an N source and 20-40 parts by weight of a B source at room temperature, and then kneading at 120-150 ℃ for 2-4 hours;
or uniformly mixing 20-40 parts by weight of an N source, 30-40 parts by weight of a P source and 20-40 parts by weight of a Si source at room temperature, and then kneading at 120-150 ℃ for 2-4 hours;
the C source is selected from any one or a combination of more of pentaerythritol, dipentaerythritol, neopentyl glycol and trimethylolpropane;
the N source is selected from any one or a combination of more of melamine, dicyandiamide, ammonium polyphosphate and ammonium pentaborate;
the P source is selected from phosphorus pentoxide, phosphorus trioxide, ammonium polyphosphate and hydroxylated phosphate;
the Si source is selected from any one or a combination of more of ethyl silicate and polymer thereof, 3-aminopropyl triethoxysilane, (aminoethyl) aminopropyl trimethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, gamma-isocyanic acid propyl triethoxysilane and 3- (acryloyloxy) propyl trimethoxysilane;
the B source is selected from any one or a combination of a plurality of boric acid, ammonium pentaborate, boron trioxide and borax pentahydrate.
2. The all-water foaming type damping and fire-resistant adhesive according to claim 1, wherein the raw materials of the fire-resistant adhesive comprise 1-3 parts by weight of reinforcing fiber and 10-15 parts by weight of filler;
the reinforcing fibers include at least one of mineral fibers and carbon fibers; the filler comprises any one or a combination of a plurality of talcum powder, quartz powder, titanium white and expandable graphite.
3. Use of the all-water foaming type damping and fireproof glue according to any one of claims 1 to 2 for preparing a new energy battery pack or a protective structure of a new energy vehicle.
CN202210925418.8A 2022-08-03 2022-08-03 All-water foaming type damping fireproof adhesive and application thereof Active CN115305039B (en)

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CN109280529A (en) * 2018-09-28 2019-01-29 五邑大学 A kind of glue and preparation method thereof of copper-clad plate aluminum substrate
CN111218196A (en) * 2020-02-24 2020-06-02 顺德职业技术学院 Water-based UV flame-retardant coating containing trinity flame retardant and preparation method thereof
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