CN115612150B - Flame-retardant microporous polyurethane foam, and preparation method and application thereof - Google Patents

Flame-retardant microporous polyurethane foam, and preparation method and application thereof Download PDF

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CN115612150B
CN115612150B CN202211360744.5A CN202211360744A CN115612150B CN 115612150 B CN115612150 B CN 115612150B CN 202211360744 A CN202211360744 A CN 202211360744A CN 115612150 B CN115612150 B CN 115612150B
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polyol
flame
retardant
polyurethane foam
microporous polyurethane
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CN115612150A (en
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金策
魏琼
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Hubei Xiangyuan New Material Technology Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/05—Forming flame retardant coatings or fire resistant coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of production of materials for power batteries, in particular to flame-retardant microporous polyurethane foam, a preparation method and application thereof. In the invention, the thickness of the polyurethane foam forming the flame-retardant microporous polyurethane foam is 2.0-3.5 mm, and the density is 280-360 kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyurethane foam has 25% compression strength of 30-80 KPa, average pore diameter of 90-180 μm, initial decomposition temperature of 180-220 ℃ in TGA test, and residual carbon content of 15-25%. The invention can reach the UL94 vertical burning V0 grade under the thinner sheet condition, keep the compression resilience force in 25% compression state lower, avoid the influence of higher stress on the service life of the battery, and simultaneously has excellent ageing resistance in the compression state. The flame-retardant grade flame-retardant material provided by the invention can be softer and thinner, and can realize good balance of aging resistance, compressibility and flame retardance.

Description

Flame-retardant microporous polyurethane foam, and preparation method and application thereof
Technical Field
The invention relates to the technical field of production of materials for power batteries, in particular to flame-retardant microporous polyurethane foam, a preparation method and application thereof.
Background
The new energy automobile is a product of the evolution of the social technology to a certain stage, is a product of people's life going to the beautiful life, and is a product meeting the demands of people on low carbon, environmental protection, convenience and the like. The growing new energy market is not free from reliable power batteries and needs to provide materials for buffering and vibration filtering under severe conditions. Particularly, the elastic material has uniform resilience when repeatedly charged and discharged, and damage caused by extrusion is avoided.
The foam in the battery liner needs to have certain hardness at first, and can keep reliable compression deformation resistance under various conditions, so that foam collapse is avoided, and certain resilience force is ensured to fix the battery core; and can play an effective buffering role.
Currently, the foam that is accepted by the automotive industry is mainly polysilane foam, but polysiloxane foam has a small compressive residual strain but contains a large amount of low molecular weight siloxane. Silica sometimes precipitates from silicone foam due to low molecular weight siloxanes. In the case of using a silicone foam as a buffer material of a battery pack, contact points on an electronic substrate mounted in the battery pack are contaminated due to precipitation of silicon dioxide, and electrical characteristics may be deteriorated. Thus, silicone foams are not suitable for use as cushioning materials for batteries.
Along with the increasing requirements of the continuous mileage of the automobile, the requirements on the flame retardance of polyurethane materials are increasingly severe, however, the addition of the flame retardant in the polyurethane matching foam body inevitably brings the defects of reduced compressibility, harder foam body, reduced adhesion and the like. Therefore, development of a flame-retardant flexible thin polyurethane foam for cushioning between power cells is particularly necessary. For such flame retardant materials, moderate hardness and good compressibility are required, and in addition, it is desirable to reduce the thickness and density of the flame retardant material and reduce the cost as much as possible while maintaining the flame retardant rating and compression resilience.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a flame-retardant microporous polyurethane foam, a preparation method and an application thereof, wherein the flame-retardant microporous polyurethane foam provided by the present invention can reach the UL94 vertical combustion V0 grade under the condition of a thinner thickness, and provides a lower compression resilience under 25% compression state under the premise of ensuring excellent aging resistance.
The invention provides a flame-retardant microporous polyurethane foam, the thickness of polyurethane foam forming the flame-retardant microporous polyurethane foam is 2.0-3.5 mm, and the density is 280-360 kg/m 3 ；
The polyurethane foam has 25% compression strength of 30-80 KPa, average pore diameter of 90-180 μm, initial decomposition temperature of 180-220 ℃ in TGA test, and residual carbon content of 15-25%.
Preferably, the flame-retardant microporous polyurethane foam is aged for 72 hours under the conditions of humidity of 85% and temperature of 85 ℃ in a compressed state of 50%, and the compression set is less than 15%.
Preferably, the flame retardant microporous polyurethane foam meets the UL94 vertical burn V0 rating.
Preferably, the preparation raw materials of the flame-retardant microporous polyurethane foam comprise a material A1;
the material A1 is prepared by mixing raw materials comprising expandable graphite, a liquid-added organic phosphate flame retardant and flame-retardant polyol;
the expandable graphite is expandable graphite powder, the initial decomposition temperature is 150-200 ℃, the expansion rate at 800 ℃ is 100-300 mL/g, and the median value of the particle size is 30-200 mu m;
the liquid additive type organic phosphate flame retardant comprises at least one of triethyl phosphate, tripropyl phosphate, triisobutyl phosphate and triaryl phosphate;
the mass content of phosphorus in the liquid additive type organic phosphate flame retardant is 10-20%, and the viscosity is 10-100 mPa.s;
The flame-retardant polyol is a phosphorus-containing polyol, the hydroxyl value of the phosphorus-containing polyol is 300-600 KOH mg/g, the mass content of phosphorus is 10-15%, and the viscosity is 100-600 mPa.s.
Preferably, the material A1 is prepared according to the following method:
adding expandable graphite, metal hydrated salt oxide and inorganic phosphorus flame retardant into liquid additive type organic phosphate flame retardant, then adding into flame retardant polyol, stirring at a rotating speed of 500-1000 r/min for 5-15 min, and then passing through a filter screen of 30-50 meshes to obtain a material A1;
the material A1 does not settle after standing for 3-6 hours, and the viscosity of the material A1 is 10000-30000 mPa.s;
the mass ratio of the expandable graphite to the metal hydrated salt oxide to the inorganic phosphorus flame retardant to the liquid-added organic phosphate flame retardant to the flame-retardant polyol is 20-30: 2 to 8:0 to 6: 5-15: 7-22.
Preferably, the metal hydrous salt oxide comprises at least one of magnesium hydroxide, aluminum hydroxide, zinc borate and montmorillonite;
the inorganic phosphorus flame retardant comprises at least one of ammonium polyphosphate and modified ammonium polyphosphate;
the median particle size of the metal hydrated salt oxide, the inorganic phosphorus flame retardant and the liquid-added organic phosphate flame retardant is 1-50 mu m.
Preferably, the preparation raw materials of the flame-retardant microporous polyurethane foam also comprise a material A2;
the material A2 is obtained by mixing raw materials comprising mixed polyol, a foaming agent, a catalyst, a cross-linking agent and a surfactant; the mass ratio of the mixed polyol to the foaming agent to the catalyst to the cross-linking agent to the surfactant is 44-72: 0 to 0.3: 0.005-0.02: 0 to 2:5 to 15;
the mixed polyol comprises polyol P1, polyol P2, polyol P3 and polyol P4;
the poly polyol P1 includes at least one of a polyether polyol and a polyester polyol; the weight average molecular weight of the polyether polyol is 400-6000, the weight average molecular weight of the polyester polyol is 400-6000, and the hydroxyl value of the poly polyol P1 is not less than 280 and not more than 380KOH mg/g;
the polyatomic alcohol P2 is polyether polyatomic alcohol, the hydroxyl value is not less than 24KOH mg/g and not more than 56KOH mg/g, and the EO content is not less than 70%;
the polyatomic alcohol P3 is polymer polyatomic alcohol with a hydroxyl value of 20-30 KOH mg/g;
the poly polyol P4 is a difunctional poly polyol with a weight average molecular weight of 2000-8000.
Preferably, the crosslinking agent comprises at least one of trimethylolpropane, ethanolamine, diethanolamine, triethanolamine and pentaerythritol;
The foaming agent comprises at least one of pure water, carbon dioxide and nitrogen;
the catalyst comprises a first catalyst and a second catalyst, wherein the first catalyst comprises at least one of organic bismuth, bismuth isooctanoate, zinc neodecanoate and zinc isooctanoate; the second catalyst comprises a polyurethane foaming catalyst;
the surfactant is a block copolymer of dimethyl siloxane and polyether.
Preferably, the preparation raw materials of the flame-retardant microporous polyurethane foam also comprise a material A3;
the material A3 comprises modified diisocyanate;
the viscosity of the modified diisocyanate at 25 ℃ is 2000-5000 mPa.s, and the mass content of NCO is 10% -20%;
the modified diisocyanate comprises liquid modification of any one or more of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate and isophorone diisocyanate.
Preferably, the polyurethane foam further comprises a film attached to the polyurethane foam;
the film is made of at least one of PET and release paper;
the thickness of the film is 0.02-0.2 mm.
The invention also provides a preparation method of the flame-retardant microporous polyurethane foam, which comprises the following steps:
A) Uniformly mixing the material A1 and the material A2 to obtain a mixed material;
the material A1 is prepared by mixing raw materials comprising expandable graphite, metal hydrated salt oxide, inorganic phosphorus flame retardant, liquid-added organic phosphate flame retardant and flame-retardant polyol;
the material A2 is obtained by mixing raw materials comprising mixed polyol, a foaming agent, a catalyst, a cross-linking agent and a surfactant;
b) Uniformly mixing the mixed material with the material A3, coating the mixture on a film, and baking and curing the mixture to obtain flame-retardant microporous polyurethane foam;
the material A3 comprises modified diisocyanate.
The invention also provides application of the flame-retardant microporous polyurethane foam or the flame-retardant microporous polyurethane foam prepared by the preparation method as a buffer material, a heat insulation material and a sealing material.
The invention provides a flame-retardant microporous polyurethane foam, which is characterized in that the thickness of polyurethane foam forming the flame-retardant microporous polyurethane foam is 2.0-3.5 mm, and the density is 280-360 kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyurethane foam has 25% compression strength of 30-80 KPa, average pore diameter of 90-180 μm, initial decomposition temperature of 180-220 ℃ in TGA test, and residual carbon content of 15-25%.
The realization result shows that the invention can reach the UL94 vertical burning V0 grade when thinner sheets such as 2.0mm, keep the compression resilience force in 25% compression state lower, avoid the influence of higher stress on the service life of the battery, and have excellent ageing resistance in the compression state. The flame-retardant grade flame-retardant material provided by the invention can be softer and thinner, and can realize better balance between compressibility and flame retardant property.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a flame-retardant microporous polyurethane foam, the thickness of polyurethane foam forming the flame-retardant microporous polyurethane foam is 2.0-3.5 mm, and the density is 280-360 kg/m 3 The flame retardant rating satisfies the UL94 vertical fire V0 rating;
the polyurethane foam has 25% compression strength of 30-80 KPa, average pore diameter of 90-180 μm, initial decomposition temperature of 180-220 ℃ in TGA test, and residual carbon content of 15-25%.
The buffer foam between the lithium ion power battery cells needs proper compression resilience force to adapt to the volume change of the battery in the cyclic use, so that the foam cells are ensured to have moderate resilience force under different working conditions to provide the buffer and shock absorption functions. The current buffer gasket for the soft-package battery core is generally of UL94HBF grade (the burning rate is less than 40 mm/min), and is particularly important for buffering foam to self-extinguish when flame rapidly spreads when the battery is in thermal runaway. Generally, the same formula is adopted, the higher the density is, the thicker the thickness is, the better the flame retardant property is, but the density, the compression strength and the maximum compression ratio generally show positive correlation, the application of the soft package battery core needs to control proper pretightening force and the maximum compression ratio, foam is too thick, the integral energy density of the battery module is affected, and the ageing resistance is poor due to the fact that the foam is too thin. Therefore, the thickness, the density and the initial decomposition temperature of the polyurethane foam forming the flame-retardant microporous polyurethane foam are controlled to present more excellent flame retardant performance in the range, meanwhile, the mixing process ensures the influence of the flame retardant on ageing resistance, and the polyurethane formula design ensures that the foam with high filler and high density has proper compression resilience. Therefore, the flame-retardant microporous polyurethane foam provided by the invention can be used as buffer foam between the battery cores of the lithium ion power battery.
In certain embodiments of the present invention, the flame retardant microporous polyurethane foam has a compression set of < 15% after aging for 72 hours at 85% humidity and 85 ℃ temperature in a compressed 50% state. The lower compression set means that the thickness change rate is smaller after aging, and the foam can be ensured to always maintain a proper compression ratio in a long-term use process.
In certain embodiments of the present invention, the flame retardant microporous polyurethane foam is prepared from a material A1. The material A1 is prepared by mixing raw materials comprising expandable graphite, a liquid-added type organic phosphate flame retardant and flame-retardant polyol, and specifically, the material A1 is prepared by mixing raw materials comprising expandable graphite, metal hydrated salt oxide, an inorganic phosphorus flame retardant, a liquid-added type organic phosphate flame retardant and flame-retardant polyol; or is obtained by mixing raw materials comprising expandable graphite, metal hydrated salt oxide, liquid-added organic phosphate flame retardant and flame-retardant poly polyol. By adopting the mode, precipitation of the additive flame retardant can be avoided, and the influence of the additive flame retardant on the catalyst is avoided while the flame retardance is ensured.
In certain embodiments of the present invention, the expandable graphite is an expandable graphite powder having an initial decomposition temperature of 150 to 200 ℃, an expansion ratio of 100 to 300mL/g at 800 ℃, and a median particle size of 30 to 200 μm. Specifically, the initial decomposition temperature is 210 ℃, 187 ℃ and 196 ℃; the expansion rate at 800 ℃ is 100-150 mL/g, 230-250 mL/g and 250-280 mL/g; the median value of the particle size is 50 μm, 70 μm, 90 μm or 180 μm. The applicant found in the study that expansion ratio and flame retardance show positive correlation, but expansion ratio and expandable graphite particle size have positive correlation, large particle size powder affects filtering efficiency, and risk of blocking production pipeline increases, so that raw materials with proper particle size are required to balance production efficiency and flame retardance, and expandable graphite powder with the above-defined parameters is preferred and can be commercially available in general.
In certain embodiments of the present invention, the liquid additive type organic phosphate flame retardant comprises at least one of triethyl phosphate, tripropyl phosphate, triisobutyl phosphate, and triaryl phosphate. The mass content of phosphorus in the liquid additive type organic phosphate flame retardant is 10-20%, and the viscosity is 10-100 mPa.s.
In certain embodiments of the invention, the flame retardant polyol is a phosphorus-containing polyol having a hydroxyl value of 300 to 600KOH mg/g, a phosphorus mass content of 10 to 15%, and a viscosity of 100 to 600 mPas. Specifically, at least one of Doher 650, clahn Exolit OP 550, and clahn Exolit OP 560 may be mentioned.
In certain embodiments of the present invention, the metal hydrous salt oxide comprises at least one of magnesium hydroxide, aluminum hydroxide, zinc borate, and montmorillonite.
In certain embodiments of the present invention, the inorganic phosphorus-based flame retardant comprises at least one of ammonium polyphosphate and modified ammonium polyphosphate.
In certain embodiments of the present invention, the median particle size of the metal hydrous salt oxide, the organic phosphate and the inorganic phosphorus flame retardant is from 1 to 50 μm.
In certain embodiments of the present invention, the mass ratio of the expandable graphite, the metal hydrous salt oxide, the inorganic phosphorus-based flame retardant, the liquid-added type organic phosphate flame retardant and the flame retardant polyol is 20 to 30:2 to 8:0 to 6: 5-15: 7-22; specifically, it may be 28.25:3.61:3.61:7.85:7.85, 29.31:3.74:0:8.14:8.14, 28.11:5.45:0:13.63:14.99, 28.11:5.45:0:13.63:17.04 or 25.26:2.1:0:6.31:21.05.
In certain embodiments of the invention, the material A1 is prepared according to the following method:
adding expandable graphite, metal hydrated salt oxide and inorganic phosphorus flame retardant into liquid additive type organic phosphate flame retardant, then adding into flame retardant polyol, stirring for 5-15 min at a rotating speed of 500-1000 r/min, and then passing through a filter screen with 30-50 meshes to obtain a material A1.
Specifically, the stirring speed is 700r/min, 1000r/min and the stirring time is 10min; the filtered solid-liquid mixture is filtered through a filter screen of 50 meshes or 30 meshes.
In certain embodiments of the invention, the material A1 does not settle after 3 to 6 hours of rest. The viscosity of the material A1 is 10000-30000 mPa.s; specifically, the viscosity may be 12000 mPas, 11000 mPas, 22000 mPas, 20000 mPas, 14000 mPas or 26000 mPas.
In some embodiments of the present invention, the preparation raw materials of the flame-retardant microporous polyurethane foam further include a material A2; the material A2 is obtained by mixing raw materials comprising mixed polyol, a foaming agent, a catalyst, a cross-linking agent and a surfactant. The mass ratio of the mixed polyol to the foaming agent to the catalyst to the cross-linking agent to the surfactant is 44-72: 0 to 0.3: 0.005-0.02: 0 to 2:5 to 15. Specifically, 58.69 may be: 0.17:0.02:1.57:8.63, 60.97:0.18:0.02:1.63:8.96, 46.34:0.14:0.02:0.85:6.82, 44.3:0.14:0.02:0.85:6.82, 46.38:0.21:0.02:0.42:13.68 or 45.52:0.21:0.02:0.42:13.68.
The mixed polyols include polyol P1, polyol P2, polyol P3 and polyol P4.
The poly polyol P1 includes at least one of a polyether polyol and a polyester polyol; the weight average molecular weight of the polyether polyol is 400-6000, the weight average molecular weight of the polyester polyol is 400-6000, and the hydroxyl value of the poly polyol P1 is not less than 280 and not more than 380KOH mg/g. Specifically, the polyol P1 may be Jiangsu clock LW-1030, VORANOL TM WK 3140Polyol、VORANOL TM CP 450 and VORANOL TM 2070 Polyol.
The polyatomic alcohol P2 is polyether polyatomic alcohol, the hydroxyl value is not less than 24KOH mg/g and not more than 56KOH mg/g, and the EO content is not lowAt 70%. Specifically, the polyol P2 may be VORANOL TM 1447Polyol and/or VORANOL TM 4701Polyol。
The polyatomic alcohol P3 is polymer polyatomic alcohol with the hydroxyl value of 20-30 KOH mg/g. Specifically, the polyol P3 may be at least one of HPOP40, POP38/26, POP36/28 and POP93/28, which are large in the east of Lanxingdong.
The poly polyol P4 is a difunctional poly polyol with a weight average molecular weight of 2000-8000. Specifically, it may be VORANOL TM 2000Polyol and VORANOL TM 4000 Polyol.
The mass ratio of the polyol P1 to the polyol P2 to the polyol P3 to the polyol P4 is 8-24: 3 to 23: 8-22: 15 to 21. Specifically, it may be 13.16:7.06:18.83:19.64, 13.66:7.33:19.54:20.44, 15.47:5.45:8.86:16.56, 15.47:5.45:6.82:16.56, 12.32:3.16:14.73:16.17 or 12.23:3.16:14.73:15.4.
In certain embodiments of the invention, the mixed polyol is prepared according to the following method:
and uniformly stirring and mixing the polyol P1, the polyol P2, the polyol P3 and the polyol P4 to obtain the mixed polyol.
The rotation speed of the stirring and mixing is 600-1000 r/min, and specifically, can be 700r/min or 1000r/min; the time is 5-15 min, specifically, 10min. The stirring and mixing can be performed in a dispersing disc.
The crosslinking agent comprises at least one of trimethylolpropane, ethanolamine, diethanolamine, triethanolamine and pentaerythritol.
The foaming agent includes at least one of pure water, carbon dioxide and nitrogen.
The catalyst comprises a first catalyst and a second catalyst, wherein the first catalyst comprises at least one of organic bismuth, bismuth isooctanoate, zinc neodecanoate and zinc isooctanoate; the second catalyst comprises a polyurethane blowing catalyst. The organobismuth may specifically be michaux NIAX MC-710. The polyurethane foaming catalyst can be FOCAT-8002. The mass ratio of the first catalyst to the second catalyst may be 0.5 to 1.5:0.5 to 1.5; specifically, it may be 1:1.
The surfactant is a block copolymer of dimethylsiloxane and polyether, which may take various forms, such as any one or more of linear, branched, or side chain, partially cross-linked polysiloxane and polyoxyalkylene block copolymers or mixtures thereof, organosiloxane-polyoxyalkylene block copolymers, silicate and trimethylsilyl copolymers. Specifically, it may be VORASURF TM DC2525、VORASURF TM DC8835 and VORASURF TM At least one of DC 2584.
In certain embodiments of the invention, the material A2 is prepared according to the following method:
and uniformly stirring the raw materials comprising the mixed polyol, the foaming agent, the catalyst, the cross-linking agent and the surfactant to obtain a material A2.
The stirring speed is 500-1000 r/min, and specifically, can be 700r/min; the time is 5-15 min, specifically, 10min.
In some embodiments of the present invention, the preparation raw materials of the flame-retardant microporous polyurethane foam further comprise a material A3. The material A3 comprises modified diisocyanate. The viscosity of the modified diisocyanate at 25 ℃ is 2000-5000 mPas, and the mass content of NCO is 10% -20%. The modified diisocyanate comprises a liquid modification of at least one of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate and isophorone diisocyanate. Specifically, it may be ISONATE TM 181MDI。
In certain embodiments of the present invention, the mass ratio of material A1, material A2, and material A3 is 38-65: 35-72: 22-62; specifically, 51.17 may be: 69.08:29.19, 49.33:71.76:29.31, 62.18:54.17:24.61, 64.23:52.13:24.61, 54.72:60.71:24.04 or 54.72:59.85:22.89.
in certain embodiments of the present invention, the flame retardant microcellular polyurethane foam further comprises a film attached to the polyurethane foam. The film is made of at least one of PET and release paper. The thickness of the film is 0.02-0.2 mm; specifically, it may be 0.05mm.
The invention also provides a preparation method of the flame-retardant microporous polyurethane foam, which comprises the following steps:
a) Uniformly mixing the material A1 and the material A2 to obtain a mixed material;
the material A1 is prepared by mixing raw materials comprising expandable graphite, metal hydrated salt oxide, inorganic phosphorus flame retardant, liquid-added organic phosphate flame retardant and flame-retardant polyol;
the material A2 is obtained by mixing raw materials comprising mixed polyol, a foaming agent, a catalyst, a cross-linking agent and a surfactant;
b) Uniformly mixing the mixed material with the material A3, coating the mixture on a film, and baking and curing the mixture to obtain flame-retardant microporous polyurethane foam;
The material A3 comprises modified diisocyanate.
In the preparation method of the flame-retardant microporous polyurethane foam, the adopted raw material components and the adopted dosage are the same, and are not repeated here.
In step A):
in some embodiments of the invention, the rotation speed of the material A1 and the material A2 which are uniformly mixed is 600-800 r/min, and specifically, can be 700r/min; the time is 5-15 min, specifically, 10min.
In step B):
uniformly mixing the mixed material with the material A3, coating the mixture on a film, and baking and curing the mixture to obtain flame-retardant microporous polyurethane foam;
the material A3 is modified diisocyanate.
In certain embodiments of the invention, the mixing is performed in a high speed mixer. The rotation speed of the uniform mixing is 1000-3000 r/min, specifically, 3000r/min.
In certain embodiments of the present invention, the baking and curing temperature is 70 to 100 ℃, specifically, may be 80 ℃; the time is 5-30 min, specifically, 30min.
The invention also provides application of the flame-retardant microporous polyurethane foam or the flame-retardant microporous polyurethane foam prepared by the preparation method as a buffer material, a heat insulation material and a sealing material. In particular to the application of the material as a buffer material, a heat insulation material and a sealing material between the battery cells of the lithium ion power battery. The flame-retardant microporous polyurethane foam is particularly suitable for buffer sealing of lithium ion power automobile batteries, softness ensures that the relatively uniform compression resilience force of the flame-retardant microporous polyurethane foam is suitable for expansion and contraction of the batteries, and high flame retardance can prevent flame from spreading when the batteries are heated in thermal runaway.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe the flame retardant microporous polyurethane foam, its preparation method and application in detail, but they should not be construed as limiting the scope of the invention.
Example 1
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 210 ℃ and an expansion rate of 100-150 mL/g at 800 ℃ and a particle size median of 50 mu m), metal hydrated salt oxide (aluminum hydroxide and inorganic phosphorus flame retardant (ammonium polyphosphate) into liquid additive type organic phosphate flame retardant (triethyl phosphate, superior product), then adding into flame retardant polyol (Corean Exolit OP 550), stirring at a rotation speed of 700r/min for 10min, and then passing through a 50-mesh filter screen to obtain a material A1, wherein the viscosity of the material A1 is 12000 mPa.s;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM WK 3140 Polyol), polyol P2 (VORANOL TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersion plate at 700r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (triethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 700r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Example 2 (flame retardant containing no inorganic phosphorus)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 210 ℃ and an expansion rate of 100-150 mL/g at 800 ℃ and a particle size median of 50 mu m) and metal hydrous salt oxide (aluminum hydroxide) into a liquid-added organic phosphate flame retardant (triethyl phosphate, industrial grade), then adding into flame-retardant polyol (Corean Exolit OP 550), stirring at a rotation speed of 700r/min for 10min, and then filtering through a 50-mesh filter screen to obtain a material A1; the viscosity of the material A1 is 11000 mPas;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM WK 3140 Polyol), polyol P2 (VORANOL TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersion plate at 700r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (triethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 700r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Example 3 (flame retardant containing no inorganic phosphorus)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 187 ℃, an expansion rate of 230-250 mL/g at 800 ℃ and a particle size median of 90 mu m) and metal hydrous salt oxide (aluminum hydroxide) into a liquid-added organic phosphate flame retardant (triethyl phosphate, industrial grade), then adding into flame-retardant polyol (Corean Exolit OP 550), stirring at a rotation speed of 700r/min for 10min, and then passing through a 50-mesh filter screen to obtain a material A1; the viscosity of the material A1 is 22000 mPas;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM CP 450), polyol P2 (VORANOL) TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersion plate at 700r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (triethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 700r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Example 4 (inorganic phosphorus-free flame retardant)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 187 ℃, an expansion rate of 230-250 mL/g at 800 ℃ and a particle size median of 90 mu m) and metal hydrous salt oxide (magnesium hydroxide) into a liquid-added organic phosphate flame retardant (triisobutyl phosphate, industrial grade), then adding into a flame-retardant polyol (Corean Exolit OP 550), stirring at a rotation speed of 700r/min for 10min, and then passing through a 50-mesh filter screen to obtain a material A1; the viscosity of the material A1 is 20000 mPas;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM CP 450), polyol P2 (VORANOL) TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersion plate at 700r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (diethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 700r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Example 5 (inorganic phosphorus-free flame retardant)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 210 ℃ and an expansion rate of 100-150 mL/g at 800 ℃ and a particle size median of 50 mu m) and metal hydrous salt oxide (magnesium hydroxide) into a liquid-added organic phosphate flame retardant (triisobutyl phosphate, industrial grade), then adding into flame-retardant polyol (Corean Exolit OP 550), stirring at a rotating speed of 1000r/min for 10min, and then passing through a 50-mesh filter screen to obtain a material A1; the viscosity of the material A1 is 14000 mPa.s;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM CP 450), polyol P2 (VORANOL) TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersing disc at 1000r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the above mixed polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (ethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 1000r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Example 6 (inorganic phosphorus-free flame retardant)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 196 ℃ and an expansion rate of 250-280 mL/g at 800 ℃ and a particle size median of 180 mu m) and metal hydrous salt oxide (zinc borate) into a liquid additive type organic phosphate flame retardant (triisobutyl phosphate, industrial grade), then adding into flame retardant polyol (Corean Exolit OP 550), stirring at a rotating speed of 1000r/min for 10min, and then passing through a 30-mesh filter screen to obtain a material A1; the viscosity of the material A1 is 26000 mPa.s;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM CP 450), polyol P2 (VORANOL) TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersing disc at 1000r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the above mixed polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (ethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 1000r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Comparative example 1 (without flame retardant polyol (Kelain Exolit OP 550) and crosslinking agent)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 196 ℃ and an expansion rate of 250-280 mL/g at 800 ℃ and a particle size median of 180 mu m), metal hydrous salt oxide (aluminum hydroxide) and inorganic phosphorus flame retardant (ammonium polyphosphate) into liquid additive type organic phosphate flame retardant (triisobutyl phosphate, industrial grade), stirring at a rotating speed of 700r/min for 10min, and then filtering through a 30-mesh filter screen to obtain a material A1; the viscosity of the material A1 is 24000 mPas;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM 3003LM Polyol), polyol P2 (VORANOL TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersing disc at 1000r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is excellent FOCAT-8002, mass ratio is 1:1), and surfactant (VOR)ASURF TM DC 8835) is stirred and mixed uniformly for 10min at 1000r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Comparative example 2 (without flame retardant polyol (Kelain Exolit OP 550))
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder, initial decomposition temperature of 210 ℃, expansion rate of 100-150 mL/g at 800 ℃, median particle size of 50 μm), metal hydrate oxide (magnesium hydroxide) and inorganic phosphorus flame retardant (ammonium polyphosphate) into liquid additive type organic phosphate flame retardant (tripropyl phosphate, industrial grade), stirring at 700r/min for 10min, and then carrying out suction filtration under vacuum condition of-0.05 MPa, wherein the filtered solid-liquid mixture is filtered through a 50-mesh filter screen to obtain a material A1; the viscosity of the material A1 was 17000 mPas;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM 3003LM Polyol), polyol P2 (VORANOL TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersion plate at 700r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the above mixed polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (ethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 700r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Comparative example 3 (inorganic phosphorus flame retardant-free)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 196 ℃ and an expansion rate of 250-280 mL/g at 800 ℃ and a particle size median of 180 mu m) and metal hydrous salt oxide (zinc borate) into a liquid-added type organic phosphate flame retardant (tripropyl phosphate, industrial grade), then adding into flame-retardant polyol (Corean Exolit OP 550), stirring at a rotation speed of 700r/min for 10min, and then passing through a 50-mesh filter screen to obtain a material A1; the viscosity of the material A1 is 24000 mPas;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM 3003LM Polyol), polyol P2 (VORANOL TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersing disc at 1000r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (diethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 1000r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Comparative example 4 (free of flame retardant polyol (Kelaine Exolit OP 550) and blowing agent)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 196 ℃ and an expansion rate of 250-280 mL/g at 800 ℃ and a particle size median of 180 mu m), metal hydrated salt oxide (aluminum hydroxide) and inorganic phosphorus flame retardant (ammonium polyphosphate) into liquid additive type organic phosphate flame retardant (tripropyl phosphate, industrial grade), stirring at a rotating speed of 1000r/min for 10min, and then passing through a 30-mesh filter screen to obtain a material A1; the viscosity of the material A1 is 14000 mPa.s;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM 3003LM Polyol), polyol P2 (VORANOL TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersing disc at 1000r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the polyol, catalyst (first catalyst is Michigan NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), cross-linking agent (ethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 700r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
Comparative example 5 (inorganic phosphorus flame retardant-free)
1) Preparation of material A1:
adding expandable graphite (expandable graphite powder with an initial decomposition temperature of 187 ℃, an expansion rate of 230-250 mL/g at 800 ℃ and a particle size median of 90 mu m) and metal hydrous salt oxide (montmorillonite) into a liquid-added type organic phosphate flame retardant (tripropyl phosphate, industrial grade), then adding into flame-retardant polyol (Corean Exolit OP 550), stirring at a rotating speed of 1000r/min for 10min, and then passing through a 50-mesh filter screen to obtain a material A1; the viscosity of the material A1 was 16000 mPas;
2) Preparation of a mixed polyol:
polyol P1 (VORANOL) TM 3003LM Polyol), polyol P2 (VORANOL TM 4701 Polyol), polyol P3 (POP 38/26, big blue star east), and Polyol P4 (VORANOL) TM 4000 Polyol) in a dispersing disc at 1000r/min for uniformly mixing for 10min to obtain mixed Polyol;
3) Preparation of material A2:
mixing the above mixed polyol, foaming agent (pure water), catalyst (first catalyst is Maifanitum NIAX MC-710, second catalyst is Rurun FOCAT-8002, mass ratio is 1:1), crosslinking agent (ethanolamine) and surfactant (VORASURF) TM DC 8835) is stirred and mixed uniformly for 10min at 1000r/min to obtain a material A2;
4) Uniformly mixing the material A1 and the material A2 at the speed of 700r/min for 10min to obtain a mixed material;
5) And uniformly mixing the mixed material with a material A3 (modified diisocyanate) (with the rotating speed of 3000 r/min), coating the mixture on a film (PET, with the thickness of 0.05 mm), and baking and curing the film at 80 ℃ for 30min to obtain the flame-retardant microporous polyurethane foam.
The raw material components and amounts of examples 1 to 6 and comparative examples 1 to 5 are shown in Table 1.
Table 1 raw material components and amounts (unit: g) of examples 1 to 6 and comparative examples 1 to 5
The properties of the flame-retardant microporous polyurethane foam prepared in examples 1 to 6 and comparative examples 1 to 5 were examined as follows:
1) Test of TGA initial decomposition temperature and residual carbon amount:
the temperature interval is between room temperature and 800 ℃, and the temperature rising rate is 10 ℃/min;
the test conditions were: 1.0-1.5 mg of sample weight, nitrogen atmosphere;
the initial decomposition temperature is defined as: the temperature was deviated from the baseline under the TGA test conditions described above.
The carbon residue is defined as: TGA, under the TGA test conditions described above, tests the ratio of endpoint residual weight to initial weight.
2) Measurement of minimum thickness required to reach UL 94V0 rating:
with reference to UL94-2016, the minimum thickness required to achieve V0 rating is tested.
3) Detection of total after flame time/s of vertical combustion:
referring to UL94-2016, a vertical burn test recorded 5 sets of burns, each set was fired twice, and after each set was tested for flame application, the foam material burned for total after flame time.
4) Measurement of density:
measurements were made with reference to ASTM3574-2017 TestA using a balance, a thickness gauge.
5) Determination of compressive Strength:
with reference to ASTM3574-2017 Test C, the stress at 25% compressive strain was recorded using a universal tensile tester at a compression rate of 5 mm/min.
6) Compression set test:
referring to ASTM3574-2017 Test D, the compression set tooling was used to fix, control the compression ratio to 50%, programmable aging oven, aging conditions: the temperature is 85 ℃, the humidity is 85 percent, and the holding time is 72 hours.
7) Oxygen index test method:
the combustion behaviour was determined by oxygen index method with reference to GB T2406.1-2008 plastics, test thickness: actual thickness.
The test results are shown in Table 2.
Table 2 results of performance tests of flame-retardant microporous polyurethane foam prepared in examples 1 to 6 and comparative examples 1 to 5
Experimental results show that by controlling the content of the proper flame retardant, the initial decomposition temperature of the TGA of the foam is controlled within a proper range between 180 ℃ and 220 ℃, the carbon residue is 15% -25%, and the requirement of UL94 vertical burning V0 is met. Meanwhile, the compressive strength under 25% compressive strain is (30-80 KPa), and the method is suitable for application between conventional soft package battery cells. The flame-retardant grade flame-retardant material provided by the invention can be softer and thinner, and can realize better balance of compressibility, aging resistance and flame retardance.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A flame-retardant microporous polyurethane foam is characterized in that the thickness of polyurethane foam forming the flame-retardant microporous polyurethane foam is 2.0-3.5 mm, and the density is 280-360 kg/m 3 ；
The 25% compression strength of the polyurethane foam is 30-80 KPa, the average pore diameter is 90-180 mu m, the initial decomposition temperature of a TGA test is 180-220 ℃, and the carbon residue is 15% -25%;
the flame-retardant microporous polyurethane foam is aged for 72 hours under the conditions of humidity of 85% and temperature of 85 ℃ in a state of being compressed by 50%, and the compression permanent deformation is less than 15%;
the preparation raw materials of the flame-retardant microporous polyurethane foam comprise a material A1;
the material A1 is prepared by mixing raw materials comprising expandable graphite, metal hydrated salt oxide, liquid-added organic phosphate flame retardant and flame-retardant polyol;
the expandable graphite is expandable graphite powder, the initial decomposition temperature is 150-200 ℃, the expansion rate at 800 ℃ is 100-300 mL/g, and the median value of the particle size is 30-200 mu m;
the liquid additive type organic phosphate flame retardant comprises at least one of triethyl phosphate, tripropyl phosphate, triisobutyl phosphate and triaryl phosphate;
the mass content of phosphorus in the liquid additive type organic phosphate flame retardant is 10% -20%, and the viscosity is 10-100 mPa.s;
The flame-retardant polyol is a phosphorus-containing polyol, the hydroxyl value of the phosphorus-containing polyol is 300-600 KOH mg/g, the mass content of phosphorus is 10-15%, and the viscosity is 100-600 mPa.s.
2. The flame retardant microporous polyurethane foam according to claim 1, wherein the flame retardant microporous polyurethane foam meets UL94 vertical burn V0 rating.
3. The flame-retardant microporous polyurethane foam according to claim 1, wherein the material A1 is prepared according to the following method:
adding expandable graphite, metal hydrated salt oxide and inorganic phosphorus flame retardant into liquid additive type organic phosphate flame retardant, then adding into flame retardant polyol, stirring at a rotating speed of 500-1000 r/min for 5-15 min, and then passing through a filter screen with 30-50 meshes to obtain a material A1;
the material A1 does not settle after standing for 3-6 hours, and the viscosity of the material A1 is 10000-30000 mPa.s;
the mass ratio of the expandable graphite to the metal hydrated salt oxide to the inorganic phosphorus flame retardant to the liquid-added organic phosphate flame retardant to the flame-retardant polyol is 20-30: 2-8: 0-6: 5-15: 7-22.
4. The flame retardant microporous polyurethane foam according to claim 3, wherein the metal hydrous salt oxide comprises at least one of magnesium hydroxide, aluminum hydroxide, zinc borate, and montmorillonite;
The inorganic phosphorus flame retardant comprises at least one of ammonium polyphosphate and modified ammonium polyphosphate;
the median particle diameters of the metal hydrated salt oxide, the inorganic phosphorus flame retardant and the liquid-added organic phosphate flame retardant are all 1-50 mu m.
5. The flame-retardant microporous polyurethane foam according to claim 1, wherein the raw materials for preparing the flame-retardant microporous polyurethane foam further comprise a material A2;
the material A2 is obtained by mixing raw materials comprising mixed polyol, a foaming agent, a catalyst, a cross-linking agent and a surfactant; the mass ratio of the mixed polyol to the foaming agent to the catalyst to the cross-linking agent to the surfactant is 44-72: 0-0.3: 0.005-0.02: 0-2: 5-15;
the mixed polyol comprises polyol P1, polyol P2, polyol P3 and polyol P4;
the poly polyol P1 includes at least one of a polyether polyol and a polyester polyol; the weight average molecular weight of the polyether polyol is 400-6000, the weight average molecular weight of the polyester polyol is 400-6000, and the hydroxyl value of the polyol P1 is not less than 280 and not more than 380 KOH mg/g;
the polyatomic alcohol P2 is polyether polyatomic alcohol, the hydroxyl value is not less than 24 KOH mg/g and not more than 56KOH mg/g, and the EO content is not less than 70%;
The polyatomic alcohol P3 is polymer polyatomic alcohol with a hydroxyl value of 20-30 KOH mg/g;
the poly polyol P4 is a difunctional poly polyol with a weight average molecular weight of 2000-8000.
6. The flame retardant microporous polyurethane foam according to claim 5 wherein the crosslinking agent comprises at least one of trimethylolpropane, ethanolamine, diethanolamine, triethanolamine, and pentaerythritol;
the foaming agent comprises at least one of pure water, carbon dioxide and nitrogen;
the catalyst comprises a first catalyst and a second catalyst, wherein the first catalyst comprises at least one of organic bismuth, bismuth isooctanoate, zinc neodecanoate and zinc isooctanoate; the second catalyst comprises a polyurethane foaming catalyst;
the surfactant is a block copolymer of dimethyl siloxane and polyether.
7. The flame-retardant microporous polyurethane foam according to claim 1, wherein the raw materials for preparing the flame-retardant microporous polyurethane foam further comprise a material A3;
the material A3 comprises modified diisocyanate;
the viscosity of the modified diisocyanate at 25 ℃ is 2000-5000 mPa.s, and the mass content of NCO is 10% -20%;
the modified diisocyanate comprises liquid modification of any one or more of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate and isophorone diisocyanate.
8. The flame retardant microcellular polyurethane foam of claim 1, further comprising a film attached to the polyurethane foam;
the film is made of at least one of PET and release paper;
the thickness of the film is 0.02-0.2 mm.
9. The method for preparing the flame-retardant microporous polyurethane foam according to any one of claims 1 to 8, comprising the following steps:
a) Uniformly mixing the material A1 and the material A2 to obtain a mixed material;
the material A1 is prepared by mixing raw materials comprising expandable graphite, metal hydrated salt oxide, inorganic phosphorus flame retardant, liquid-added organic phosphate flame retardant and flame-retardant polyol;
the material A2 is obtained by mixing raw materials comprising mixed polyol, a foaming agent, a catalyst, a cross-linking agent and a surfactant;
b) Uniformly mixing the mixed material with the material A3, coating the mixture on a film, and baking and curing the mixture to obtain flame-retardant microporous polyurethane foam;
the material A3 comprises modified diisocyanate.
10. The use of the flame-retardant microporous polyurethane foam according to any one of claims 1 to 8 or the flame-retardant microporous polyurethane foam produced by the production method according to claim 9 as a cushioning material, a heat insulating material and a sealing material.
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