CN110845689A - High-flame-retardant graphite rigid polyurethane foam material and preparation method thereof - Google Patents

High-flame-retardant graphite rigid polyurethane foam material and preparation method thereof Download PDF

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Publication number
CN110845689A
CN110845689A CN201810949010.8A CN201810949010A CN110845689A CN 110845689 A CN110845689 A CN 110845689A CN 201810949010 A CN201810949010 A CN 201810949010A CN 110845689 A CN110845689 A CN 110845689A
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CN
China
Prior art keywords
parts
component
rigid polyurethane
polyurethane foam
flame
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Application number
CN201810949010.8A
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Chinese (zh)
Inventor
邓万学
褚明
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Hubei Hengyuan Yu Plastic Co Ltd
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Hubei Hengyuan Yu Plastic Co Ltd
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Priority to CN201810949010.8A priority Critical patent/CN110845689A/en
Publication of CN110845689A publication Critical patent/CN110845689A/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/542—Polycondensates of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Abstract

The invention discloses a high flame-retardant graphite rigid polyurethane foam material and a preparation method thereof, belonging to the technical field of polyurethane materials and comprising a component A and a component B; the component A comprises the following components in parts by mass: 100 parts of polymethylene polyphenyl polyisocyanate; the component B comprises the following components in parts by mass: 60-80 parts of phenolic resin polyol, 10-25 parts of foaming agent, 1-10 parts of chain extender, 2-6 parts of foam stabilizer, 2-10 parts of cross-linking agent, 0.5-8 parts of catalyst, 8-15 parts of expanded graphite and 8-30 parts of glass fiber, wherein the diameter of the glass fiber is 0.2-0.4 mm.

Description

High-flame-retardant graphite rigid polyurethane foam material and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to a high-flame-retardant graphite rigid polyurethane foam material and a preparation method thereof.
Background
The rigid polyurethane foam material, polyurethane rigid foam for short, is mostly of a closed-cell structure, has the excellent characteristics of good heat insulation effect, light weight, large specific strength, convenient construction and the like, has the characteristics of sound insulation, shock resistance, electric insulation, heat resistance, cold resistance, solvent resistance and the like, and is widely applied to the fields of heat insulation materials of refrigerator bodies of refrigerators and freezer cases, refrigerator houses, refrigerated trucks and the like, heat insulation materials of buildings, storage tanks, pipelines and the like.
However, the high flame-retardant graphite rigid polyurethane foam material in the prior art has limited application in some fields due to the flammability and the release of toxic gases such as carbon monoxide caused by melting and dripping during combustion.
Disclosure of Invention
The invention provides a high flame-retardant graphite rigid polyurethane foam material and a preparation method thereof for overcoming the problems in the prior art, wherein a composite flame-retardant technology is adopted, the flame-retardant property reaches the B1-grade standard, and the phenolic resin polyol and the expanded graphite have the advantages of good flame-retardant effect, low combustion smoke quantity, lasting flame-retardant effect, high strength, light weight, low heat conduction, good dimensional stability and the like.
In order to solve the problems in the prior art, the following technical scheme is adopted.
A high flame-retardant graphite rigid polyurethane foam material is characterized in that: consists of a component A and a component B;
the component A comprises the following components in parts by mass: 100 parts of polymethylene polyphenyl polyisocyanate;
the component B comprises the following components in parts by mass: 60-80 parts of phenolic resin polyol, 10-25 parts of foaming agent, 1-10 parts of chain extender, 2-6 parts of foam stabilizer, 2-10 parts of cross-linking agent, 0.5-8 parts of catalyst, 8-15 parts of expanded graphite and 8-30 parts of glass fiber, wherein the diameter of the glass fiber is 0.2-0.4 mm.
Further, the mass fraction of NCO of the polymethylene polyphenyl polyisocyanate is 30-32%
Further, the catalyst is an amine and/or organometallic catalyst.
Further, the foaming agent is one of HFC-245fa, n-pentane and isopentane.
Further, the chain extender is one or more of ethylene glycol, glycerol, trimethylolpropane and 1, 4-cyclohexanol.
A preparation method of a high flame-retardant graphite rigid polyurethane foam material is characterized by comprising the following steps: and adding the component A into the component B, and stirring at a high speed to enable the component A to foam freely, wherein the free foaming temperature is 10-50 ℃, and the time is 30-40 min.
Compared with the prior art, the invention has the following beneficial effects:
the high-flame-retardant graphite rigid polyurethane foam material disclosed by the invention adopts a composite flame-retardant technology, the flame-retardant property reaches the B1-grade standard, and the phenolic resin polyol and the expanded graphite have the advantages of good flame-retardant effect, low combustion smoke generation amount, lasting flame-retardant effect, high strength, light weight, low heat conduction, good size stability and the like.
Detailed Description
The technical solution of the invention will be clearly and completely described below with reference to the embodiments of the invention. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
A high flame-retardant graphite rigid polyurethane foam material consists of a component A and a component B;
the component A comprises the following components in parts by mass: 100 parts of polymethylene polyphenyl polyisocyanate, wherein the mass fraction of NCO is 30%;
the component B comprises the following components in parts by mass: 80 parts of phenolic resin polyol, 25 parts of HFC-245fa, 6 parts of glycerol, 6 parts of foam stabilizer, 2 parts of cross-linking agent, 5 parts of amine catalyst, 15 parts of expanded graphite and 19 parts of glass fiber, wherein the diameter of the glass fiber is 0.3 mm.
The preparation method of the high flame-retardant graphite rigid polyurethane foam material comprises the following steps: adding the component A into the component B, and stirring at high speed to allow the component A to foam freely at the temperature of 50 ℃ for 40 min.
Example 2
A high flame-retardant graphite rigid polyurethane foam material consists of a component A and a component B;
the component A comprises the following components in parts by mass: 100 parts of polymethylene polyphenyl polyisocyanate, wherein the NCO mass fraction is 31%;
the component B comprises the following components in parts by mass: 60 parts of phenolic resin polyol, 20 parts of isopentane, 10 parts of 1, 4-cyclohexanol, 2 parts of foam stabilizer, 6 parts of cross-linking agent, 8 parts of organic metal catalyst, 8 parts of expanded graphite and 30 parts of glass fiber, wherein the diameter of the glass fiber is 0.4 mm.
The preparation method of the high flame-retardant graphite rigid polyurethane foam material comprises the following steps: adding the component A into the component B, and stirring at high speed to allow the component A to foam freely at the temperature of 30 ℃ for 40 min.
Example 3
A high flame-retardant graphite rigid polyurethane foam material consists of a component A and a component B;
the component A comprises the following components in parts by mass: 100 parts of polymethylene polyphenyl polyisocyanate, wherein the NCO mass fraction is 32%;
the component B comprises the following components in parts by mass: 70 parts of phenolic resin polyol, 10 parts of n-pentane, 1 part of ethylene glycol, 4 parts of foam stabilizer, 10 parts of cross-linking agent, 0.5 part of organic metal catalyst, 10 parts of expanded graphite and 8 parts of glass fiber, wherein the diameter of the glass fiber is 0.2 mm.
The preparation method of the high flame-retardant graphite rigid polyurethane foam material comprises the following steps: adding the component A into the component B, and stirring at high speed to allow the component A to foam freely at the temperature of 10 ℃ for 35 min.
The high-flame-retardant graphite rigid polyurethane foam material disclosed by any one embodiment adopts a composite flame-retardant technology, the flame retardant property reaches the B1-grade standard, and the phenolic resin polyol and the expanded graphite have the advantages of good flame retardant effect, low combustion smoke generation amount, lasting flame retardant effect, high strength, light weight, low heat conduction, good dimensional stability and the like.

Claims (6)

1. A high flame-retardant graphite rigid polyurethane foam material is characterized in that: consists of a component A and a component B;
the component A comprises the following components in parts by mass: 100 parts of polymethylene polyphenyl polyisocyanate;
the component B comprises the following components in parts by mass: 60-80 parts of phenolic resin polyol, 10-25 parts of foaming agent, 1-10 parts of chain extender, 2-6 parts of foam stabilizer, 2-10 parts of cross-linking agent, 0.5-8 parts of catalyst, 8-15 parts of expanded graphite and 8-30 parts of glass fiber, wherein the diameter of the glass fiber is 0.2-0.4 mm.
2. The high flame retardant graphite rigid polyurethane foam according to claim 1, characterized in that: the mass fraction of NCO in the polymethylene polyphenyl polyisocyanate is 30-32%.
3. The high flame retardant graphite rigid polyurethane foam according to claim 1, characterized in that: the catalyst is an amine and/or organometallic catalyst.
4. The high flame retardant graphite rigid polyurethane foam according to claim 1, characterized in that: the foaming agent is one of HFC-245fa, n-pentane and isopentane.
5. The high flame retardant graphite rigid polyurethane foam according to claim 1, characterized in that: and the chain extender is one or more than one of ethylene glycol, glycerol, trimethylolpropane and 1, 4-cyclohexanol.
6. A method for preparing a high flame retardant graphite rigid polyurethane foam material according to any one of claims 1 to 5, characterized in that: and adding the component A into the component B, and stirring at a high speed to enable the component A to foam freely, wherein the free foaming temperature is 10-50 ℃, and the time is 30-40 min.
CN201810949010.8A 2018-08-20 2018-08-20 High-flame-retardant graphite rigid polyurethane foam material and preparation method thereof Withdrawn CN110845689A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111961333A (en) * 2020-08-30 2020-11-20 宁波耀众模塑科技有限公司 Preparation formula of polyurethane foaming product based on graphite material
CN114381111A (en) * 2021-11-30 2022-04-22 山东一诺威新材料有限公司 Pentane type multicomponent high-flame-retardant polyurethane composite phenolic aldehyde continuous plate composite material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111961333A (en) * 2020-08-30 2020-11-20 宁波耀众模塑科技有限公司 Preparation formula of polyurethane foaming product based on graphite material
CN114381111A (en) * 2021-11-30 2022-04-22 山东一诺威新材料有限公司 Pentane type multicomponent high-flame-retardant polyurethane composite phenolic aldehyde continuous plate composite material and preparation method thereof

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Application publication date: 20200228