CN113372528A - High-strength flame-retardant polyurethane foam plastic and preparation method thereof - Google Patents

High-strength flame-retardant polyurethane foam plastic and preparation method thereof Download PDF

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Publication number
CN113372528A
CN113372528A CN202110028761.8A CN202110028761A CN113372528A CN 113372528 A CN113372528 A CN 113372528A CN 202110028761 A CN202110028761 A CN 202110028761A CN 113372528 A CN113372528 A CN 113372528A
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parts
polyurethane foam
particles
agent
nucleating agent
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杜广杰
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Anhui University of Science and Technology
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Anhui University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/50Polyethers having heteroatoms other than oxygen
    • C08G18/5021Polyethers having heteroatoms other than oxygen having nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/487Polyethers containing cyclic groups
    • C08G18/4883Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085Use of fibrous compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00Manufacture of cellular products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/08Polyurethanes from polyethers

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

Abstract

The invention discloses a high-strength flame-retardant polyurethane foam plastic and a preparation method thereof, wherein the raw material of the polyurethane foam plastic is prepared by mixing and reacting combined polyether and isocyanate according to the parts by weight, and the weight part ratio of the combined polyether to the isocyanate is 1: 0.9-1.3; the composite polyether comprises the following components in parts by weight: 75-90 parts of polyhydroxy compound, 5-15 parts of glass fiber, 2-10 parts of foaming agent, 6-12 parts of stabilizer, 0.2-0.8 part of catalyst, 2-5 parts of antistatic agent, 1.5-3.5 parts of flame retardant, 0.5-4 parts of nucleating agent, 10-20 parts of ethanol, 1-4 parts of smoke suppressant and 5-8 parts of water. According to the polyurethane foam plastic, the flame retardant is added to enhance the flame retardant property, block a fire source, reduce smoke release by a smoke suppressant and reduce the harm of harmful gases, so that the problems of poor flame retardant property, large smoke release amount during combustion and the like of common rigid polyurethane foam plastic are effectively solved, and the glass fiber increases the strength of the foam plastic; ethanol increases the diffusion rate of the mixed particles, so that the particles are uniformly diffused.

Description

High-strength flame-retardant polyurethane foam plastic and preparation method thereof
Technical Field
The invention relates to a foamed plastic, in particular to a high-strength flame-retardant polyurethane foamed plastic and a preparation method thereof.
Background
Rigid polyurethane foam (RPU for short) is one of the most important varieties in polyurethane material systems, and has excellent physical and mechanical properties, acoustic properties, electrical properties, acid resistance and alkali resistance. The material has a closed pore rate of more than 90 percent, belongs to a hydrophobic material, has better moisture-proof and waterproof performance, good heat insulation, sound insulation and earthquake resistance, has strong cohesive force, and can be widely used as heat insulation materials of petrochemical pipelines, refrigeration equipment, transportation equipment, buildings and the like. However, the RPU without flame retardant treatment has low density, large specific surface area, poor flame retardancy, and oxygen index of about 17%, and is flammable material, and after the RPU catches fire, the flame spreads rapidly, and releases a large amount of toxic fumes (such as CO, CO2, HCN, etc.), which brings great difficulty to fire extinguishing and fire escape.
Disclosure of Invention
The invention aims to provide a high-strength flame-retardant polyurethane foam plastic and a preparation method thereof, wherein the raw material of the polyurethane foam plastic is prepared by mixing and reacting combined polyether and isocyanate; the composite polyether comprises the following components: the flame retardant is added to enhance the flame retardant performance, block a fire source, reduce smoke release by the smoke suppressant and reduce the harm of harmful gases, so that the problems of poor flame retardant performance, large smoke release amount during combustion and the like of common rigid polyurethane foam plastics are effectively solved, and the glass fiber increases the strength of the foam plastics and improves the bearing capacity; the addition of the nucleating agent reduces the heat conductivity of the rigid polyurethane foam plastic by 1-10%, the ethanol accelerates the flow of mixed particles, increases the diffusion rate, enables the particles to be uniformly diffused, and then is volatilized and removed, so that special treatment is not needed, the cost is reduced, and the antistatic agent avoids static electricity caused by friction.
The purpose of the invention can be realized by the following technical scheme:
the high-strength flame-retardant polyurethane foam plastic is prepared by mixing and reacting combined polyether and isocyanate according to parts by weight, wherein the weight ratio of the combined polyether to the isocyanate is 1: 0.9-1.3.
The composite polyether comprises the following components in parts by weight: 75-90 parts of polyhydroxy compound, 5-15 parts of glass fiber, 2-10 parts of foaming agent, 6-12 parts of stabilizer, 0.2-0.8 part of catalyst, 2-5 parts of antistatic agent, 1.5-3.5 parts of flame retardant, 0.5-4 parts of nucleating agent, 10-20 parts of ethanol, 1-4 parts of smoke suppressant and 5-8 parts of water.
The nucleating agent is Al2O3Particles, ZrO2Particles and SiO2One or more of the particles, Al2O3Particles and ZrO2The particle diameter of the particles is 10-30 mu m, SiO2The grain diameter of the grain is less than 100nm, the grain of the nucleating agent is spherical, and the ethanol assists the nucleating agent to accelerate the dispersion and then volatilize.
Furthermore, the polyhydroxy compound is one or a mixture of amine polyether polyol and sucrose polyether polyol.
Further, the foaming agent is selected from one or more of n-pentane, cyclopentane and isopentane, HFC-134a, HFC-245fa and HFC-365 mfc.
Further, the stabilizer is one or more of foam stabilizer AK8805 and foam stabilizer L6950.
Further, the catalyst is selected from one or a mixture of tertiary ammonia and organic tin.
Further, the smoke suppressant is selected from one or more of zinc borate, aluminum hydroxide and magnesium hydroxide.
Further, the antistatic agent is one or more of carbon black, amine derivatives, phosphate esters and polyethylene glycol derivatives.
A preparation method of high-strength flame-retardant polyurethane foam comprises the following steps:
s1, detecting the grain size of the nucleating agent particles, pouring the non-conforming nucleating agent into a grinder to grind and sieve;
s2, sequentially adding the multi-hydroxyl compound, the foaming agent, the antistatic agent, the flame retardant, the smoke suppressant, the stabilizer, the glass fiber, the nucleating agent and the ethanol in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 2500-5000 rpm, and the stirring time is 10-20 min;
s3, adding the isocyanate and the catalyst in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 3000-6000 rpm, and the mixing time is less than or equal to 5 min;
s4, adding the mixture obtained in the step S3 into the mixture obtained in the step S2, adding water, mixing, and stirring uniformly at the rotating speed of 2000rpm-3500rpm for less than or equal to 1 min;
s5, feeding the mixture obtained in the step S4 into a foaming machine die, wherein the foaming pressure is 120-180 bar, and the foaming temperature is 20-30 ℃.
The invention has the beneficial effects that:
1. according to the polyurethane foam plastic, the flame retardant is added to enhance the flame retardant property, block a fire source, reduce smoke release by a smoke suppressant and reduce the harm of harmful gases, so that the problems of poor flame retardant property, large smoke release amount during combustion and the like of common rigid polyurethane foam plastic are effectively solved, the glass fiber increases the strength of the foam plastic, and the bearing capacity is improved;
2. the addition of the nucleating agent of the polyurethane foam plastic reduces the heat conductivity of the rigid polyurethane foam plastic by 1-10%, the ethanol accelerates the flow of mixed particles, increases the diffusion rate, ensures the particles to be uniformly diffused, and then volatilizes and removes the particles without special treatment, reduces the cost, and the antistatic agent avoids generating static electricity caused by friction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The high-strength flame-retardant polyurethane foam plastic is prepared by mixing and reacting combined polyether and isocyanate according to parts by weight, wherein the weight ratio of the combined polyether to the isocyanate is 1: 0.9-1.3.
The composite polyether comprises the following components in parts by weight: 75-90 parts of polyhydroxy compound, 5-15 parts of glass fiber, 2-10 parts of foaming agent, 6-12 parts of stabilizer, 0.2-0.8 part of catalyst, 2-5 parts of antistatic agent, 1.5-3.5 parts of flame retardant, 0.5-4 parts of nucleating agent, 10-20 parts of ethanol, 1-4 parts of smoke suppressant and 5-8 parts of water.
The polyhydroxy compound is one or a mixture of amine polyether polyol and sucrose polyether polyol.
The foaming agent is one or more of n-pentane, cyclopentane and isopentane, HFC-134a, HFC-245fa and HFC-365 mfc.
The stabilizer is one or more of foam stabilizer AK8805 and foam stabilizer L6950.
The catalyst is selected from one or a mixture of tertiary ammonia and organic tin.
The smoke suppressant is selected from one or more of zinc borate, aluminum hydroxide and magnesium hydroxide.
The antistatic agent is one or more of carbon black, amine derivatives, phosphate and polyethylene glycol derivatives.
The nucleating agent is Al2O3Particles, ZrO2Particles and SiO2One or more of the particles, Al2O3Particles and ZrO2The particle diameter of the particles is 10-30 mu m, SiO2The grain diameter of the grain is less than 100nm, the grain of the nucleating agent is spherical, and the ethanol assists the nucleating agent to accelerate the dispersion and then volatilize.
A preparation method of high-strength flame-retardant polyurethane foam comprises the following steps:
s1, detecting the grain size of the nucleating agent particles, pouring the non-conforming nucleating agent into a grinder to grind and sieve;
s2, sequentially adding the multi-hydroxyl compound, the foaming agent, the antistatic agent, the flame retardant, the smoke suppressant, the stabilizer, the glass fiber, the nucleating agent and the ethanol in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 2500-5000 rpm, and the stirring time is 10-20 min;
s3, adding the isocyanate and the catalyst in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 3000-6000 rpm, and the mixing time is less than or equal to 5 min;
s4, adding the mixture obtained in the step S3 into the mixture obtained in the step S2, adding water, mixing, and stirring uniformly at the rotating speed of 2000rpm-3500rpm for less than or equal to 1 min;
s5, feeding the mixture obtained in the step S4 into a foaming machine die, wherein the foaming pressure is 120-180 bar, and the foaming temperature is 20-30 ℃.
Example 1
The composite polyether comprises the following components in parts by weight: 75 parts of a polyhydroxy compound, 5 parts of glass fiber, 2 parts of a foaming agent, 6 parts of a stabilizer, 0.2 part of a catalyst, 2 parts of an antistatic agent, 1.5 parts of a flame retardant, 0.5 part of a nucleating agent, 10 parts of ethanol, 1 part of a smoke suppressant and 5 parts of water.
S1, detecting the grain size of the nucleating agent particles, pouring the non-conforming nucleating agent into a grinder to grind and sieve;
s2, sequentially adding the multi-hydroxyl compound, the foaming agent, the antistatic agent, the flame retardant, the smoke suppressant, the stabilizer, the glass fiber, the nucleating agent and the ethanol in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 2500rpm, and the stirring time is 10-20 min;
s3, adding the isocyanate and the catalyst in parts by weight into a stirrer for uniform mixing, wherein the mixing time is less than or equal to 5min at the rotating speed of the stirrer of 3000 rpm;
s4, adding the mixture obtained in the step S3 into the mixture obtained in the step S2, adding water, mixing, and stirring uniformly, wherein the mixing time is less than or equal to 1min at the rotating speed of 2000 rpm;
s5, feeding the mixture obtained in the step S4 into a foaming machine die, wherein the foaming pressure is 120bar, and the foaming temperature is 20-30 ℃.
Example 2
The high-strength flame-retardant polyurethane foam plastic is prepared by mixing and reacting combined polyether and isocyanate according to parts by weight, wherein the weight ratio of the combined polyether to the isocyanate is 1: 1-1.3.
The composite polyether comprises the following components in parts by weight: 90 parts of multi-hydroxyl compound, 15 parts of glass fiber, 10 parts of foaming agent, 12 parts of stabilizer, 0.8 part of catalyst, 5 parts of antistatic agent, 3.5 parts of flame retardant, 4 parts of nucleating agent, 20 parts of ethanol, 4 parts of smoke suppressant and 8 parts of water,
s1, detecting the grain size of the nucleating agent particles, pouring the non-conforming nucleating agent into a grinder to grind and sieve;
s2, sequentially adding the multi-hydroxyl compound, the foaming agent, the antistatic agent, the flame retardant, the smoke suppressant, the stabilizer, the glass fiber, the nucleating agent and the ethanol in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 5000rpm, and the stirring time is 10-20 min;
s3, adding the isocyanate and the catalyst in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 6000rpm, and the mixing time is less than or equal to 5 min;
s4, adding the mixture obtained in the step S3 into the mixture obtained in the step S2, adding water, mixing, and stirring uniformly at the rotation speed of 3500rpm for less than or equal to 1 min;
s5, feeding the mixture obtained in the step S4 into a foaming machine die, wherein the foaming pressure is 180bar, and the foaming temperature is 20-30 ℃.
The composition ratios of the components in the embodiment 1 and the embodiment 2 are different, and both the components are within the set range, and the high flame retardant property and the high strength property are both provided.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.

Claims (8)

1. The high-strength flame-retardant polyurethane foam plastic is characterized in that the raw material of the polyurethane foam plastic is prepared by mixing and reacting combined polyether and isocyanate according to the parts by weight, wherein the weight ratio of the combined polyether to the isocyanate is 1: 0.9-1.3;
the composite polyether comprises the following components in parts by weight: 75-90 parts of a polyhydroxy compound, 5-15 parts of glass fiber, 2-10 parts of a foaming agent, 6-12 parts of a stabilizer, 0.2-0.8 part of a catalyst, 2-5 parts of an antistatic agent, 1.5-3.5 parts of a flame retardant, 0.5-4 parts of a nucleating agent, 10-20 parts of ethanol, 1-4 parts of a smoke suppressant and 5-8 parts of water;
the nucleating agent is Al2O3Particles, ZrO2Particles and SiO2One or more of the particles, Al2O3Particles and ZrO2The particle diameter of the particles is 10-30 mu m, SiO2The grain diameter of the grain is less than 100nm, the grain of the nucleating agent is spherical, and the ethanol assists the nucleating agent to accelerate the dispersion and then volatilize.
2. The high-strength flame-retardant polyurethane foam as claimed in claim 1, wherein the polyol is one or a mixture of amine polyether polyol and sucrose polyether polyol.
3. The high-strength flame-retardant polyurethane foam as claimed in claim 1, wherein the blowing agent is one or more selected from n-pentane, cyclopentane and isopentane, HFC-134a, HFC-245fa and HFC-365 mfc.
4. The high-strength flame-retardant polyurethane foam according to claim 1, wherein the stabilizer is one or more of foam stabilizer AK8805 and foam stabilizer L6950.
5. The high-strength flame-retardant polyurethane foam as claimed in claim 1, wherein the catalyst is selected from one or a mixture of tertiary ammonia and organic tin.
6. The high strength flame retardant polyurethane foam according to claim 1, wherein the smoke suppressant is one or more selected from the group consisting of zinc borate, aluminum hydroxide and magnesium hydroxide.
7. The high-strength flame-retardant polyurethane foam according to claim 1, wherein the antistatic agent is one or more selected from carbon black, amine derivatives, phosphate esters and polyethylene glycol derivatives.
8. The method for preparing a high-strength flame-retardant polyurethane foam according to any one of claims 1 to 7, wherein the polyurethane foam is prepared by the following steps:
s1, detecting the grain size of the nucleating agent particles, pouring the non-conforming nucleating agent into a grinder to grind and sieve;
s2, sequentially adding the multi-hydroxyl compound, the foaming agent, the antistatic agent, the flame retardant, the smoke suppressant, the stabilizer, the glass fiber, the nucleating agent and the ethanol in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 2500-5000 rpm, and the stirring time is 10-20 min;
s3, adding the isocyanate and the catalyst in parts by weight into a stirrer for uniform mixing, wherein the rotating speed of the stirrer is 3000-6000 rpm, and the mixing time is less than or equal to 5 min;
s4, adding the mixture obtained in the step S3 into the mixture obtained in the step S2, adding water, mixing, and stirring uniformly at the rotating speed of 2000rpm-3500rpm for less than or equal to 1 min;
s5, feeding the mixture obtained in the step S4 into a foaming machine die, wherein the foaming pressure is 120-180 bar, and the foaming temperature is 20-30 ℃.
CN202110028761.8A 2021-01-11 2021-01-11 High-strength flame-retardant polyurethane foam plastic and preparation method thereof Pending CN113372528A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101125910A (en) * 2006-08-16 2008-02-20 广东科龙电器股份有限公司 Hard polyurethane foam plastic and producing method thereof
CN102875770A (en) * 2012-09-20 2013-01-16 吴江市天源塑胶有限公司 Preparation method of high-temperature-resistant modified polyisocyanurate foamed plastic
CN103826853A (en) * 2011-07-26 2014-05-28 陶氏环球技术有限责任公司 An isocyanate-based polymer foam composite with improved thermal insulation properties
CN104829809A (en) * 2014-02-11 2015-08-12 王祖文 High-molecular foam material
CN106893074A (en) * 2017-03-03 2017-06-27 公安部天津消防研究所 A kind of preparation method of high fire-retardance smoke-inhibiting type RPUF

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101125910A (en) * 2006-08-16 2008-02-20 广东科龙电器股份有限公司 Hard polyurethane foam plastic and producing method thereof
CN103826853A (en) * 2011-07-26 2014-05-28 陶氏环球技术有限责任公司 An isocyanate-based polymer foam composite with improved thermal insulation properties
CN102875770A (en) * 2012-09-20 2013-01-16 吴江市天源塑胶有限公司 Preparation method of high-temperature-resistant modified polyisocyanurate foamed plastic
CN104829809A (en) * 2014-02-11 2015-08-12 王祖文 High-molecular foam material
CN106893074A (en) * 2017-03-03 2017-06-27 公安部天津消防研究所 A kind of preparation method of high fire-retardance smoke-inhibiting type RPUF

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Application publication date: 20210910