CN113603927A - Flame-retardant polyurethane foam and preparation method thereof - Google Patents
Flame-retardant polyurethane foam and preparation method thereof Download PDFInfo
- Publication number
- CN113603927A CN113603927A CN202111010414.9A CN202111010414A CN113603927A CN 113603927 A CN113603927 A CN 113603927A CN 202111010414 A CN202111010414 A CN 202111010414A CN 113603927 A CN113603927 A CN 113603927A
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- CN
- China
- Prior art keywords
- polyurethane foam
- flame
- graphene
- retardant
- polydopamine
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 61
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 61
- 239000003063 flame retardant Substances 0.000 title claims abstract description 47
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 48
- 229920001690 polydopamine Polymers 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229960003638 dopamine Drugs 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000000707 layer-by-layer assembly Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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
- C08J9/36—After-treatment
- C08J9/365—Coating
-
- 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
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- 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
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
Abstract
The invention belongs to the technical field of flame-retardant materials, and particularly relates to flame-retardant polyurethane foam which is composed of polyurethane foam and a flame retardant containing polydopamine and graphene materials, wherein the flame retardant is fixed on the surface of the polyurethane foam in a layer-by-layer assembly mode. According to the invention, the stable surface coating is formed by utilizing polydopamine and graphene materials, so that not only can the excellent mechanical property of polyurethane foam be maintained, but also effective flame retardance can be provided, and meanwhile, the polydopamine flame-retardant layer assembled layer by layer has excellent comprehensive performance, so that the potential safety problem and the potential safety hazard in the practical application of polyurethane foam products can be effectively reduced, and the application range of the product is expanded.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to flame-retardant polyurethane foam and a preparation method thereof.
Background
Polyurethane foams are widely used for soft-furniture and insulation applications because of their low cost, light weight, adjustable compressibility, and most importantly durability. However, polyurethane foam articles face safety issues in practical applications due to the inherent flammability and toxic degradation products of polyurethane. Pure polyurethane foam burns violently and produces a large amount of toxic gases such as carbon monoxide, hydrogen cyanide and the like, which have obvious harm to human health and environment. To address this problem, flame retardants represented by halogen-containing compounds are added to polyurethanes for flame-retardant treatment, but the halogen-containing compounds also cause emission of harmful gases during combustion. Furthermore, current flame retardants are often incorporated into the polymer in a physically mixed manner, and they may also leach/detach from the foam over time, leading to concerns over human exposure and bio-accumulation. Thus, there is a need in the market for new flame retardants that can provide effective flame retardancy without fear of easy migration/absorption into the human body, while also retaining the inherent mechanical properties of polyurethane foams.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the flame-retardant polyurethane foam, the stable surface coating is formed by utilizing the polydopamine and graphene materials, the excellent mechanical property of the polyurethane foam can be kept, the effective flame retardance can be provided, meanwhile, the comprehensive performance of the polydopamine-based flame-retardant layer assembled layer by layer is excellent, the potential safety problem hazard in the practical application of the polyurethane foam product can be effectively reduced, and the application range of the polyurethane foam product is expanded.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
the flame-retardant polyurethane foam consists of a flame retardant and polyurethane foam, wherein the flame retardant comprises polydopamine and graphene materials.
The mass ratio of the flame retardant is 1-20%, and the mass ratio of the polyurethane foam is 80-99%.
The graphene material is one of graphene, graphene oxide or graphene oxide liquid crystal,
the preparation method of the flame-retardant polyurethane foam comprises the following steps:
step 1, adding a graphene material into a solvent, stirring to obtain a graphene turbid liquid, and repeatedly dipping and extruding polyurethane foam in the graphene turbid liquid to form a conformal coating; the graphene material is one of graphene, graphene oxide or graphene oxide liquid crystal, the solvent is water or ethanol, and the mass concentration of the graphene suspension is 1-30 g/L;
step 2, soaking polyurethane foam containing a conformal coating into a dopamine aqueous solution, adjusting the pH value to perform a self-polymerization reaction to obtain a poly-dopamine coating, wherein the mass concentration of the dopamine aqueous solution is 1-2g/L, the pH value of the self-polymerization reaction is 8.5, and the pH value is adjusted by hydrochloric acid;
and 3, repeating the step 1 and the step 2 to form an alternate conformal coating and a polydopamine film, and drying to obtain the flame-retardant polyurethane foam.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the application difficulty of the flame retardant in polyurethane, and the stable surface coating is formed by utilizing polydopamine and graphene materials, so that the excellent mechanical property of polyurethane foam can be maintained, and effective flame retardance can be provided.
2. The polydopamine/graphene composite flame retardant disclosed by the invention takes polydopamine and graphene materials as a composite flame retardant, and is green, environment-friendly, nontoxic and harmless.
3. The polydopamine and graphene materials form a layer-by-layer assembled alternating structure, so that the graphene materials are immobilized by effectively utilizing the adhesion and fixation characteristics of the polydopamine, and the leaching/separation risk caused by physical mixing of the graphene materials is effectively solved.
4. The flame retardant is fixed on the surface of polyurethane foam in a layer-by-layer assembly characteristic, the flame retardant property of the poly-dopamine is fully utilized, the heat insulation effect of multilayer barrier is realized, meanwhile, the high heat conductivity of graphene per se homogenizes the heat between adjacent poly-dopamine layers, and the problem of local heat accumulation on the surface of the poly-dopamine is effectively solved.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
The flame-retardant polyurethane foam comprises 1 mass percent of flame retardant and 99 mass percent of polyurethane foam, wherein the flame retardant consists of polydopamine and graphene in a mass ratio of 1: 1.
A method of preparing a flame retardant polyurethane foam comprising:
step 1, adding graphene into water, stirring to obtain 1g/L graphene turbid liquid, and repeatedly dipping and extruding polyurethane foam in the graphene turbid liquid to form a shape-preserving coating;
step 2, soaking polyurethane foam containing a conformal coating into 1g/L dopamine aqueous solution, and adjusting by using hydrochloric acid to form a weak alkaline environment with the pH value of more than 8.5 for carrying out self-polymerization reaction to obtain a polydopamine coating;
and 3, repeating the step 1 and the step 2 to form an alternate conformal coating and a polydopamine film, and drying to obtain the flame-retardant polyurethane foam.
The polyurethane foam prepared in example 1 was tested for flame retardancy and had significant anti-drip properties, with a peak heat release rate reduced by 70%.
Example 2
The flame-retardant polyurethane foam comprises 20% of flame retardant by mass and 80% of polyurethane foam by mass, wherein the flame retardant consists of polydopamine and graphene in a mass ratio of 1: 2.
A method of preparing a flame retardant polyurethane foam comprising:
step 1, adding graphene oxide into water, stirring to obtain a 30g/L graphene oxide turbid liquid, and repeatedly dipping and extruding polyurethane foam in the graphene oxide turbid liquid to form a shape-preserving coating;
step 2, soaking polyurethane foam containing a conformal coating into 2g/L dopamine aqueous solution, and adjusting by using hydrochloric acid to form a weak alkaline environment with the pH value of more than 8.5 for carrying out self-polymerization reaction to obtain a polydopamine coating;
and 3, repeating the step 1 and the step 2 to form an alternate conformal coating and a polydopamine film, and drying to obtain the flame-retardant polyurethane foam.
The polyurethane foam prepared in example 2 was tested for flame retardancy and had significant anti-drip properties, with peak heat release rate reduced by 65%.
Example 3
The flame-retardant polyurethane foam comprises 10% of flame retardant by mass and 90% of polyurethane foam by mass, wherein the flame retardant consists of polydopamine and graphene in a mass ratio of 2: 1.
A method of preparing a flame retardant polyurethane foam comprising:
step 1, adding graphene oxide liquid crystal into water, stirring to obtain a 20g/L graphene oxide liquid crystal suspension, and repeatedly dipping and extruding polyurethane foam in the graphene oxide liquid crystal suspension to form a shape-preserving coating;
step 2, soaking polyurethane foam containing a conformal coating into 2g/L dopamine aqueous solution, and adjusting by using hydrochloric acid to form a weak alkaline environment with the pH value of more than 8.5 for carrying out self-polymerization reaction to obtain a polydopamine coating;
and 3, repeating the step 1 and the step 2 to form an alternate conformal coating and a polydopamine film, and drying to obtain the flame-retardant polyurethane foam.
The polyurethane foam prepared in example 3 was tested for flame retardancy and had significant anti-drip properties, with the peak heat release rate being reduced by 80%.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (9)
1. The flame-retardant polyurethane foam consists of a flame retardant and polyurethane foam, wherein the flame retardant comprises polydopamine and graphene materials.
2. The flame retarded polyurethane foam according to claim 1 wherein: the mass ratio of the flame retardant is 1-20%, and the mass ratio of the polyurethane foam is 80-99%.
3. The flame retarded polyurethane foam according to claim 1 wherein: the graphene material is one of graphene, graphene oxide or graphene oxide liquid crystal.
4. The flame retarded polyurethane foam according to claim 1 wherein: the preparation method of the flame-retardant polyurethane foam comprises the following steps:
step 1, adding a graphene material into a solvent, stirring to obtain a graphene turbid liquid, and repeatedly dipping and extruding polyurethane foam in the graphene turbid liquid to form a conformal coating;
step 2, soaking polyurethane foam containing the conformal coating into a polydopamine aqueous solution, adjusting the pH value to perform a self-polymerization reaction, and obtaining a polydopamine coating;
and 3, repeating the step 1 and the step 2 to form an alternate conformal coating and a polydopamine film, and drying to obtain the flame-retardant polyurethane foam.
5. The flame retarded polyurethane foam according to claim 4, wherein: the graphene material in the step 1 is one of graphene, graphene oxide or graphene oxide liquid crystal.
6. The flame retarded polyurethane foam according to claim 4, wherein: the solvent is water or ethanol.
7. The flame retarded polyurethane foam according to claim 4, wherein: the mass concentration of the graphene suspension is 1-30 g/L.
8. The flame retarded polyurethane foam according to claim 4, wherein: the mass concentration of the dopamine aqueous solution in the step 2 is 1-2 g/L.
9. The flame retarded polyurethane foam according to claim 4, wherein: the pH of the self-polymerization reaction in the step 2 is 8.5, and the pH is adjusted by hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111010414.9A CN113603927A (en) | 2021-08-31 | 2021-08-31 | Flame-retardant polyurethane foam and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111010414.9A CN113603927A (en) | 2021-08-31 | 2021-08-31 | Flame-retardant polyurethane foam and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113603927A true CN113603927A (en) | 2021-11-05 |
Family
ID=78309782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111010414.9A Pending CN113603927A (en) | 2021-08-31 | 2021-08-31 | Flame-retardant polyurethane foam and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113603927A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107570127A (en) * | 2017-09-08 | 2018-01-12 | 浙江工业大学 | A kind of graphene-based water-oil separating foamed material and its preparation method and application |
-
2021
- 2021-08-31 CN CN202111010414.9A patent/CN113603927A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107570127A (en) * | 2017-09-08 | 2018-01-12 | 浙江工业大学 | A kind of graphene-based water-oil separating foamed material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| HANIM KIM ET.AL.: "Polydopamine-Graphene Oxide Flame Retardant Nanocoatings Applied via an Aqueous Liquid Crystalline Scaffold", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| 林冬梅: "棉织物和聚氨酯海绵表面超疏水阻燃涂层的构造与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211105 |
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