CN114409870A - Polyurethane foam material for high-flame-retardant vehicle seat prepared based on modified isocyanate - Google Patents
Polyurethane foam material for high-flame-retardant vehicle seat prepared based on modified isocyanate Download PDFInfo
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- CN114409870A CN114409870A CN202210109280.4A CN202210109280A CN114409870A CN 114409870 A CN114409870 A CN 114409870A CN 202210109280 A CN202210109280 A CN 202210109280A CN 114409870 A CN114409870 A CN 114409870A
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- polyol
- polyurethane foam
- modified isocyanate
- flame
- retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- 239000012948 isocyanate Substances 0.000 title claims abstract description 56
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 53
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 35
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 56
- 150000003077 polyols Chemical class 0.000 claims abstract description 55
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 239000006260 foam Substances 0.000 claims abstract description 20
- 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 claims description 50
- 239000000126 substance Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 229920002545 silicone oil Polymers 0.000 claims description 11
- 239000004088 foaming agent Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- -1 polydimethylsiloxane Polymers 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 238000006757 chemical reactions by type Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002666 chemical blowing agent Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 33
- 238000012360 testing method Methods 0.000 abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000008094 contradictory effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DKRWGRQBYLWNKR-UHFFFAOYSA-N OC(O)(O)[PH2]=O Chemical compound OC(O)(O)[PH2]=O DKRWGRQBYLWNKR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000004643 cyanate ester Substances 0.000 description 2
- 150000004826 dibenzofurans Chemical class 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 231100000021 irritant Toxicity 0.000 description 2
- 239000002085 irritant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000012970 tertiary amine catalyst Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
-
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a polyurethane foam material for a high-flame-retardant vehicle seat, which is prepared based on modified isocyanate, and belongs to the technical field of polyurethane materials. The proportion of the polyether polyol and the modified isocyanate in the passenger car seat combination is as follows: (110-150) oxygen index of a passenger car seat produced by mass ratio, wherein the oxygen index of the 26.3% foam TVOC is 35 mu gC/g, the odor grade (80 ℃) is 3.5, the formaldehyde emission is 6.3mg/kg, and the fog test is 3.68 mg.
Description
Technical Field
The invention relates to a polyurethane foam material for a high-flame-retardant vehicle seat, which is prepared based on modified isocyanate, and belongs to the technical field of polyurethane materials.
Background
The annual total production of global polyurethane is about 2000 million tons, the national production accounts for about 55 percent of the world production, the product which is most widely applied and has the largest use amount is a foam product and accounts for about 40 percent of the product. The polyurethane foam products with the largest consumption are soft sponges for seats of vehicles such as mattresses, sofas, automobiles and the like and hard foams for heat preservation of buildings such as refrigerators, refrigeration houses, houses and the like, and the polyurethane foams in many application fields need to have good flame retardant capability and good environmental protection performances such as smell and TVOC.
On the one hand, flame retardancy has become a bottleneck problem for polyurethane foams used in the fields of passenger cars, trains, public homes, etc. Polyurethane foam is inherently flammable as a foam if a flame retardant is not added. The combustion characteristic of the GB38262-2019 passenger car interior material is implemented in 7-1.7.2020, and the horizontal combustion of the polyurethane seat is regulated to be A0 grade, and the vertical combustion is less than or equal to 100 mm/min; the polyurethane thermal insulation noise reduction material needs oxygen index to meet 25 percent and 28 percent besides horizontal/vertical combustion. In the field of trains: the oxygen indexes of the flame retardant performance of the seats in high-speed rail and common trains respectively meet the requirements of 28 percent (the technical conditions of flame retardant of the built-in material for the motor train unit 2010 TBT 3237-.
Polyurethane foam is formed by reacting isocyanate and polyol two components, and most of the research for improving the flame retardance of polyurethane foam plastics at present focuses on the polyol component, and the following methods are mainly adopted:
1. the problems of strong plasticizing effect, flame retardant migration and the like exist when a phosphorus or halogen liquid flame retardant is added into the polyol component;
2. the development of the polyhydric alcohol with flame retardant elements such as phosphorus, nitrogen, halogen and the like has the problems of poor physical properties, undesirable flame retardant effect and high cost;
3. the flame retardant is realized by adding solid flame retardants such as expandable graphite, aluminum hydroxide and the like, and the product and process range is narrow.
In the first method, the smoke amount of the halogen flame retardant is large, the released hydrogen halide is corrosive or irritant, toxic carcinogenic substances such as polybrominated dioxin and polybrominated dibenzofuran can be generated, most halogen organic substances are environmental hormone substances, and the organic substances can induce organism mutation, influence the immune system, the endocrine system and the reproductive system of a human body and influence the normal metabolism of the human body.
And in the second method, novel polyether polyol is developed, and halogen is introduced to a molecular chain by a chemical grafting method to improve the flame retardance. However, the novel polyether can hinder the reaction of-OH and-NCO to a certain extent in the process of forming polyurethane foam, so that the formed foam hardness is increased, the elongation at break is obviously reduced, and the physical properties are poorer. Affecting the experience of the passengers.
In the third method, the addition of the expandable graphite and the aluminum hydroxide can improve the overall viscosity of the polyether component, so that quality risks such as uneven mixing and the like easily occur in the production process, and meanwhile, the solid powder can abrade a mixing chamber of a high-pressure foaming machine, so that the process surface is narrow.
On the other hand, environmental issues such as TVOC and odor are another bottleneck problem in polyurethane flame retardant foams for enclosed space applications such as in vehicles. For example, chinese article 2018.6.23 reports that "the rejuvenate number frequently suffers complaints of peculiar smell in the car, the medium-iron total: and (5) carrying out self-checking and strictly controlling raw material purchasing. Flame retardance and environmental protection are mutually contradictory indexes, and the flame retardant is one of the factors which have the greatest contribution to TVOC and smell.
The difficulty of the problem is that high flame retardance and low TVOC and low odor are two mutually contradictory indexes, because the physically added flame retardant is one of the factors which most contribute to the TVOC and odor of the flame-retardant soft foam.
At present, in order to meet the requirement that the oxygen index of a passenger car seat for a high-speed rail respectively reaches 28% (technical conditions for flame-retardant materials for a TBT 3237-.
At present, the polyurethane foam material which can perfectly solve the problems that the vehicle seat simultaneously satisfies the conditions that the oxygen index is more than or equal to 26 percent, the TVOC is less than or equal to 50 mu gC/g, the odor grade (80 ℃) is less than or equal to 3.5, the formaldehyde emission is less than or equal to 10mg/kg, and the fog test is less than or equal to 5mg is not available.
Therefore, there is a need for a polyurethane foam for high flame retardancy vehicle seats based on modified isocyanates which solves the above-mentioned technical problems.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a polyurethane foam material for a high-flame-retardant vehicle seat, which is prepared based on modified isocyanate and can solve the technical problems, wherein the oxygen index of the passenger car seat produced by the high-flame-retardant polyurethane foam material is 26.3%, the TVOC is 35 mu gC/g, the odor grade (80 ℃) is 3.5, the formaldehyde emission is 6.3mg/kg, and the fog test is 3.68 mg.
One of the objectives of the present invention is to provide a polyurethane foam material for high flame retardant vehicle seats, which is prepared based on modified isocyanate and can solve the above technical problems, wherein the polyurethane foam material is characterized by comprising the modified isocyanate and polyol, the mass ratio of the modified isocyanate and the polyol is (110) and 150), and the chemical structural formula of the modified isocyanate is as follows:
the P content of the modified isocyanate was 4.7%, the N content was 12.7%, and the NCO% content was 19%.
The polyol comprises: polyether polyol, polymer polyol, a chemical foaming agent and a reactive auxiliary agent; the polyether polyol accounts for 55-60% of the total weight of the polyol component; the polymer polyol comprises 35-40% of the total weight of the polyol component; the chemical foaming agent accounts for 3-4% of the total weight of the polyol component; the reactive auxiliary agent accounts for 0.8-1.2% of the total weight of the polyol component.
The polyether polyol is high-activity polyether which takes glycerol as an initiator, propylene oxide and ethylene oxide as polymerization monomers and is subjected to end capping by ethylene oxide;
the polymer polyol is formed by graft copolymerization of general polyether, styrene and acrylonitrile; such as polymer polyol POP3081 from east major ltd, blue star, Shandong.
The chemical foaming agent is water;
the reactive auxiliary agent comprises two components of a foam surfactant and a reactive catalyst, and the mass ratio of the surfactant to the reactive catalyst is 1 (0.8-2.6).
The foam surfactant is silicone oil, and the silicone oil is polydimethylsiloxane;
the reaction type catalyst is a tertiary amine catalyst; DABCO-T (winning specialty Chemicals (Shanghai) Co., Ltd.), ZF-10 (Henscman), cat8154 (catalyst, winning specialty Chemicals (Shanghai) Co., Ltd.) are preferred.
The invention also aims to provide a synthetic method of the polyurethane foam material for the high-flame-retardant vehicle seat, which is prepared on the basis of the modified isocyanate, and is characterized in that the polyurethane foam material is prepared by polymerizing the modified isocyanate and a polyol component, wherein the modified isocyanate is obtained by polymerizing trihydroxymethyl phosphine oxide and TDI, and the reaction equation is as follows:
the invention aims to ensure that the passenger car seat simultaneously meets the following requirements: the oxygen index was 26.3%, TVOC was 35. mu. gC/g, odor grade (80 ℃) was 3.5, formaldehyde emission was 6.3mg/kg, and fog test was 3.68 mg. The modified isocyanate is used for replacing the conventional isocyanate TDI or MDI, the content of P of the modified isocyanate is 4.7 percent, and the phosphorus content of the foam obtained by combining polyether polyol in a proportion of (110-; no additive physical flame retardant and other plasticizer are added in the system, so that a relatively low fog test value is obtained. Meanwhile, melamine modified flame-retardant polyether is not needed in the system, and good formaldehyde emission data is obtained.
The polyurethane foam material for the high-flame-retardant vehicle seat, which is prepared based on the modified isocyanate, can be added with no physical flame retardant, so that the aim of preventing the flame retardant from reducing the environmental protection index while greatly improving the flame retardance of the polyurethane foam is fulfilled. Meanwhile, the polyurethane foam developed by the invention does not contain halogen, has small combustion smoke quantity, does not release corrosive or irritant hydrogen halide gas, does not generate toxic carcinogenic substances of polybrominated dioxin and polybrominated dibenzofuran, and does not contain an environmental hormone substance of a halogen organic substance, thereby avoiding the long-term influence of the material on the environment.
The polyurethane foam material for the high-flame-retardant vehicle seat, which is prepared based on the modified isocyanate and can solve the technical problems, has the shape of a final product which depends on the shape of a mould used in production, and can be used for producing seat cushions, headrests, backs and other components with various patterns, shapes and sizes by using different moulds.
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.
Example 1
The polyurethane foam material for the high-flame-retardant vehicle seat, which is prepared based on the modified isocyanate and can solve the technical problems, comprises the modified isocyanate and the polyol, wherein the mass ratio of the modified isocyanate to the polyol is (110) -150), and the modified isocyanate has the following chemical structural formula:
the P content of the modified isocyanate was 4.7%, the N content was 12.7%, and the NCO% content was 19%.
The polyurethane foam material for the high-flame-retardant vehicle seat, which is prepared based on the modified isocyanate, is prepared by polymerizing the modified isocyanate and a polyol component, wherein the modified isocyanate is obtained by polymerizing trihydroxymethyl phosphine oxide and TDI, and the reaction equation is as follows:
the reference synthesis process of the modified isocyanate comprises the following steps:
(1) heating the reaction kettle to 48-52 ℃;
(2) according to the following tris (hydroxymethyl) phosphine oxide (available from Hubei Xingsheng chemical group Ltd.): adding all TDI with the molar ratio of (4-8) first, and then adding all the tris (hydroxymethyl) phosphine oxide at a constant speed;
(3) heating the reaction kettle to 78-82 ℃, and then reacting for 1.9-2.2 h;
(4) removing unreacted excessive TDI by using a thin film evaporator;
(5) then cooling the reaction kettle to 48-52 ℃, taking out of the kettle and packaging to obtain a product with the P content of 4.7%, the N content of 12.7% and the NCO% content of 19%.
The polyhydric alcohol includes: polyether polyol, polymer polyol, a chemical foaming agent and a reactive auxiliary agent; the polyether polyol accounts for 55-60% of the total weight of the polyol component; the polymer polyol comprises 35-40% of the total weight of the polyol component; the chemical foaming agent accounts for 3-4% of the total weight of the polyol component; the reactive auxiliary agent accounts for 0.8-1.2% of the total weight of the polyol component.
Polyether polyol is a highly reactive polyether which uses glycerin as an initiator, propylene oxide and ethylene oxide as polymerization monomers and is capped by ethylene oxide, such as F3135 from Wanhua chemical Co., Ltd, and 330NG from Shandong Lanxingdong Co., Ltd.
The polymer polyol is prepared by graft copolymerization of general polyether, styrene and acrylonitrile, and has the principle that the styrene and the acrylonitrile are introduced into the general polyether, so that the polymer polyol has the advantages of low toxicity, high processing tolerance, high yellowing resistance and the like, and the excellent polymer polyol is obtained by grafting the co-polystyrene, the acrylonitrile and other nano-scale powder and the synergistic effect of macromolecular dispersoid under the condition of ensuring the activity of the general polyether. Such as polymer polyol POP3081 from east major ltd, blue star, Shandong.
The chemical foaming agent is mainly water, can effectively participate in the reaction of isocyanate, and improves the hard chain component in the foam.
The reactive auxiliary agent comprises two components of a foam surfactant and a reactive catalyst. And the mass ratio of the surfactant to the reactive catalyst is 1 (0.8-2.6).
The foam surfactant is silicone oil, the silicone oil is polydimethylsiloxane, and the silicone oil can adopt 8715 silicone oil produced by Shanghai Special chemistry (Shanghai) Co., Ltd.) or C2525 silicone oil produced by Dow Corning Co., Ltd.;
the reaction type catalyst is a tertiary amine catalyst; DABCO-T (winning specialty Chemicals (Shanghai) Co., Ltd.), ZF-10 (Henscman), cat8154 (catalyst, winning specialty Chemicals (Shanghai) Co., Ltd.) are preferred.
Test examples
The formulation of the combined polyether polyol of this test example is as follows:
| name (R) | Weight percent of |
| F3135 (polyether polyol, Wanhua chemical group Co., Ltd.) | 60 |
| POP3081 (poly)Compound polyol, Shandong Lanxing Dongda Co., Ltd.) | 35 |
| Chemical foaming agent | 3.5 |
| B8715 Silicone oil (Silicone oil, Shanghai specialty Chemicals (Shanghai) Co., Ltd.) | 0.6 |
| DABCO-T (Yingchuang specialty Chemicals (Shanghai) Co., Ltd.) | 0.3 |
| cat8154 (catalyst, Shanghai specialty Chemicals (Shanghai) Co., Ltd.) | 0.5 |
| ZF-10 (Hensman) | 0.1 |
| Total of | 100 |
Using 100 parts of the above-mentioned combination polyether polyol and the total parts of the isocyanate component and the physical flame retardant component of each test example in the following table, a foamed article was produced by mixing and stirring.
The isocyanate component and the additive-type flame retardant component of each test example were:
the molar amounts of isocyanate groups (-NCO) in test examples 1, 2 and 3 were equal to each other in accordance with the formulation fractions shown in the above tables, and the molar amount of isocyanate groups (-OH) in 100 parts of the combined polyether polyol was 1.05:1, and a little more than 5% of isocyanate groups ensured sufficient reaction.
The flame retardant and environmental protection performance of each test example is tested as follows:
TVOC test standard: the VDA277 of the series, 1995,
odor rating test criteria: the VDA270:1992, the VDA270,
and (3) testing the formaldehyde emission standard: the VDA275:1994, the molecular weight of the polypeptide,
fog test standard: Q/ZK JS 364-,
in the above test examples 1, 2 and 3, the molar number of isocyanate groups (-NCO) in the reaction system was maintained by designing the isocyanate ratio: the ratio of the number of moles of hydroxyl (-OH) groups was 1.05: 1.
Experimental example 2 on the basis of the experimental example 1, the physical flame retardant component TCPP is added, all other things are unchanged, the oxygen index is increased from 19.2% of non-flame-retardant property to 25.7% of flame-retardant property, but at the same time, the TVOC is increased from 38 mu gC/g to 291 mu gC/g, the odor grade (80 ℃) is increased from 3.5 to 4, the formaldehyde emission is increased from 6.9 to 7.3mg/Kg, and the fog is increased from 4.72 to 78mg, so that the environmental protection performance of the material is seriously influenced while the flame-retardant property of the foam is increased by the physical flame retardant component TCPP.
In the case that the index of the experimental example 3 and the index of the experimental example 1 are kept unchanged (the index is 1.05, namely the ratio of the index to the number of moles of hydroxyl (-OH) of the number of moles of isocyanate (-NCO)), the oxygen index is increased from 19.2% of non-flame-retardant to 26.3% of flame-retardant without adding a physical flame retardant, TVOC is 38 mu gC/g and 34 mu gC/g respectively, the odor grade (80 ℃) is 3.5 and 3.5 which are not changed greatly, the formaldehyde release amount is 6.3 and 6.9mg/Kg respectively, the fog test is 3.68 and 4.72mg respectively, the indexes meet the interior decoration standards of vehicles, and the modified isocyanate can achieve the purpose of improving the flame retardance of polyurethane foam and avoiding the reduction of the environmental protection indexes of the flame retardant at the same time. The difficult problem that environmental protection indexes such as high flame retardance, low TVOC and low odor are mutually contradictory is solved.
Test example 3 index and test example 2 with the system index kept constant (index 1.05), test examples 3 and 2 respectively improved the foam flame retardance by the use of modified isocyanate, the addition of the physical flame retardant component TCPP to an oxygen index that was comparable, but the TVOCs of test examples 3 and 2 were 35 μ gC/g, 291 μ gC/g, respectively, and the odor ratings (80 ℃) were 3.5, 4, respectively. The formaldehyde release amounts are respectively 6.3mg/Kg and 7.3mg/Kg, the fog tests are respectively 3.68mg and 78mg, the fog index rises by 20 times, the TVOC index rises by 8 times and seriously exceeds the standard, and the improvement of flame retardance by using the modified isocyanate has obvious advantages in environmental protection compared with the use of the physical flame retardant component TCPP.
In each of the above test examples 3, 4 and 5, 114 parts of isocyanate was used by keeping the amount of isocyanate constant.
Experimental example 5 on the basis of the experimental example 4, the physical flame retardant component TCPP is added, all the other things are unchanged, the oxygen index is increased from 19.5% of non-flame-retardant property to 26.1% of flame-retardant property, but at the same time, the TVOC is increased from 31 mu gC/g to 343 mu gC/g, the odor grade (80 ℃) is increased from 3.5 to 4, the formaldehyde emission is not changed greatly, but the fog is increased from 5.33 to 103mg, and the physical flame retardant component TCPP seriously influences the environmental protection property of the material while increasing the flame-retardant property of the foam.
Under the condition that the indexes of the embodiment 3 and the embodiment 4 keep that the quantity of the cyanate ester is 114 parts, the oxygen index is increased from 19.5 percent of non-flame-retardant to 26.3 percent of flame-retardant without adding a physical flame retardant, simultaneously, the TVOC is 34 mu gC/g and 31 mu gC/g respectively, and the odor grade (80 ℃) is 3.5 and 3.5 respectively, so that the change is not large, which shows that the modified isocyanate can realize the purpose of simultaneously improving the flame retardance of the polyurethane foam and avoiding the reduction of the environmental protection index of the flame retardant. The difficult problem that environmental protection indexes such as high flame retardance, low TVOC and low odor are mutually contradictory is solved.
Experimental example 3 index and experimental example 5 in the case where both the amounts of cyanate ester were maintained at 114 parts, experimental examples 3 and 5 respectively improved the flame retardancy of the foams by using the modified isocyanate compound, adding the physical flame retardant component TCPP until the oxygen indexes differed little, but the TVOCs of experimental examples 3 and 5 were 35 μ gC/g, 343 μ gC/g, respectively, and the odor ratings (80 ℃) were 3.5, 4, respectively. Particularly, TVOC and fog tests are changed by orders of magnitude, which shows that the modified isocyanate compound has obvious advantages in environmental protection compared with the physical flame retardant component TCPP.
Example 6 the modified isocyanate ratio and the polyol weight ratio were 1.5:1, the phosphorus content in the foam system increased to 2.82%, the oxygen index increased to above 28%, and environmental protection indicators such as TVOC, odor rating (80 ℃), formaldehyde emission, and fog experiments remained essentially unchanged, indicating that the modified isocyanate compound of the present invention can achieve the purpose of simultaneously improving the flame retardancy of polyurethane foam while avoiding the reduction of the environmental protection indicators by the flame retardant. The difficult problem that environmental protection indexes such as high flame retardance, low TVOC and low odor are mutually contradictory is solved.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (7)
1. The polyurethane foam material for the high-flame-retardant vehicle seat prepared on the basis of the modified isocyanate is characterized by comprising the modified isocyanate and polyol, wherein the mass ratio of the modified isocyanate to the polyol is (110) -150), and the chemical structural formula of the modified isocyanate is as follows:
the polyol comprises: polyether polyol, polymer polyol, a chemical foaming agent and a reactive auxiliary agent; the polyether polyol accounts for 55-60% of the total weight of the polyol component; the polymer polyol comprises 35-40% of the total weight of the polyol component; the chemical foaming agent accounts for 3-4% of the total weight of the polyol component; the reactive auxiliary agent accounts for 0.8-1.2% of the total weight of the polyol component.
2. Polyurethane foam for high flame retardant vehicle seats made on the basis of modified isocyanates according to claim 1, characterized in that the modified isocyanates have a P content of 4.7%, an N content of 12.7% and an NCO% content of 19%.
3. The polyurethane foam for high flame retardant vehicle seats prepared based on modified isocyanate according to claim 1, wherein the polyether polyol is a high activity polyether having glycerin as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide as a terminal.
4. The polyurethane foam for high flame-retardant vehicle seats prepared based on modified isocyanate according to claim 1, wherein the polymer polyol is a general-purpose polyether graft-copolymerized with styrene and acrylonitrile.
5. Polyurethane foam for high flame retardancy vehicle seats made on the basis of modified isocyanates according to claim 1, characterized in that the chemical blowing agent is water.
6. The polyurethane foam material for high flame-retardant vehicle seats prepared on the basis of the modified isocyanate according to claim 1, wherein the reaction type auxiliary comprises two components of a foam surfactant and a reaction type catalyst, and the mass ratio of the surfactant to the reaction type catalyst is 1 (0.8-2.6).
7. The polyurethane foam for high flame-retardant vehicle seats prepared based on modified isocyanate according to claim 6, wherein the foam surfactant is silicone oil, and the silicone oil is polydimethylsiloxane.
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