CN112646167B - Flame-retardant polyether polyol for high-resilience polyurethane foam and preparation method thereof - Google Patents
Flame-retardant polyether polyol for high-resilience polyurethane foam and preparation method thereof Download PDFInfo
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- CN112646167B CN112646167B CN202110074545.7A CN202110074545A CN112646167B CN 112646167 B CN112646167 B CN 112646167B CN 202110074545 A CN202110074545 A CN 202110074545A CN 112646167 B CN112646167 B CN 112646167B
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- 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 64
- 239000003063 flame retardant Substances 0.000 title claims abstract description 64
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 63
- 229920000570 polyether Polymers 0.000 title claims abstract description 63
- 229920005862 polyol Polymers 0.000 title claims abstract description 63
- 150000003077 polyols Chemical class 0.000 title claims abstract description 63
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 31
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 36
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 33
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940072056 alginate Drugs 0.000 claims abstract description 23
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 23
- 229920000615 alginic acid Polymers 0.000 claims abstract description 23
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940083037 simethicone Drugs 0.000 claims abstract description 23
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002472 Starch Polymers 0.000 claims abstract description 22
- 235000019698 starch Nutrition 0.000 claims abstract description 22
- 239000008107 starch Substances 0.000 claims abstract description 22
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 21
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 21
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 21
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 21
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 235000010407 ammonium alginate Nutrition 0.000 claims description 4
- 239000000728 ammonium alginate Substances 0.000 claims description 4
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 235000010408 potassium alginate Nutrition 0.000 claims description 3
- 239000000737 potassium alginate Substances 0.000 claims description 3
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 239000000779 smoke Substances 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229920002545 silicone oil Polymers 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 229920000881 Modified starch Polymers 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BICAGYDGRXJYGD-UHFFFAOYSA-N hydrobromide;hydrochloride Chemical compound Cl.Br BICAGYDGRXJYGD-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
Abstract
The invention discloses a flame-retardant polyether polyol for high-resilience polyurethane foam, which particularly relates to the technical field of polyether polyol and comprises the following raw materials: propylene oxide, ethylene oxide, ammonium phosphate, melamine, simethicone, tetrabromobisphenol a, salicyl alcohol, starch, alginate and a catalyst. The invention strictly controls the content of tetrabromobisphenol A, can effectively reduce harmful gases generated in the processing and using process, contains more phosphorus and nitrogen flame-retardant elements, does not generate harmful gases in the using process, and is a silicon flame-retardant element, so that the dimethyl silicone oil can be polymerized with propylene oxide and ethylene oxide and can be penetrated with each other, a carbon layer is formed on the surface of polyether polyol, the generation of smoke and the development of flame can be prevented, and the high-elasticity polyether polyol can be prepared by ring-opening polymerization with propylene oxide and ethylene oxide through the addition of salicyl alcohol and a catalyst, thereby generating the polyurethane foam with high rebound.
Description
Technical Field
The invention relates to the technical field of polyether polyol, in particular to flame-retardant polyether polyol for high-resilience polyurethane foam and a preparation method thereof.
Background
The rigid polyurethane foam has the advantages of good heat insulation effect, high strength, weather resistance, firm adhesion and the like, and is widely used in the fields of building outer wall heat insulation materials, household appliance heat insulation materials, shipbuilding aviation heat insulation materials and the like. The existing polyurethane hard foam flame-retardant technology mainly comprises an additive flame retardant, and when the additive flame retardant is used in the polyurethane hard foam, the additive flame retardant often migrates to the surface over time to cause precipitation, so that the flame retardant performance of the polyurethane hard foam is reduced or even not flame retardant. When the flame-retardant polyether in the prior art is applied to polyurethane rigid foam, unstable phenomena such as prolonged curing time of foam, large consumption of catalyst, shrinkage, cracking, burning, reduced heat conductivity coefficient and compressive strength of the foam are caused.
At present, two modes of flame retardant treatment are adopted for polyurethane hard foam: one method is to add a flame retardant, such as melamine or melamine derivatives, which are nitrogen-rich compounds, which are most commonly used as additive flame retardants because they have a six-membered heterocyclic structure with excellent thermal stability. Although the flame retardant performance of the polyurethane rigid foam can be improved to a certain extent by the additive flame retardance, the problem of flame retardance failure is caused by dialysis migration of the flame retardant. In the other method, in the process of synthesizing polyether polyol by taking polyol or organic amine as an initiator and reacting with propylene oxide (or derivatives thereof) at high temperature and high pressure, flame retardant elements (such as phosphorus, halogen, nitrogen and the like) or flame retardant structures (such as large heterocycle) are introduced into the molecular chain structure of the polyether polyol through modification or grafting. The halogen-containing flame-retardant polyether polyol is most widely used, but has the serious defects of high raw material price, high production danger, high smoke toxicity and the like.
Most of the existing polyurethane foam flame-retardant treatment is to synthesize polyether polyol by modifying or grafting flame-retardant elements, the most widely used halogen flame-retardant elements are halogen flame-retardant elements, and the halogen flame-retardant element polyether polyol is easy to produce substances such as hydrogen chloride and hydrogen bromide which damage central nerves of human bodies in the processing and using processes, so that a large amount of toxic black dense smoke is easy to produce in the combustion process, and the polyurethane foam produced by the halogen flame-retardant element polyether polyol has insufficient elasticity and cannot meet the use demands of people.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a flame-retardant polyether polyol for high-resilience polyurethane foam and a preparation method thereof, and the problems to be solved by the invention are as follows: how to improve the flame retardance of polyether polyol and the elasticity of polyurethane foam produced by flame-retardant polyether polyol.
In order to achieve the above purpose, the present invention provides the following technical solutions: the flame-retardant polyether polyol for the high-resilience polyurethane foam comprises the following raw materials in parts by weight: 500-800 parts of propylene oxide, 400-600 parts of ethylene oxide, 40-60 parts of ammonium phosphate, 2-10 parts of melamine, 20-40 parts of simethicone, 2-10 parts of tetrabromobisphenol A, 10-20 parts of salicyl alcohol, 15-25 parts of starch, 1-5 parts of alginate and 0.5-1 part of catalyst.
In a preferred embodiment, the composition comprises the following raw materials in parts by weight: 600-700 parts of propylene oxide, 450-550 parts of ethylene oxide, 45-55 parts of ammonium phosphate, 5-7 parts of melamine, 25-35 parts of simethicone, 5-7 parts of tetrabromobisphenol A, 14-16 parts of salicyl alcohol, 18-22 parts of starch, 2-4 parts of alginate and 0.7-0.8 part of catalyst.
In a preferred embodiment, the composition comprises the following raw materials in parts by weight: 650 parts of propylene oxide, 500 parts of ethylene oxide, 50 parts of ammonium phosphate, 6 parts of melamine, 30 parts of simethicone, 6 parts of tetrabromobisphenol A, 15 parts of salicyl alcohol, 20 parts of starch, 3 parts of alginate and 0.75 part of catalyst.
In a preferred embodiment, the alginate is one of sodium alginate, potassium alginate and ammonium alginate and the catalyst is a mixture of an alkali metal catalyst, a double metal cyanide complex catalyst and a phosphazene catalyst.
In a preferred embodiment, the mass ratio of the alkali metal catalyst, the double metal cyanide complex catalyst and the phosphazene catalyst is 1:0.1-0.5:1-2, wherein the alkali metal catalyst is potassium hydroxide, the double metal cyanide complex catalyst is MMC catalyst, and the phosphazene catalyst is hexachlorocyclotrilin nitrile.
The invention also provides a preparation method of the flame-retardant polyether polyol for the high-resilience polyurethane foam, which comprises the following specific preparation steps:
step one: weighing the raw materials according to the weight parts, putting the weighed starch and alginate into a reaction container, heating to 60-70 ℃ by using nitrogen replacement while stirring, and preserving heat for 15-25min at 60-70 ℃;
step two: adding ammonium phosphate, melamine, simethicone and tetrabromobisphenol A into the reaction container in the first step, uniformly stirring, curing, adding part of ethylene oxide and propylene oxide after curing, and uniformly stirring to obtain a product A for later use;
step three: placing salicyl alcohol and a catalyst into a reaction kettle, replacing with nitrogen, heating to 80-90 ℃, then adding part of ethylene oxide and propylene oxide for polymerization reaction, curing after the reaction is finished, and obtaining a product B;
step four: and (3) mixing the product A obtained in the step (II) and the product B obtained in the step (III), and carrying out adsorption, drying and filtration after uniformly mixing to obtain the flame-retardant polyether polyol.
In a preferred embodiment, the second curing temperature is 115-130℃and the curing time is 2-4 hours, and the ethylene oxide and propylene oxide are added in the second step in an amount of two thirds of the total amount.
In a preferred embodiment, the ethylene oxide and propylene oxide are added in the step three in an amount of one third of the total amount.
In a preferred embodiment, the curing temperature in the third step is 100-120 ℃, the curing time is 2-4 hours, and the monomers are removed in vacuum for 1-1.5 hours after curing.
In a preferred embodiment, the adsorption mode of the step four is silicate adsorption, and the drying is vacuum nitrogen-blowing drying at 100-110 ℃ until the moisture is less than or equal to 0.2%.
The invention has the technical effects and advantages that:
1. according to the flame-retardant polyether polyol for the high-resilience polyurethane foam, which is prepared by adopting the raw material formula, ammonium phosphate, simethicone, tetrabromobisphenol A, salicyl alcohol and a catalyst are added into propylene oxide and ethylene oxide, tetrabromobisphenol A is a halogen flame retardant, the content of tetrabromobisphenol A is strictly controlled, harmful gas generated in the processing and using processes can be effectively reduced, the flame-retardant effect of the polyether polyol is assisted by the ammonium phosphate and the simethicone, more phosphorus and nitrogen flame-retardant elements are contained in the ammonium phosphate, harmful gas is not generated in the using process, the simethicone is a silicon flame-retardant element, the simethicone can be polymerized with propylene oxide and ethylene oxide mutually, and can be penetrated mutually, a carbon layer is formed on the surface of the polyether polyol, so that the critical oxygen index can be improved, the flame ship speed can be reduced, the generation of smoke and the development of flame can be prevented, the better flame-retardant effect can be achieved, and the high-resilience polyether polyol can be prepared by the addition of the salicyl alcohol and the catalyst, and the propylene oxide through the ring-opening polymerization, so that the high-resilience polyurethane foam is generated;
2. according to the invention, the starch and the alginate are added, and the alginate and the starch are firstly mixed during processing, so that the alginate is used for modifying the starch, the flame retardant property of the modified starch on the polyether polyol is obviously improved, and the adhesive property of the polyether polyol is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the invention provides a flame-retardant polyether polyol for high-resilience polyurethane foam, which comprises the following raw materials in parts by weight: 500 parts of propylene oxide, 400 parts of ethylene oxide, 40 parts of ammonium phosphate, 2 parts of melamine, 20 parts of simethicone, 2 parts of tetrabromobisphenol A, 10 parts of salicyclic alcohol, 15 parts of starch, 1 part of alginate and 0.5 part of catalyst.
In a preferred embodiment, the alginate is sodium alginate and the catalyst is a mixture of an alkali metal catalyst, a double metal cyanide complex catalyst and a phosphazene catalyst.
In a preferred embodiment, the mass ratio of the alkali metal catalyst, the double metal cyanide complex catalyst and the phosphazene catalyst is 1:0.1-0.5:1-2, wherein the alkali metal catalyst is potassium hydroxide, the double metal cyanide complex catalyst is MMC catalyst, and the phosphazene catalyst is hexachlorocyclotrilin nitrile.
The invention also provides a preparation method of the flame-retardant polyether polyol for the high-resilience polyurethane foam, which comprises the following specific preparation steps:
step one: weighing the raw materials according to the weight parts, putting the weighed starch and alginate into a reaction container, heating to 65 ℃ by using nitrogen substitution while stirring, and preserving heat for 20min at 65 ℃;
step two: adding ammonium phosphate, melamine, simethicone and tetrabromobisphenol A into the reaction container in the first step, uniformly stirring, curing, adding part of ethylene oxide and propylene oxide after curing, and uniformly stirring to obtain a product A for later use;
step three: placing salicyl alcohol and a catalyst into a reaction kettle, replacing with nitrogen, heating to 85 ℃, then adding part of ethylene oxide and propylene oxide for polymerization reaction, curing after the reaction is finished, and obtaining a product B;
step four: and (3) mixing the product A obtained in the step (II) and the product B obtained in the step (III), and carrying out adsorption, drying and filtration after uniformly mixing to obtain the flame-retardant polyether polyol.
In a preferred embodiment, the second curing temperature is 125℃and the curing time is 3 hours, and the ethylene oxide and propylene oxide are added in the second step in an amount of two thirds of the total amount.
In a preferred embodiment, the ethylene oxide and propylene oxide are added in the step three in an amount of one third of the total amount.
In a preferred embodiment, the curing temperature in the third step is 110 ℃, the curing time is 3 hours, and the monomers are removed in vacuum for 1 hour after curing.
In a preferred embodiment, the adsorption mode of the step four is silicate adsorption, and the drying is vacuum nitrogen-blowing drying at 105 ℃ until the moisture is less than or equal to 0.2%.
Example 2:
unlike example 1, the flame retardant polyether polyol for high resilience polyurethane foam comprises the following raw materials in parts by weight: 650 parts of propylene oxide, 500 parts of ethylene oxide, 50 parts of ammonium phosphate, 6 parts of melamine, 30 parts of simethicone, 6 parts of tetrabromobisphenol A, 15 parts of salicyl alcohol, 20 parts of starch, 3 parts of alginate and 0.75 part of catalyst.
Example 3:
unlike examples 1-2, the flame retardant polyether polyol for high resilience polyurethane foam comprises the following raw materials in parts by weight: 800 parts of propylene oxide, 600 parts of ethylene oxide, 60 parts of ammonium phosphate, 10 parts of melamine, 40 parts of simethicone, 10 parts of tetrabromobisphenol A, 20 parts of salicyclic alcohol, 25 parts of starch, 5 parts of alginate and 1 part of catalyst.
The polyether polyols produced in examples 1, 2 and 3 above were selected as test group 1, 2 and 3, respectively, and the critical oxygen index and reaction time of the polyether polyols were tested according to GB2406-1993 using commercially available ordinary polyether polyols as control groups, and the tensile strength of the selected polyether polyols was tested. The measurement results are shown in Table I:
| critical oxygen index (DOI) | Reaction time(s) | Tensile Strength (KPa) | |
| Experiment group 1 | 27.8% | 33 | 15.2 |
| Experiment group 2 | 28.9% | 34 | 15.8 |
| Experiment group 3 | 28.3% | 35 | 15.4 |
| Control group | 24.6% | 60 | 13 |
List one
As can be seen from the table, the critical oxygen index and the tensile strength of the polyether polyol produced by the invention are higher than those of the conventional polyether polyol, the ammonium phosphate, the simethicone, the tetrabromobisphenol A, the salicyl alcohol and the catalyst are added into the propylene oxide and the ethylene oxide, the tetrabromobisphenol A is a halogen flame retardant, the content of the tetrabromobisphenol A is strictly controlled, the harmful gas generated in the processing and using process can be effectively reduced, the flame retardant effect of the polyether polyol is assisted by the ammonium phosphate and the simethicone, the ammonium phosphate contains more phosphorus and nitrogen flame retardant elements, the harmful gas can not be generated in the using process, the simethicone is a silicon flame retardant element, the simethicone can be mutually polymerized with the propylene oxide and the ethylene oxide, and a carbon layer is formed on the surface of the polyether polyol, the smoke generation and the flame development can be prevented, the better flame retardant effect is achieved, the high-resilience polyether polyol is prepared by the addition of the salicyl alcohol and the catalyst, and the propylene oxide can be subjected to ring-opening polymerization to the ring-opening polymerization to generate the high-resilience polyurethane, and the high-resilience polyurethane foam is obtained.
Example 4:
the invention provides a flame-retardant polyether polyol for high-resilience polyurethane foam, which comprises the following raw materials in parts by weight: 650 parts of propylene oxide, 500 parts of ethylene oxide, 50 parts of ammonium phosphate, 6 parts of melamine, 30 parts of simethicone, 6 parts of tetrabromobisphenol A, 15 parts of salicyl alcohol, 20 parts of starch and 0.75 part of catalyst.
In a preferred embodiment, the catalyst is a mixture of an alkali metal catalyst, a double metal cyanide complex catalyst and a phosphazene catalyst.
In a preferred embodiment, the mass ratio of the alkali metal catalyst, the double metal cyanide complex catalyst and the phosphazene catalyst is 1:0.1-0.5:1-2, wherein the alkali metal catalyst is potassium hydroxide, the double metal cyanide complex catalyst is MMC catalyst, and the phosphazene catalyst is hexachlorocyclotrilin nitrile.
The invention also provides a preparation method of the flame-retardant polyether polyol for the high-resilience polyurethane foam, which comprises the following specific preparation steps:
step one: weighing the raw materials according to the weight parts; adding weighed ammonium phosphate, starch, melamine, simethicone and tetrabromobisphenol A into a reaction container, uniformly stirring, curing, adding part of ethylene oxide and propylene oxide after curing is finished, and uniformly stirring to obtain a product A for later use;
step two: placing salicyl alcohol and a catalyst into a reaction kettle, replacing with nitrogen, heating to 85 ℃, then adding part of ethylene oxide and propylene oxide for polymerization reaction, curing after the reaction is finished, and obtaining a product B;
step three: and (3) mixing the product A obtained in the step (II) and the product B obtained in the step (III), and carrying out adsorption, drying and filtration after uniformly mixing to obtain the flame-retardant polyether polyol.
In a preferred embodiment, the first curing temperature is 125℃and the curing time is 3 hours, and the ethylene oxide and propylene oxide are added in the second step in an amount of two thirds of the total amount.
In a preferred embodiment, the ethylene oxide and propylene oxide are added in the step two in an amount of one third of the total.
In a preferred embodiment, the curing temperature in the second step is 110 ℃, the curing time is 3 hours, and the monomers are removed in vacuum for 1 hour after curing.
In a preferred embodiment, the adsorption mode of the step three is silicate adsorption, and the drying is vacuum nitrogen-blowing drying at 105 ℃ until the moisture is less than or equal to 0.2%.
Example 5:
unlike example 2, the alginate was potassium alginate.
Example 6:
unlike example 2, the alginate was ammonium alginate.
The polyether polyols produced in example 2, example 4, example 5 and example 6 were selected and measured for critical oxygen index, reaction time and tensile strength, respectively, as shown in Table II:
| critical oxygen index (DOI) | Reaction time(s) | Tensile Strength (KPa) | |
| Example 2 | 28.9% | 34 | 15.8 |
| Example 4 | 26.3 | 42 | 15.3 |
| Example 5 | 28.7 | 33 | 15.7 |
| Example 6 | 29.2 | 34 | 15.8 |
Watch II
As can be seen from Table II, in the invention, the starch is not modified by the alginate in the embodiment 4, the critical oxygen index of the polyether polyol produced in the embodiment 4 is obviously lower than that of the polyether polyols produced in the embodiments 2, 5 and 6, and the tensile strength of the polyether polyol is not greatly changed, which means that the alginate and the starch are firstly mixed, so that the modified starch can be used for modifying the starch, the flame retardant property of the modified starch on the polyether polyol is obviously improved, and the adhesive property of the polyether polyol is improved, and the comparison of the embodiment 2, 5 and 6 shows that when the ammonium alginate is selected for modifying the starch, the critical oxygen index of the polyether polyol is higher, and the flame retardant effect of the polyether polyol is better.
Finally: the foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A flame retardant polyether polyol for high resilience polyurethane foam, characterized in that: the composite material comprises the following raw materials in parts by weight: 500-800 parts of propylene oxide, 400-600 parts of ethylene oxide, 40-60 parts of ammonium phosphate, 2-10 parts of melamine, 20-40 parts of simethicone, 2-10 parts of tetrabromobisphenol A, 10-20 parts of salicyl alcohol, 15-25 parts of starch, 1-5 parts of alginate and 0.5-1 part of catalyst;
the preparation method of the flame-retardant polyether polyol for the high-resilience polyurethane foam comprises the following specific preparation steps:
step one: weighing the raw materials according to the weight parts, putting the weighed starch and alginate into a reaction container, heating to 60-70 ℃ by using nitrogen replacement while stirring, and preserving heat for 15-25min at 60-70 ℃;
step two: adding ammonium phosphate, melamine, simethicone and tetrabromobisphenol A into the reaction container in the first step, uniformly stirring, curing, adding part of ethylene oxide and propylene oxide after curing, and uniformly stirring to obtain a product A for later use;
step three: placing salicyl alcohol and a catalyst into a reaction kettle, replacing with nitrogen, heating to 80-90 ℃, then adding part of ethylene oxide and propylene oxide for polymerization reaction, curing after the reaction is finished, and obtaining a product B;
step four: and (3) mixing the product A obtained in the step (II) and the product B obtained in the step (III), and carrying out adsorption, drying and filtration after uniformly mixing to obtain the flame-retardant polyether polyol.
2. A flame retardant polyether polyol for high resilience polyurethane foam according to claim 1, wherein: the composite material comprises the following raw materials in parts by weight: 600-700 parts of propylene oxide, 450-550 parts of ethylene oxide, 45-55 parts of ammonium phosphate, 5-7 parts of melamine, 25-35 parts of simethicone, 5-7 parts of tetrabromobisphenol A, 14-16 parts of salicyl alcohol, 18-22 parts of starch, 2-4 parts of alginate and 0.7-0.8 part of catalyst.
3. A flame retardant polyether polyol for high resilience polyurethane foam according to claim 1, wherein: the composite material comprises the following raw materials in parts by weight: 650 parts of propylene oxide, 500 parts of ethylene oxide, 50 parts of ammonium phosphate, 6 parts of melamine, 30 parts of simethicone, 6 parts of tetrabromobisphenol A, 15 parts of salicyl alcohol, 20 parts of starch, 3 parts of alginate and 0.75 part of catalyst.
4. A flame retardant polyether polyol for high resilience polyurethane foam according to claim 1, wherein: the alginate is one of sodium alginate, potassium alginate and ammonium alginate, and the catalyst is a mixture of an alkali metal catalyst, a double metal cyanide complex catalyst and a phosphazene catalyst.
5. A flame retardant polyether polyol for high resilience polyurethane foam according to claim 4, wherein: the mass ratio of the alkali metal catalyst to the double metal cyanide complex catalyst to the phosphazene catalyst is 1:0.1-0.5:1-2, wherein the alkali metal catalyst is potassium hydroxide, the double metal cyanide complex catalyst is MMC catalyst, and the phosphazene catalyst is hexachlorocyclotrilin nitrile.
6. A flame retardant polyether polyol for high resilience polyurethane foam according to claim 1, wherein: the second curing temperature is 115-130 ℃, the curing time is 2-4h, and the addition amount of ethylene oxide and propylene oxide in the second curing step is two thirds of the total amount.
7. A flame retardant polyether polyol for high resilience polyurethane foam according to claim 1, wherein: the addition amount of ethylene oxide and propylene oxide in the step three is one third of the total amount.
8. A flame retardant polyether polyol for high resilience polyurethane foam according to claim 1, wherein: and in the third step, the curing temperature is 100-120 ℃, the curing time is 2-4h, and the monomers are removed in vacuum for 1-1.5h after curing is finished.
9. A flame retardant polyether polyol for high resilience polyurethane foam according to claim 1, wherein: the adsorption mode in the fourth step is silicate adsorption, and the drying is vacuum nitrogen-blowing drying at 100-110 ℃ until the moisture is less than or equal to 0.2%.
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