CN105131226A - Fire-retardant B1-level polyurethane rigid foam and preparation method thereof - Google Patents
Fire-retardant B1-level polyurethane rigid foam and preparation method thereof Download PDFInfo
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- CN105131226A CN105131226A CN201510630640.5A CN201510630640A CN105131226A CN 105131226 A CN105131226 A CN 105131226A CN 201510630640 A CN201510630640 A CN 201510630640A CN 105131226 A CN105131226 A CN 105131226A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/14—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—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
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- 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
- C08K3/16—Halogen-containing compounds
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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- 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
- C08K3/16—Halogen-containing compounds
- C08K2003/164—Aluminum halide, e.g. aluminium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides fire-retardant B1-level polyurethane rigid foam, which is prepared from a component A and a component B, wherein the component A is prepared from an antiflaming polyether polyol with a nitrogen containing structure, a halogen-free reaction type phosphorus/silicon synergistic flame retardant, a kicker, a foam stabilizer, a physical foaming agent and water, and the component B is polymethylene polyphenyl polyisocyanate. The invention also provides a preparation method of the polyurethane rigid foam, comprising the steps of adding the halogen-free reaction type phosphorus/silicon synergistic flame retardant, the kicker, the foam stabilizer, the physical foaming agent and the water into the antiflaming polyether polyol with the nitrogen containing structure, and stirring and mixing uniformly to obtain the component A; then adding the component B into the component A, quickly stirring for 5 to 20 second, and pouring into a mold for solidification to obtain the fire-retardant B1-level polyurethane rigid foam; the obtained fire-retardant B1-level polyurethane rigid foam has the density of 36.5 to 38.4kg/m<3>, the compression strength of 175 to 185kPa, and a limit oxygen index of 30.4 to 32.5 percent.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of hard polyurethane foam, specifically a kind of difficult combustion B1 level hard polyurethane foam and preparation method thereof.
Background technology
Hard polyurethane foam is called for short hard polyurethane foam, is by polyether glycol, polyester polyol or both composite uses, prepares gained with MDI polyreaction.Without the oxygen index of the hard polyurethane foam of fire-retardant finish about 18, belong to inflammable material.Carrying out fire-retardant finish to it mainly contains two kinds of methods at present: one is additional fire retardant method, as Mg (OH)
2, Al (OH)
3, weisspiessglanz, the organic compound such as mineral compound or Halogen, phosphorus, nitrogen such as ammonium polyphosphate, reach flame retardant effect.Though this kind of fire-retardant mode is simple and convenient, because not yet solving fire retardant in the dispersed of hard polyurethane foam and mortise, thus must introduces fire retardant in a large number, can fire retardation be played.Another kind is structure flame-retarded technology, and this method is incorporated on polyether segment or isocyanic ester by ignition-proof element (phosphorus, chlorine, bromine etc.) or fire-retardant group (phenyl ring, large heterocycle etc.) by chemical bond, and its stability is better, not easily moves.But the structural anti-inflaming polyurethane hard foam material mainly containing halogen-containing (Cl and Br) supplied in the market, this kind of material has that price is high, combustion gases toxicity large more, the smog defect such as heavily, limits it to a great extent and applies.
Based on above background, in the urgent need to developing a kind of structural anti-inflaming polyurethane hard foam material of without halide with low cost, high flame-retardant property.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of difficult combustion B1 level hard polyurethane foam and preparation method thereof, described this difficulty combustion B1 level hard polyurethane foam and preparation method thereof solves the technical problem that hard polyurethane foam price of the prior art is high, combustion gases toxicity is large, smog is heavy.
The invention provides a kind of difficult combustion B1 level hard polyurethane foam, be made up of component A and B component, the weight ratio of component A and B component is 1:(1 ~ 1.7);
Wherein, described component A, is made up of the raw material of following parts by weight:
Containing N structure flame retardant polyether polyol 20 ~ 40 parts,
Non-halogen reacting phosphorus/silicon synergistic fire retardant 5 ~ 10 parts,
Kicker 1 ~ 5 part,
Suds-stabilizing agent 0.5 ~ 1.0 part,
Pneumatogen 1 ~ 3 part,
1 ~ 3 part, water;
B component is polyphenyl polymethylene polyisocyanates.
Further, described kicker is one or more the mixture in triethylene diamine, triethylamine, diethylenetriamine, trolamine, diethanolamine, thanomin, N, N-dimethyl cyclohexane, Tetramethyl Ethylene Diamine or dimethylethanolamine.
Further, the mixture that described suds-stabilizing agent is silicone oil, silicon-carbon type stablizer or silicone oil and silicon-carbon type stablizer form.
Further, described pneumatogen is one or more the mixture in HCFC-141b, pentamethylene, methyl-formiate, F-11 or HFC-245fa.
Present invention also offers the preparation method of above-mentioned a kind of difficulty combustion B1 level hard polyurethane foam, comprise the steps:
(1) non-halogen reacting phosphorus/silicon synergistic fire retardant, kicker, suds-stabilizing agent, pneumatogen and water is taken according to weight ratio, containing in N structure flame retardant polyether polyol, add non-halogen reacting phosphorus/silicon synergistic fire retardant, kicker, suds-stabilizing agent, pneumatogen and water, after being uniformly mixed, obtain component A;
(2) polyphenyl polymethylene polyisocyanates is taken, by the mass ratio of A and B component, B component is joined in component A again, rapid stirring 5 ~ 20s, pour in Teflon mould and solidify 30 ~ 60s, at room temperature after fixing, obtains difficult combustion B1 level hard polyurethane foam.
Further, the preparation method of described non-halogen reacting phosphorus/silicon synergistic fire retardant is: take methylvinyldichlorosilane, dimethylphosphite, aluminum chloride, described methylvinyldichlorosilane, the mol ratio of dimethylphosphite and aluminum chloride is 1:(1.0 ~ 2.0): (0.1 ~ 0.5), by methylvinyldichlorosilane, dimethylphosphite, aluminum chloride joins in a reaction vessel successively, warming while stirring to 50 DEG C ~ 80 DEG C, reaction 12 ~ 24h, cool the temperature to 60 DEG C ~ 80 DEG C again, add water, described water and the mol ratio of methylvinyldichlorosilane are 3 ~ 8:1, , naturally room temperature is down to after continuing reaction 2 ~ 6h, underpressure distillation under vacuum tightness-0.1 ~-0.5MPa after extraction, gained viscous liquid is non-halogen reacting phosphorus/silicon synergistic fire retardant.
The present invention is raw material based on methylvinyldichlorosilane, dimethylphosphite, take aluminum chloride as catalyzer, obtain non-halogen reacting phosphorus/silicon synergistic fire retardant, and then prepare anti-inflaming polyurethane hard foam with polyether glycol, isocyanate reaction, the anti-inflaming polyurethane hard foam obtained has even compact, regular hexagon foam structure, and its density is 36.5 ~ 38.4kg/m
3, compressive strength is 175 ~ 185kPa, and limiting oxygen index(LOI) is 30.4 ~ 32.5%.
The present invention compares with prior art, and its technical progress is significant.The present invention is cheaply easy to get because of raw material, thus greatly reduces production cost, and the production for low-cost flame-retardant hard polyurethane foam provides a kind of brand-new technological approaches.The invention solves the single type fire retardant technical problem that flame retardant effect is still undesirable under high introduction volume, overcome the technical problem of the ubiquitous ignition-proof element migration of additive flame retardant and dialysis, avoid the technical problem that traditional Halogen structure anti-inflaming polyurethane hard foam produces mortality gas in combustion.
Embodiment
Below by embodiment, the present invention is described in further detail, but do not limit the present invention.
embodiment 1
(1) according to the mol ratio of 1:1.6:0.5, methylvinyldichlorosilane, dimethylphosphite, aluminum chloride are joined successively in four neck flasks, warming while stirring to 50 DEG C, reaction 16h.Then cool the temperature to 75 DEG C, add 5g water, be naturally down to room temperature, underpressure distillation under vacuum tightness-0.1MPa after extraction after continuing reaction 4h, obtain non-halogen reacting phosphorus/silicon synergistic fire retardant.
(2) above-mentioned for 2.10g non-halogen reacting phosphorus/silicon synergistic fire retardant, 8.04g polyether glycol, 1.76g kicker, 0.78gHCFC-141b, 0.25g suds-stabilizing agent and 0.68g water are joined in the plastic containers of volume 1L, control rotating speed at 300rmp, stirring at room temperature 20s, obtains difficult combustion B1 level polyurethane rigid foam combination material component A.
(3) get component A 1 part that above-mentioned steps (2) obtains and B component 1.5 parts at room temperature to foam to obtain and difficultly fire B1 level hard polyurethane foam.
The difficulty combustion B1 level hard polyurethane foam of above-mentioned gained, recording its limiting oxygen index(LOI) according to GB/T2406.2-2009 standard is 30.3%, is 36.5kg/m according to its density of GB/T6343-1995 standard test
3, be 176kPa according to its compressive strength of GB/T8813-2008 standard test.
embodiment 2
(1) according to the mol ratio of 1:1.6:0.5, methylvinyldichlorosilane, dimethylphosphite, aluminum chloride are joined successively in four neck flasks, under nitrogen protection, warming while stirring to 50 DEG C, reaction 16h.Then cool the temperature to 75 DEG C, add 5g water, be naturally down to room temperature, underpressure distillation under vacuum tightness-0.1MPa after extraction after continuing reaction 4h, obtain non-halogen reacting phosphorus/silicon synergistic fire retardant.
(2) above-mentioned for 1.99g non-halogen reacting phosphorus/silicon synergistic fire retardant, 8.15g polyether glycol, 1.50g catalyzer, 0.81gHCFC-141b, 0.31g suds-stabilizing agent and 0.65g water are joined in the plastic containers of volume 1L, control rotating speed at 300rmp, stirring at room temperature 20s, obtains difficult combustion B1 level polyurethane rigid foam combination material component A.
(3) get component A 1 part that above-mentioned steps (2) obtains and B component 1.5 parts at room temperature to foam to obtain and difficultly fire B1 level hard polyurethane foam.
The difficulty combustion B1 level hard polyurethane foam of above-mentioned gained, recording its limiting oxygen index(LOI) is 31.2%, and density is 37.1kg/m
3, compressive strength is 179kPa.
embodiment 3
(1) according to the mol ratio of 1:1.6:0.5, during methylvinyldichlorosilane, dimethylphosphite, aluminum chloride are joined successively, warming while stirring to 50 DEG C, reaction 16h.Then cool the temperature to 75 DEG C, add 5g water, be naturally down to room temperature, underpressure distillation under vacuum tightness-0.1MPa after extraction after continuing reaction 4h, obtain non-halogen reacting phosphorus/silicon synergistic fire retardant.
(2) above-mentioned for 2.22g non-halogen reacting phosphorus/silicon synergistic fire retardant, 8.21g polyether glycol, 2.17g catalyzer, 0.84gHCFC-141b, 0.30g suds-stabilizing agent and 0.77g water are joined in the plastic containers of volume 1L, control rotating speed at 300rmp, stirring at room temperature 20s, obtains difficult combustion B1 level polyurethane rigid foam combination material component A.
(3) get component A 1 part that above-mentioned steps (2) obtains and B component 1.5 parts at room temperature to foam to obtain and difficultly fire B1 level hard polyurethane foam.
The difficulty combustion B1 level hard polyurethane foam of above-mentioned gained, recording its limiting oxygen index(LOI) is 31.6%, and density is 36.8kg/m
3, compressive strength is 180kPa.
embodiment 4
(1) according to the mol ratio of 1:1.6:0.5, methylvinyldichlorosilane, dimethylphosphite, aluminum chloride are joined successively in four neck flasks, warming while stirring to 50 DEG C, then reaction 16h cools the temperature to 75 DEG C, add 5g water, naturally be down to room temperature, underpressure distillation under vacuum tightness-0.1MPa after extraction after continuing reaction 4h, obtain non-halogen reacting phosphorus/silicon synergistic fire retardant.
(2) above-mentioned for 2.18g non-halogen reacting phosphorus/silicon synergistic fire retardant, 8.01g polyether glycol, 1.76g catalyzer, 0.88gHCFC-141b, 0.32g suds-stabilizing agent and 0.72g water are joined in the plastic containers of volume 1L, control rotating speed at 300rmp, stirring at room temperature 20s, obtains difficult combustion B1 level polyurethane rigid foam combination material component A.
(3) get component A 1 part that above-mentioned steps (2) obtains and B component 1.5 parts at room temperature to foam to obtain and difficultly fire B1 level hard polyurethane foam.
The difficulty combustion B1 level hard polyurethane foam of above-mentioned gained, recording its limiting oxygen index(LOI) is 32.4%, and density is 37.2kg/m
3, compressive strength is 183kPa.
Above said content be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (6)
1. a difficult combustion B1 level hard polyurethane foam, it is characterized in that: be made up of component A and B component, the weight ratio of component A and B component is 1:(1 ~ 1.7);
Wherein, described component A, is made up of the raw material of following parts by weight:
Containing N structure flame retardant polyether polyol 20 ~ 40 parts,
Non-halogen reacting phosphorus/silicon synergistic fire retardant 5 ~ 10 parts,
Kicker 1 ~ 5 part,
Suds-stabilizing agent 0.5 ~ 1.0 part,
Pneumatogen 1 ~ 3 part,
1 ~ 3 part, water;
B component is polyphenyl polymethylene polyisocyanates.
2. a kind of difficult combustion B1 level hard polyurethane foam as claimed in claim 1, it is characterized in that: described kicker is one or more the mixture in triethylene diamine, triethylamine, diethylenetriamine, trolamine, diethanolamine, thanomin, N, N-dimethyl cyclohexane, Tetramethyl Ethylene Diamine or dimethylethanolamine.
3. combustion B1 level hard polyurethane foam as claimed in claim 1 a kind of difficult and preparation method thereof, is characterized in that: the mixture that described suds-stabilizing agent is silicone oil, silicon-carbon type stablizer or silicone oil and silicon-carbon type stablizer form.
4. a kind of difficult combustion B1 level hard polyurethane foam as claimed in claim 1, is characterized in that: described pneumatogen is one or more the mixture in HCFC-141b, pentamethylene, methyl-formiate, F-11 or HFC-245fa.
5. the preparation method of a kind of difficulty combustion B1 level hard polyurethane foam according to claim 1, is characterized in that comprising the steps:
(1) non-halogen reacting phosphorus/silicon synergistic fire retardant, kicker, suds-stabilizing agent, pneumatogen and water is taken according to weight ratio, containing in N structure flame retardant polyether polyol, add non-halogen reacting phosphorus/silicon synergistic fire retardant, kicker, suds-stabilizing agent, pneumatogen and water, after being uniformly mixed, obtain component A;
(2) take polyphenyl polymethylene polyisocyanates, then join in component A by the mass ratio of A and B component by B component, rapid stirring 5 ~ 20s, pours in Teflon mould, at room temperature solidifies 30 ~ 60s, obtains difficult combustion B1 level hard polyurethane foam.
6. the preparation method of a kind of difficulty combustion B1 level hard polyurethane foam according to claim 5, it is characterized in that: the preparation method of described non-halogen reacting phosphorus/silicon synergistic fire retardant is: take methylvinyldichlorosilane, dimethylphosphite, aluminum chloride, described methylvinyldichlorosilane, the mol ratio of dimethylphosphite and aluminum chloride is 1:(1.0 ~ 2.0): (0.1 ~ 0.5), by methylvinyldichlorosilane, dimethylphosphite, aluminum chloride joins in a reaction vessel successively, warming while stirring to 50 DEG C ~ 80 DEG C, reaction 12 ~ 24h, cool the temperature to 60 DEG C ~ 80 DEG C again, add water, described water and the mol ratio of methylvinyldichlorosilane are 3 ~ 8:1, naturally room temperature is down to after continuing reaction 2 ~ 6h, underpressure distillation under vacuum tightness-0.1 ~-0.5MPa after extraction, gained viscous liquid is non-halogen reacting phosphorus/silicon synergistic fire retardant.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669937A (en) * | 2016-04-26 | 2016-06-15 | 滕钜海 | Environment-friendly flame-retardant hard polyurethane foaming plastic |
| CN106008916A (en) * | 2016-07-11 | 2016-10-12 | 河南省煤炭化工研究所有限责任公司 | Preparation method of flame-retardant polyurethane foam plastic |
| CN108559047A (en) * | 2018-01-27 | 2018-09-21 | 华北科技学院 | A kind of preparation method of flame retardant polyurethane interpenetrating net polymer |
| CN109082106A (en) * | 2018-07-23 | 2018-12-25 | 德清顾舒家华高分子材料有限公司 | A kind of polyurethane foam containing organic silicon-phosphorus synergistic fire retardant |
| CN109651584A (en) * | 2018-11-20 | 2019-04-19 | 黎明化工研究设计院有限责任公司 | A kind of response type phosphate ester flame retardants and preparation method thereof and the application in polyurethane foam |
| WO2023241155A1 (en) * | 2022-06-17 | 2023-12-21 | 天长市伯士的环保新材料有限公司 | High-oxygen-index flame-retardant rigid polyurethane foam, composition therefor, and preparation method therefor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669937A (en) * | 2016-04-26 | 2016-06-15 | 滕钜海 | Environment-friendly flame-retardant hard polyurethane foaming plastic |
| CN106008916A (en) * | 2016-07-11 | 2016-10-12 | 河南省煤炭化工研究所有限责任公司 | Preparation method of flame-retardant polyurethane foam plastic |
| CN106008916B (en) * | 2016-07-11 | 2018-07-17 | 河南省煤炭化工研究所有限责任公司 | A kind of preparation method of flame-retardant polyurethane foam plastic |
| CN108559047A (en) * | 2018-01-27 | 2018-09-21 | 华北科技学院 | A kind of preparation method of flame retardant polyurethane interpenetrating net polymer |
| CN109082106A (en) * | 2018-07-23 | 2018-12-25 | 德清顾舒家华高分子材料有限公司 | A kind of polyurethane foam containing organic silicon-phosphorus synergistic fire retardant |
| CN109651584A (en) * | 2018-11-20 | 2019-04-19 | 黎明化工研究设计院有限责任公司 | A kind of response type phosphate ester flame retardants and preparation method thereof and the application in polyurethane foam |
| CN109651584B (en) * | 2018-11-20 | 2021-10-08 | 黎明化工研究设计院有限责任公司 | Reactive phosphorus-containing flame retardant, preparation method thereof and application thereof in polyurethane foam |
| WO2023241155A1 (en) * | 2022-06-17 | 2023-12-21 | 天长市伯士的环保新材料有限公司 | High-oxygen-index flame-retardant rigid polyurethane foam, composition therefor, and preparation method therefor |
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