CN105801833A - Preparation method and application of reactive type halogen-free flame-retardant polyether glycol - Google Patents
Preparation method and application of reactive type halogen-free flame-retardant polyether glycol Download PDFInfo
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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
- 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
- C08G65/2639—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 elements other than oxygen, nitrogen or sulfur
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/5078—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
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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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Abstract
The invention relates to a preparation method of reactive type halogen-free flame-retardant polyether glycol and belongs to the field of organic synthesis.The preparation method comprises the steps that tetramethylol phosphide is subjected to a formaldehyde removal reaction under the action of a catalyst, and then an oxidation reaction is conducted in certain solvent and at a certain temperature, so that trisphosphine oxide is prepared ; after purification is conducted, a product and epoxypropane/oxirane are subjected to an addition reaction in a certain pressure environment and a catalyst condition, so that a product, namely reactive type halogen-free flame-retardant polyether glycol, is obtained.By means of the method, raw materials are low in price and easy to obtain, the reactions are simple and controllable, the yield reaches 95% or above, the obtained reactive type halogen-free flame-retardant polyether glycol is medium in viscosity and good in compatibility with foaming agents and other auxiliary agents, a combined material compounded with the reactive type halogen-free flame-retardant polyether glycol is uniform, transparent, good in fluidity and good in stability, and certain industrial prospect is achieved.
Description
Technical field
The present invention relates to a kind of preparation method that can be used for the fire-retardant response type halogen-free flameproof polyether polyol of hard polyurethane foam material and purposes, belong to organic synthesis field.
Background technology
Rigid polyurethane foam heat-insulating property is excellent, light weight, good stability of the dimension, and convenient formation is widely used in the fields such as building heat preservation, cold preservation, transport and chemical industry usually used as insulation material.But its inflammability is the greatest problem of restriction rigid polyurethane foam range of application.Currently, solving this problem main path is realized by interpolation fire retardant in material preparation process.Fire retardant suitable in rigid polyurethane foam can be divided into addition type and the big class of response type two.Wherein, additive flame retardant is containing ignition-proof elements such as certain chlorine, bromine, phosphorus or nitrogen but without any compound with reaction active groups；Reactive flame retardant then comprises ignition-proof element and reaction active groups simultaneously, and it directly as the raw material of hard polyurethane material, can participate in the chemical reaction of polyurethane.Additive flame retardant mostly is micromolecular compound, can move out problem with the ageing process of material, and material itself is had certain plasticization effect；And reactive flame retardant is fixed in material this subject with chemical bond form, there is lasting flame retardant effect, and add number more time, the mechanical performance of foamed materials can't be had much impact, thus be requisite composition in high performance polyurethane insulation material formula.
The preparation method that Chinese patent 103497322 reports a kind of response type Halogen flame retardant polyether polyol, every 100 formula add 20 parts of this fire retardants and can pass through Germany's DIN4102B level test, but there is a large amount of halogen atom in this based flame retardant, a large amount of toxic gas can be produced during burning, do not meet day by day harsh environmental requirement.US Patent No. 5049697 reports a kind of brominated reaction-type flame-retarding polyethers, this flame retarding polyether is reacted with diglycol and propylene glycol by PHT4 and prepares, its feature is that bromine content is high, stable in properties, with polyhydric alcohol and foaming agent, there is the good compatibility, current Albemarle company has corresponding commercially produced product SaytexRB-79, but it is excessive that the typical problem of this based flame retardant is viscosity, need during use with other non-reactive low viscosity fire retardant with the use of, and equally exist the problem containing a large amount of halogens.Chinese Patent Application No. a kind of reaction-type flame-retarding polyether polyol prepared by polyhydric alcohol, epoxide and tribromphenol that has been the patent Introduction of 20101029581.6, and it is applied to the preparation of hard polyurethane foam material, owing to molecular weight of product is relatively big and viscosity is too high, during practical application, there is the problem mixing difficulty with foaming agent；Chinese Patent Application No. 201110249069.4 discloses a kind of method that phosphorous Halogen flame retardant polyester polyhydric alcohol is prepared in reaction by phosphoryl chloride phosphorus oxychloride Yu brominated dihydroxylic alcohols, the fire resistance of polyurethane material can be greatly improved after adding a certain amount of this polyester, but in its preparation process, use expensive acid binding agent in a large number, preparation cost is excessive, and to have viscosity big due to polyester itself, the problem that degree of functionality is low, the addition in hard polyurethane foam formula is limited.
Summary of the invention
It is an object of the invention to overcome above-mentioned deficiency, it is provided that the preparation method of a kind of response type halogen-free flameproof polyether polyol and purposes, solve current flame retarding polyether ubiquitous on the high side, viscosity is excessive, and degree of functionality is on the low side and containing the problem of a large amount of halogens.The method utilizes cheap tetra methylol phosphide (about 75wt%) that piptonychia aldehyde reaction occurs under catalyst action, then occur oxidation reaction to prepare trihydroxy methyl phosphorous oxide under certain solvent and temperature environment, after purified, occur additive reaction to prepare product response type halogen-free flameproof polyether polyol under certain pressure environment and catalysts conditions in product and expoxy propane/oxirane.The method raw material is cheap and easy to get, and reaction is simple, has great industrial prospect.
Another object of the present invention is to utilize the halogen-free flameproof polyether polyol prepared, phosphorus flame retardant in conjunction with addition type, strengthened the flame retardant effect of flame retardant polyether polyol by certain synergism, while improving hard polyurethane foam anti-flammability, give the mechanical property of its excellence.
The object of the present invention is achieved like this: the preparation method of a kind of response type halogen-free flameproof polyether polyol, comprises the following steps:
(1) tetra methylol phosphide prepares trihydroxy methyl phosphorus with the reactant aqueous solution generation piptonychia aldehyde reaction of alkali compounds, and reaction temperature is-20～20 DEG C, and the response time is 2～8 hours.
(2) organic solvent is added after trihydroxy methyl phosphorus elimination water step (1) obtained, then remove solid by-product by centrifugation, finally heated it is obtained by reacting trihydroxy methyl phosphorous oxide, reaction temperature is 50～90 DEG C, response time is 2～6 hours, and reaction terminates in 80～100 DEG C of decompressions (5～10mmHg) and organic solvent is distilled off.
(3) trihydroxy methyl phosphorous oxide step (2) obtained adds autoclave, under certain catalysts conditions, additive reaction is carried out with little Molecular Ring oxygen compound, prepare response type halogen-free flameproof polyether polyol, reaction temperature is 60～120 DEG C, response time is 3～7 hours, and reaction pressure is 0.2～0.6MPa.
Wherein:
Tetra methylol phosphide described in step (1) is the one in THPC, tetra methylol phosphonium bromide, tetra methylol fluoride phosphorus, tetra methylol phosphoric sulfide or tetrakis hydroxymetyl phosphonium sulfuric, alkali compounds used is the combination of one or more (containing two kinds) in sodium hydroxide, potassium hydroxide, Lithium hydrate, calcium hydroxide, ammonia, ethylenediamine or triethylamine, the mol ratio of tetra methylol phosphide used and alkali compounds is 0.2～2:1, it is preferable that 0.3～0.5:1；Reaction temperature is-20～20 DEG C, it is preferable that-20～0 DEG C；Response time is 2～8 hours, it is preferable that 3～5 hours.
In step (2), organic solvent used is methanol, ethanol, isopropanol, n-butyl alcohol, ethylene glycol, oxolane, dioxane, N, the combination of one or more (containing two kinds) in dinethylformamide, acetone or butanone, it is preferable that ethanol and dioxane；The mass ratio of trihydroxy methyl phosphorus used and solvent is 1～4:1, it is preferable that 2～3:1；Reaction temperature is 50～90 DEG C, it is preferable that 70～80 DEG C；Response time is 2～6 hours, it is preferable that 2～3 hours.
Little Molecular Ring oxygen compound described in step (3) is the combination of one or more (containing two kinds) in oxirane, expoxy propane or epoxychloropropane, the mol ratio of trihydroxy methyl phosphorous oxide used and epoxide is 0.1～1:1, it is preferable that 0.2～0.4:1.
Catalyst described in step (3) is the combination of one or more (containing two kinds) in sodium hydroxide, potassium hydroxide, cyclohexylamine or triethylamine, the mass ratio of used catalyst and trihydroxy methyl phosphorous oxide is 0.001～0.01:1, it is preferable that 0.005～0.08:1；Reaction temperature is 60～120 DEG C, it is preferable that 90～110 DEG C；Response time is 3～7 hours, it is preferable that 6～7 hours；Reaction pressure is 0.2～0.6MPa, it is preferable that 0.4～0.5MPa.
Response type halogen-free flameproof polyether polyol prepared by the present invention is as the reactive flame retardant preparation for flame retardant polyurethane material, described flame retardant polyurethane material includes but not limited to the materials such as polyurethane foam, polyurethane elastomer, polyurethane adhesive, polyurethane sealant and polyurethane coating, optimization polyurethane foamed materials, it is preferred that hard polyurethane foam material.
Compared with prior art, the method have the advantages that
1, in the present invention, tetra methylol phosphide raw material used is cheap and easy to get, reacts simply controlled, and reaction yield reaches more than 95%.
2, the present invention utilizes the additive reaction that carries out of trihydroxy methyl phosphorous oxide and epoxide to prepare 3 degree of functionality polyether polyol, this raw material is adopted to add in the formula of hard polyurethane foam as reactive flame retardant, even if during large usage quantity, produce to significantly affect without to the mechanical performance of foamed materials.
3, the response type halogen-free flameproof polyether polyol modest viscosity that prepared by the present invention, good with foaming agent and other auxiliary agent compatibility, with the premixed systems homogeneous transparent of its configuration, mobility is good, good stability.Add a small amount of this flame retardant polyether polyol, coordinate other phosphorus flame retardant, the B1 level insulation material that there is excellent mechanical performance, oxygen index (OI) more than 30 can be prepared.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, it is necessary to explanation, and embodiment is not intended that the restriction to claimed scope.
Embodiment 1
Weighing tetrakis hydroxymetyl phosphonium sulfuric aqueous solution 271g (containing tetrakis hydroxymetyl phosphonium sulfuric 203g), 56g potassium hydroxide joins in the 1L there-necked flask with mechanical agitation, thermometer and condensing tube, maintains this temperature and stir 5 hours after being cooled to 0 DEG C.
The product that 1st step is obtained by reacting is distilled off aqueous solvent by decompression, then add at normal temperatures after product is dissolved by 62g ethanol and send into centrifuge removing solid by-product, and post-heating was to 80 DEG C of stirring reactions 3 hours, after reaction terminates, decompression is distilled off ethanol and obtains product trihydroxy methyl phosphorous oxide, reaction yield 96%.
Weigh the product 124g that the 3rd step is obtained by reacting, triethylamine 0.62g joins with in pressure reaction still, treat that temperature rises to about 80 DEG C and starts to pass into expoxy propane, maintaining pressure in still during reaction is 0.3MPa, and temperature in the kettle, at 95 DEG C, passes into 232g expoxy propane altogether in 3 hours, reaction continues stirring 1 hour after terminating at 95 DEG C, last evacuation removes unreacted expoxy propane, obtains response type halogen-free flameproof polyether polyol, reaction yield 95%.
Embodiment 2
Weighing THPC aqueous solution 253g (containing THPC 190g), 148g calcium hydroxide joins in the 1L there-necked flask with mechanical agitation, thermometer and condensing tube, maintains this temperature and stir 3 hours after being cooled to-10 DEG C.
The product that 1st step is obtained by reacting is distilled off aqueous solvent by decompression, then add at normal temperatures after product is dissolved by 41g methanol and send into centrifuge removing solid by-product, and post-heating was to 70 DEG C of stirring reactions 2 hours, after reaction terminates, decompression distillation for removing methanol obtains product trihydroxy methyl phosphorous oxide, reaction yield 95%.
Weigh the product 130g that the 3rd step is obtained by reacting, potassium hydroxide 1g joins with in pressure reaction still, treat that temperature rises to about 75 DEG C and starts to pass into expoxy propane, maintaining pressure in still during reaction is 0.5MPa, and temperature in the kettle, at 90 DEG C, passes into 135g expoxy propane altogether in 6 hours, reaction continues stirring 1 hour after terminating at 90 DEG C, last evacuation removes unreacted expoxy propane, obtains response type halogen-free flameproof polyether polyol, reaction yield 95%.
Embodiment 3
Weighing tetra methylol phosphonium bromide aqueous solution 314g (containing tetra methylol phosphonium bromide 235g), 200g sodium hydroxide joins in the 1L there-necked flask with mechanical agitation, thermometer and condensing tube, maintains this temperature and stir 8 hours after being cooled to-20 DEG C.
The product that 1st step is obtained by reacting is distilled off aqueous solvent by decompression, then add at normal temperatures after product is dissolved by 31g acetone and send into centrifuge removing solid by-product, and post-heating was to 50 DEG C of stirring reactions 5 hours, after reaction terminates, decompression is distilled off acetone and obtains product trihydroxy methyl phosphorous oxide, reaction yield 95%.
Weigh the product 132g that the 3rd step is obtained by reacting, sodium hydroxide 0.8g joins with in pressure reaction still, treat that temperature rises to about 75 DEG C and starts to pass into oxirane, maintaining pressure in still during reaction is 0.4MPa, and temperature in the kettle, at 100 DEG C, passes into 440g oxirane altogether in 4 hours, reaction continues stirring 1 hour after terminating at 100 DEG C, last evacuation removes unreacted expoxy propane, obtains response type halogen-free flameproof polyether polyol, reaction yield 95%.
Embodiment 4
Weigh tetra methylol phosphoric sulfide aqueous solution 207g (containing tetra methylol phosphoric sulfide 155g), 33g triethylamine and Lithium hydrate 4.8g join in the 1L there-necked flask with mechanical agitation, thermometer and condensing tube, maintain this temperature and stir 4 hours after being cooled to-5 DEG C.
The product that 1st step is obtained by reacting is distilled off aqueous solvent by decompression, then add at normal temperatures after product is dissolved by 30g dioxane and 20g methanol and send into centrifuge removing solid by-product, and post-heating was to 65 DEG C of stirring reactions 2 hours, after reaction terminates, decompression is distilled off acetone and obtains product trihydroxy methyl phosphorous oxide, reaction yield 95%.
Weigh the product 132g that the 3rd step is obtained by reacting, sodium hydroxide 0.3g, potassium hydroxide 0.2g joins with in pressure reaction still, treat that temperature rises to about 75 DEG C and starts to pass into oxirane and expoxy propane, maintaining pressure in still during reaction is 0.3MPa, temperature in the kettle is at 100 DEG C, 44g oxirane is altogether passed in 3 hours, 116g expoxy propane, reaction continues stirring 1 hour after terminating at 100 DEG C, last evacuation removes unreacted expoxy propane, obtains response type halogen-free flameproof polyether polyol, reaction yield 95%.
Embodiment 5
Weigh THPC aqueous solution 253g (containing THPC 190g), 30g ethylenediamine and hydroxide first 28g join in the 1L there-necked flask with mechanical agitation, thermometer and condensing tube, maintain this temperature and stir 3 hours after being cooled to 0 DEG C.
The product that 1st step is obtained by reacting is distilled off aqueous solvent by decompression, then add at normal temperatures after product is dissolved by 50g ethanol and 70g butanone and send into centrifuge removing solid by-product, and post-heating was to 70 DEG C of stirring reactions 4 hours, after reaction terminates, decompression is distilled off acetone and obtains product trihydroxy methyl phosphorous oxide, reaction yield 95%.
Weigh the product 132g that the 3rd step is obtained by reacting, hydroxide first 0.3g, cyclohexylamine 0.1g joins with in pressure reaction still, treat that temperature rises to about 70 DEG C and starts to pass into oxirane and expoxy propane, maintaining pressure in still during reaction is 0.2MPa, temperature in the kettle is at 110 DEG C, 88g oxirane is altogether passed in 3 hours, 116g expoxy propane, reaction continues stirring 1 hour after terminating at 110 DEG C, last evacuation removes unreacted expoxy propane, obtains response type halogen-free flameproof polyether polyol, reaction yield 95%.
Based on the response type halogen-free flameproof polyether polyol of the embodiment of the present invention 2 preparation, conventionally formula prepares combined polyether, then with polymeric MDI mixed at high speed after carry out foaming experiment.
Correlation analysis test result is in Table 1
Table 1 adopts formula and the performance test results of the hard polyurethane foam of the response type halogen-free flameproof polyether polyol that common polyether and the present invention prepare.
Test result shows: add the response type halogen-free flameproof polyether polyol of 50 parts of present invention in the formula of hard polyurethane foam, the hard polyurethane foam material that flame retardant rating is B2 level can be obtained, add the response type halogen-free flameproof polyether polyol of 100 parts of present invention, can obtain hard polyurethane foam material that flame retardant rating is B1 level and, other performances for foam that add of response type halogen-free flameproof polyether polyol are substantially free of impact, therefore, response type halogen-free flameproof polyether polyol provided by the invention is preparing polyurethane material, the preparation in the hard polyurethane foam material that high fire-retardance requires particularly is had to be likely to there is great application prospect.
Claims (6)
1. the preparation method of a response type halogen-free flameproof polyether polyol, it is characterised in that: said method comprising the steps of:
(1) preparing trihydroxy methyl phosphorus with the reactant aqueous solution generation piptonychia aldehyde reaction of tetra methylol phosphide Yu alkali compounds, reaction temperature is-20～20 DEG C, and the response time is 2～8 hours；
(2) organic solvent is added after trihydroxy methyl phosphorus elimination water step (1) obtained, then removing solid by-product by centrifugation, finally heated be obtained by reacting trihydroxy methyl phosphorous oxide, reaction temperature is 50～90 DEG C, response time is 2～6 hours, and reaction terminates in 80～100OC decompression is distilled off organic solvent；
(3) trihydroxy methyl phosphorous oxide step (2) obtained adds autoclave, under certain catalysts conditions, additive reaction is carried out with little Molecular Ring oxygen compound, prepare response type halogen-free flameproof polyether polyol, reaction temperature is 60～120 DEG C, response time is 3～7 hours, and reaction pressure is 0.2～0.6MPa.
2. the preparation method of a kind of response type halogen-free flameproof polyether polyol according to claim 1, it is characterized in that tetra methylol phosphide described in step (1) is the one in THPC, tetra methylol phosphonium bromide, tetra methylol fluoride phosphorus, tetra methylol phosphoric sulfide or tetrakis hydroxymetyl phosphonium sulfuric, alkali compounds used is one or more the combination in sodium hydroxide, potassium hydroxide, Lithium hydrate, calcium hydroxide, ammonia, ethylenediamine or triethylamine, and the mol ratio of tetra methylol phosphide used and alkali compounds is 0.2～2:1.
3. the preparation method of a kind of response type halogen-free flameproof polyether polyol according to claim 1, it is characterized in that in step (2), organic solvent used is methanol, ethanol, isopropanol, n-butyl alcohol, ethylene glycol, oxolane, dioxane, N, the mass ratio of one or more the combination in dinethylformamide, acetone or butanone, trihydroxy methyl phosphorus used and solvent is 1～4:1.
4. the preparation method of a kind of response type halogen-free flameproof polyether polyol according to claim 1, it is characterized in that little Molecular Ring oxygen compound described in step (3) is one or more the combination in oxirane or expoxy propane or epoxychloropropane, the mol ratio of trihydroxy methyl phosphorous oxide used and epoxide is 0.1～1:1.
5. the preparation method of a kind of response type halogen-free flameproof polyether polyol according to claim 1, it is characterized in that catalyst described in step (3) is one or more the combination in sodium hydroxide, potassium hydroxide, cyclohexylamine or triethylamine, the mass ratio of used catalyst and trihydroxy methyl phosphorous oxide is 0.001～0.01:1.
6. the response type halogen-free flameproof polyether polyol that prepared by a method as according to any one of claim 1 or 2 or 3 or 4 or 5 application in flame retardant polyurethane hard foam.
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| CN106366302A (en) * | 2016-08-26 | 2017-02-01 | 东华大学 | Flame-retardant hydrophilic polyester resin and preparing method thereof |
| CN106750248A (en) * | 2017-01-24 | 2017-05-31 | 中国科学技术大学 | A kind of hyperbranched flame retardant polyether polyol and preparation method thereof |
| CN107141467A (en) * | 2017-06-28 | 2017-09-08 | 山东诺威新材料有限公司 | The preparation method of phosphorus chlorine composite flame-proof polyethers |
| CN107459620A (en) * | 2017-08-14 | 2017-12-12 | 淄博联创聚氨酯有限公司 | The preparation method of flame-proof polyol and its polyurethane foam of preparation and polyurethane sealant |
| CN107840938A (en) * | 2017-11-27 | 2018-03-27 | 山东诺威新材料有限公司 | Combined polyether, ageing-resistant complete water type foam board and preparation method thereof |
| CN109400866A (en) * | 2018-09-29 | 2019-03-01 | 山东诺威新材料有限公司 | Flame retardant type sponge polyether polyol and preparation method thereof |
| CN110054803A (en) * | 2019-04-25 | 2019-07-26 | 中国科学技术大学 | A kind of phosphorus-nitrogen containing flame-proof polyol, preparation method and its preparing the application in resistance combustion polyurethane foam |
| CN110862526A (en) * | 2019-11-01 | 2020-03-06 | 上海应用技术大学 | Preparation method of high-activity flame-retardant polyether polyol |
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| CN111333831A (en) * | 2020-04-22 | 2020-06-26 | 山东福瑞斯新材料科技有限公司 | Continuous preparation method of flame-retardant polyether polyol |
| CN113882029A (en) * | 2021-11-04 | 2022-01-04 | 唐山三友集团兴达化纤有限公司 | High-strength washable phosphorus-nitrogen flame-retardant viscose fiber and preparation method thereof |
| CN115232287A (en) * | 2022-08-08 | 2022-10-25 | 南京金栖化工集团有限公司 | Flame-retardant slow-rebound polyurethane sponge and preparation method thereof |
| CN115304762A (en) * | 2022-08-11 | 2022-11-08 | 山东一诺威新材料有限公司 | Preparation method and application of reactive halogen-free flame-retardant polyether polyol |
| WO2022238293A1 (en) | 2021-05-11 | 2022-11-17 | Clariant International Ltd | Flexible foams comprising flame-retardant polyurethane, a process for their production and use thereof |
| WO2022238196A1 (en) | 2021-05-11 | 2022-11-17 | Clariant International Ltd | Alkoxylates of methylol-organyl-phosphine oxides, process for manufacture thereof, flame-retardant polymers and use thereof |
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