CN1228446A - Fire resistant polymer polylol and its use - Google Patents
Fire resistant polymer polylol and its use Download PDFInfo
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- CN1228446A CN1228446A CN 99112035 CN99112035A CN1228446A CN 1228446 A CN1228446 A CN 1228446A CN 99112035 CN99112035 CN 99112035 CN 99112035 A CN99112035 A CN 99112035A CN 1228446 A CN1228446 A CN 1228446A
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Abstract
The present invention uses halogen-contained vinyl monomer (vinyl tetrahalogen phthalate), phenylethyelne and cyanoethylene as raw material, and makes them produce free radical copolymerization reaction in polymether polyol in the pressure of dispersant to prepare fire-retardant polymer polyol with characteristics of low cost, high solid content, low viscosity, good inflaming retarding property, simple preparation and easily foaming. The obtained fire-retardant polymer polyol can be reacted with diisocyanate compound to obtain the fire-retardant polyurethane foam material with higher bearing capacity and higher inflaming retardting property (self-extinguishment).
Description
The present invention relates to a kind of fire resistant polymer polylol and application thereof, belong to polymer polyatomic alcohol and Application Areas thereof.
Polyurethane foamed material is a kind of superpolymer with special performance and many-sided purposes.It is to be basic raw material with polyvalent alcohol and diisocyanate, allocates less water, filler, organic silicon surfactant, whipping agent into, forms under the acting in conjunction of organotin and tertiary amine catalyst.Can make hard, semi-rigid and flexible urethane foam with it, be applied to the aspects such as saddle of cushion, back cushion, inside gadget and the motorcycle of vehicle mainly as cushioning material, also can be used for making simultaneously civilian industries such as sofa, mattress, finishing material.
Polymer polyatomic alcohol is that vinyl monomer is in the presence of dispersion agent, polymerized product in polyether glycol, the used vinyl monomer of polymer polyatomic alcohol at the beginning of the seventies is a vinyl cyanide, its solid content (polymer content) is in 5%～25% (weight), viscosity height, look Huang, easily makes the heartburn variable color of polyurethane foam; The mid-80 prepares polymer polyatomic alcohol with vinyl cyanide and vinylbenzene mix monomer, and its solid content is in 20%～30% (weight), and styrene content is more than 50% (weight); At the initial stage nineties, abroad some companies release one after another solid content more than 40% (weight), and viscosity is lower than the polymer polyatomic alcohol of 5500mPas (25 ℃), as European patent Ep778,301; PCT.Int.Appl.Wo.97,15,605; PCT.Int.Appl.Wo.97,15,606 disclosed polymer polyatomic alcohols, but these polymer polyatomic alcohols all do not have flame retardant resistance, do not have flame retardant resistance with its prepared polyurethane foam.
The urethane foam goods very easily burn, fire-retardant difficulty, and flame resistant method commonly used at present is to add fire retardant in the raw material of producing urethane mostly, used fire retardant mainly contains reaction-type flame-retarding polyether glycol and non-response type small molecules fire retardant; The reaction-type flame-retarding polyether glycol mainly is phosphorous chlorine polyether glycol, and is low with the prepared polyurethane foam cost of this polyether glycol height, bearing capacity; The kind of non-response type small molecules fire retardant mainly contains Sb
2O
3, liquid or solid compounds such as melamine class, phosphoric acid ester and chloride-based, use the non-reacted fire retardant of liquid, volatilize gradually with the use fire retardant of foam materials, flame retardant effect descends, environment causes certain harm side by side; Use the non-reactive flame retardant of solid can obviously increase the viscosity of polyether glycol, increase the foam process difficulty, reduce the percentage of open area of foams, and make the density of foams uneven up and down.This based flame retardant uses trouble, and difficulty mixes, large usage quantity, fire-retardant cost height.
U.S. Pat-4,214,055, US-3,953,393 use the fire resistant polymer polylol of two or more mix monomer copolymerization in vinylchlorid, vinylidene chloride, vinylbenzene, the vinyl cyanide, and prepare resistance combustion polyurethane foam with it.But the homopolymer of vinylchlorid, vinylidene chloride and multipolymer are normally heat-labile, emit deleterious hydrogen chloride gas in foaming process, and foaming machine is had corrodibility; Japanese Patent Jpn.Kokai.Tokyo.JP.0959, the employed fire-retardant thing of 341 disclosed fire resistant polymer polylols is a polyvinyl chloride, equally also is heat-labile; U.S. Pat-5,250,581 disclose with tribromo-benzene ethene and vinyl cyanide mix monomer copolymerization polymer polyatomic alcohol, have certain flame retardant resistance with the prepared urethane foam of this polymer polyatomic alcohol, but tribromo-benzene ethene synthesizes difficulty, price is high, is difficult to obtain; PCT.Int.Appl.WO.97,44,368 disclose with flame-retardant ethylene base monomer and vinylbenzene, acrylonitrile compolymer with following structure and have prepared fire resistant polymer polylol:
Wherein X is a bromine, is its flame-retardant composition; R is O-CH
2-C (OH) H-CH
2-O-CO-C (CH
3)=CH
2, be the copolymerization group.The fire-retardant monomeric bromine content of this bromated vinyl is lower, the preparation difficulty.And the dispersion agent that this patent is used is the polyether glycol of vinylsiloxane modification, its synthesis condition harshness, cost height.
The objective of the invention is to overcome above-mentioned defective, provide a kind of raw material to be easy to get, cost is low, Heat stability is good, flame retardant properties is excellent, viscosity is little, the fire resistant polymer polylol of easy foaming.
Another object of the present invention is to utilize fire resistant polymer polylol and polyether glycol, polymer polyatomic alcohol to mix foaming preparation resistance combustion polyurethane foam with any ratio.
The stable polymer colloidal dispersion system that fire resistant polymer polylol of the present invention is made up of the polyether glycol two-phase of the flame-retardant polymer microballoon of disperse phase and external phase.
The flame-retardant polymer microballoon of above-mentioned disperse phase be by the polyether glycol of one or more vinyl monomer, vinyl modification, flame-retardant ethylene base monomer polyether glycol mutually in free-radical polymerized formation.The structural unit that has following constitutional features in its copolymer molecule chain structure:
In the formula: R
1=H, CH
3, CH
2-CH
3, CH
2-CH
2-CH
3, CH (CH
3)
2, CH
2-CH
2-O-CO-CH=CH
2, CH
2=CH-CONH, CH
2-CH (OH)-CH
2-O-CO-CH=CH
2, CH
2-CH (OH)-CH
2-O-CO-C (CH
3)=CH
2, CH
2-CH=CH
2, CH
2-CH
2-CH=CH
2, CH
2-C (CH
3)=CH
2, CH
2-CH
2-C (CH
3)=CH
2In a kind of;
R
2=H, CH
3, CH
2-CH
3, CH
2-CH
2-CH
3, CH (CH
3)
2, CH
2-CH
2-O-CO-CH=CH
2, CH
2=CH-CONH, CH
2-CH (OH)-CH
2-O-CO-CH=CH
2, CH
2-CH (OH)-CH
2-O-CO-C (CH
3)=CH
2, CH
2-CH=CH
2, CH
2-CH
2-CH=CH
2, CH
2-C (CH
3)=CH
2, CH
2-CH
2-C (CH
3)=CH
2In a kind of.
X=F, Cl, Br, I; N=1,2,3,4; Be preferably X=Br, n=4.
At above-mentioned R
1, R
2In have at least one have can radical polymerization the carbon-carbon double bond group.Above-mentioned R
1, R
2Be respectively: CH
2-CH=CH
2, H, CH
2A kind of among the=CH-CONH.
The weight (solid content) of the flame-retardant polymer microballoon of the disperse phase in the above-mentioned polymeric colloid dispersion system accounts for 15%～45% of whole polymeric colloid dispersion system weight.
The viscosity of above-mentioned polymeric colloid dispersion system is at 1000mPas～5500mPas (25 ℃).
The particle diameter of above-mentioned disperse phase flame-retardant polymer microballoon (scanning electron microscopy particle diameter) is between 0.05 μ m～10 μ m.
Above-mentioned vinyl monomer can be vinylbenzene, alpha-methyl styrene, bromstyrol, methyl acrylate, ethyl propenoate, butyl methacrylate, vinyl cyanide, Alpha-Methyl vinyl cyanide, vinyl acetate, vinyl acetate between to for plastic, acrylamide etc. one or more have the monomer that carbon-carbon double bond can carry out radical polymerization.
The polyether glycol of above-mentioned external phase is homopolymer or the propylene oxide and the ethylene oxide copolymer of propylene oxide, and its functionality is between 2～8, and hydroxyl value is between 20mgKOH/g～700mgKOH/g, and proportion of primary OH groups is between 2%～95%.
The manufacture method of fire resistant polymer polylol of the present invention is as follows:
(1) with polyether glycol, join in the reactor that has agitator, thermometer and condensing reflux pipe, make temperature rise to 85 ℃～140 ℃.
(2) vinyl monomer, flame-proof ethylene base monomer, dispersion agent, initiator, polyether glycol are packed in the feeder, stir.
(3) feed liquid in the feeder is evenly added in the reactor, polyreaction under 85 ℃～140 ℃ temperature makes fire resistant polymer polylol.
Polyether glycol in above-mentioned (1), (2) is homopolymer or the propylene oxide and the ethylene oxide copolymer of propylene oxide, and its functionality is between 2～8, and hydroxyl value is between 20mgKOH/g～700mgKOH/g, and proportion of primary OH groups is between 5%～90%.
Dispersion agent in above-mentioned (2) is the polyether glycol of vinyl modification, and its add-on accounts for 6%～30% of whole vinyl monomer weight, preferably 8%～25%.
Vinyl monomer in above-mentioned (2) can be vinylbenzene, alpha-methyl styrene, bromstyrol, methyl acrylate, ethyl propenoate, butyl methacrylate, vinyl cyanide, Alpha-Methyl vinyl cyanide, vinyl acetate, vinyl acetate between to for plastic, acrylamide etc. one or more have the monomer that carbon-carbon double bond can carry out radical polymerization.
Flame-proof ethylene base monomer in above-mentioned (2) has following constitutional features.
R in the formula
1, R
2, X, n as previously mentioned.Its add-on adds with 0.3%～10% of all vinyl monomer weight according to different fire-retardant requirements.
Initiator in above-mentioned (2) is azo-initiator or peroxide initiator or the mixture of the two.
Above-mentioned azo-initiator is one or both mixtures in Diisopropyl azodicarboxylate, the 2,2'-Azobis(2,4-dimethylvaleronitrile).
Above-mentioned peroxide initiator is one or more mixtures in dicumyl peroxide, dibenzoyl peroxide, the peroxidized t-butyl perbenzoate.
The obtained fire resistant polymer polylol of the present invention has solid content height (greater than 40%), viscosity is low (under identical solid content condition, the low 300mPa.s of glutinous-Du Bi prior art), flame retardant properties is excellent, cost is low (under identical flame retardant effect condition, required bromine content is than prior art low 20%), the effect of Heat stability is good (heat decomposition temperature of flame-retardant polymer is up to 420 ℃).
Fire resistant polymer polylol of the present invention can be mixed with any ratio with polyether glycol, polymer polyatomic alcohol, again with diisocyanate prepared in reaction resistance combustion polyurethane foam.Contain the flame-retardant polymer microballoon in the resistance combustion polyurethane foam of preparation, its bromine content mostly is 1.6% of whole weight polyurethanes most, and fire-retardant rank is pressed combustion test standard batten 1.27 * 10.16 * 35.56cm of MVSS-302
3Test is better than the SE level.
The flame-retardant polyurethane foam is mainly used in automobile, train, motorcycle cushion, back cushion, the lining of Spring mattress carpet, and wrapping material and finishing material have performances such as bearing capacity height, rebound resilience be good, fire-retardant, and cost are low.
The foam process of preparation flame-retardant polyurethane can adopt traditional foam process such as manual foaming, flat-top foaming, vertical foaming and molding foaming.Its basic raw material consists of common polyether glycol, fire resistant polymer polylol of the present invention, diisocyanate, water, pneumatogen, tensio-active agent, oxidation inhibitor, anti-aging agent, organotin catalysts and tertiary amine catalyst.
The consumption of above-mentioned diisocyanate is calculated as follows:
Wherein: W
Always-required isocyanide ester gross weight, Kg
W
AlcoholThe gross weight Kg of polyvalent alcohol in the-prescription
The gross weight of water in the W-water prescription, Kg
The index of I-isocyanide ester
The equivalent of C-isocyanide ester
The purity of ρ-isocyanide ester
OH
nThe hydroxyl value mgKOH/g of-polyvalent alcohol wherein G of toluene diisocyanate (TDI) is 87, and the G of ditane diisocyanate (MDI) is 125
Above-mentioned OH
nHydroxyl value for common polyether glycol and flame retardant polyether polyol mixture
Above-mentioned I is calculated as follows:
I generally gets 85～130.
Above-mentioned organotin catalysts mainly contains organotin catalysts commonly used such as dibutyl tin laurate, two 2 ethyl hexanoic acid dibutyl tins, dibutyltin diacetate, stannous octoate, stannous oleate.
Above-mentioned tertiary amine catalyst mainly contains the Sanya ethylene diamine; Triethylamine; N, N, N ', N ＇-tetramethyl--1,3 ,-butanediamine; N-Ethylmorphine quinoline; Two (beta-dimethyl-amine ethyl) ether etc.
Above-mentioned pneumatogen mainly contains F
11, F
12, F
113Deng pneumatogen.
Basic recipe (weight part) is as follows:
Common polyether glycol: 100～0
Flame retardant polyether polyol of the present invention: 0～100
Water: 0～3.5
Stannous octoate: 0.1～0.3
Sanya ethylene diamine: 0.1～0.3
Silicone oil (tensio-active agent): 0.1～1.3
TDI index: 85～130
Have good bearing capacity and flame retardant resistance with the prepared urethane foam of fire resistant polymer polylol of the present invention, and cost is low.
Above-mentioned bearing capacity characterizes with 50% compressive hardness, progressively increase in the increase of its size under the same foam density conditions with fire resistant polymer polylol solid content of proportion and fire resistant polymer polylol in whole polyvalent alcohol, when flame-retardant polymer (solid content 40%) polyvalent alcohol consumption is 20% (accounting for the weight of polyvalent alcohol), its 50% compressive hardness increases by 100%; When consumption is 40%, its 50% compressive hardness increases more than 130%; When whole employing fire resistant polymer polylol, its bearing capacity can reach 5 times with common polyether glycol.The tensile strength of polyurethane foam and tear strength also increase with solid content and its ratio shared in whole polyvalent alcohol of fire resistant polymer polylol, and slightly increase respectively and bigger increase, but its rebound resilience then slightly reduces.
Above-mentioned Flame Retardancy of Polyurethane Foam is with the increase of content of halogen, and its fire-retardant rank is also got thereupon and improved.
Above-mentioned fire-retardant rank is according to combustion test standard batten 1.27 * 10.16 * 35.56cm of MVSS-302
3Test has following rank:
(1) DNI: can not light.
(2) SE: put out certainly, light, burning extent less than 3.81cm from putting out.
(3) SE/NBR602: light in 60 seconds and put out certainly, burning extent is greater than 3.81cm, less than 8.89cm.
(4) SE/BX: burn and put out certainly after 60 seconds, burning extent is greater than 8.89cm, less than 34.29cm.
(5) BX: can not put out certainly.
The present invention will be further described (below be weight part) below in conjunction with embodiment:
Embodiment 1: 1. in the reactor that thermometer, temperature controller, condenser and feeder are housed, add polyether glycol N330 (three-functionality-degree, hydroxyl value are propylene oxide, the ethylene oxide copolymer of 36mgKOH/g) 667 parts, be heated to 110 ℃.2. with 40.3 parts of the polyether glycols of 600 parts of vinylbenzene, vinyl modification, in 200 parts of vinyl cyanide, 8 parts of Diisopropyl azodicarboxylates, 30.1 parts of tetrabromophthalate allyl esters, 335 parts of adding feeders of polyether glycol N330.3. will the material in the feeder add in the reactor reaction 6 hours, after filtration, vacuumize, demonomerization and take off flavor after, obtain the fire resistant polymer polylol of white.Solid content is 43%, and viscosity is 5200mPas (25 ℃), bromine content 0.98%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 1 hurdle.
Embodiment 2: 1. in the reactor that thermometer, temperature controller, condenser and feeder are housed, add polyether glycol N330 (three-functionality-degree, hydroxyl value are propylene oxide, the ethylene oxide copolymer of 36mgKOH/g) 667 parts, be heated to 110 ℃.2. with 28 parts of the polyether glycols of 430 parts of vinylbenzene, vinyl modification, in 107 parts of vinyl cyanide, 5.5 parts of Diisopropyl azodicarboxylates, 30.1 parts of tetrabromophthalate allyl alcohol esters, 330 parts of adding feeders of polyether glycol N330.3. the material in the feeder was added reaction kettle for reaction after 6 hours, after filtration, vacuumize, demonomerization and take off flavor after, discharging obtains the fire resistant polymer polylol of white.Solid content is 34%, viscosity is 4240mPas (25 ℃), bromine content 1.33%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 2 hurdles.
Embodiment 3: feed way and feeding quantity just make polyether glycol N330 into polyether glycol 3050 (three-functionality-degree, hydroxyl value are the homopolymer of propylene oxide of 56mgKOH/g), the fire resistant polymer polylol that obtains with example 1.Solid content is 42.5%, viscosity 4960mPas (25 ℃), bromine content 0.97%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 3 hurdles.
Embodiment 4: feed way and feeding quantity just make polyether glycol N330 into polyether glycol 551C (three-functionality-degree, hydroxyl value are propylene oxide, the ethylene oxide copolymer of 56mgKOH/g), the fire resistant polymer polylol that obtains with example 1.Solid content is 41.5%, viscosity 5146mPas (25 ℃), bromine content 0.96%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 4 hurdles.
Embodiment 5: feed way and feeding quantity just make polyether glycol N330 into polyether glycol 3050 (three-functionality-degree, hydroxyl value are the homopolymer of propylene oxide of 56mgKOH/g) with example 2, and temperature of reaction is 140 ℃ of fire resistant polymer polylols that obtain.Solid content is 33%, viscosity 5900mPas (25 ℃), bromine content 1.4%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 5 hurdles.
Embodiment 6: feed way and feeding quantity just are decided to be 90 ℃ with temperature of reaction, the fire resistant polymer polylol that obtains with example 2.Solid content is 33.5%, viscosity 24055mPas (25 ℃), bromine content 1.34%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 6 hurdles.
Embodiment 7: feed way is with example 1, and the add-on that feeding quantity is removed the tetrabromophthalate allyl ester is 55 parts, and other add-ons are with example 1, the fire resistant polymer polylol that obtains.Solid content is 42.7%, viscosity 5310mPas (255 ℃), bromine content 1.79%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 7 hurdles.
Embodiment 8: feed way is with example 7, and feeding quantity is except that the add-on of tetrabromophthalate allyl ester is 90 parts, and other add-ons are with example 7, the fire resistant polymer polylol that obtains.Solid content is 43.5%, viscosity 5410mPas (25 ℃), bromine content 3%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 8 hurdles.
Embodiment 9 (comparison example): feed way is with example 8, and feeding quantity is except that the add-on of tetrabromophthalate allyl ester is 0 part, and other add-ons are with example 8, the fire resistant polymer polylol that obtains.Solid content is 43.5%, viscosity 5160mPas (25 ℃), bromine content 0%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 9 hurdles.
Embodiment 10 (comparison example): feed way is with example 4, and feeding quantity is except that the add-on of tetrabromophthalate allyl ester is 0 part, and other add-ons are with example 4, the fire resistant polymer polylol that obtains.Solid content is 42.5%, viscosity 5230mPas (25 ℃), bromine content 0%.See synthetic, the performance of fire resistant polymer polylol and use synopsis embodiment 10 hurdles.
Embodiment 11: with 50 parts of the foregoing description 1～8 prepared fire resistant polymer polylols, put into agitator respectively, add 50 parts of polyether glycols, 3.5 parts in water, 0.2 part of stannous octoate, 0.2 part of Sanya ethylene diamine, 0.9 part of silicone oil more respectively, stir, under 25 ℃～30 ℃ conditions, add 48 parts of toluene two different eyeball acid esters (TDI), high-speed stirring, pour into rapidly in the foam box then, foaming makes the flame-retardant polyurethane foam.Its performance is seen the synthetic of fire resistant polymer polylol, performance B and flame retardant resistance column in performance and the application synopsis.
Embodiment 12: with 50 parts of the foregoing description 9～10 prepared polymer polyatomic alcohols, put into agitator respectively, add 50 parts of polyether glycols, 3.5 parts in water, 0.2 part of stannous octoate, 0.2 part of Sanya ethylene diamine, 0.9 part of silicone oil more respectively, stir, under 25 ℃～30 ℃ conditions, add 51 parts of toluene two different eyeball acid esters (TDI), high-speed stirring, pour into rapidly in the foam box then, foaming makes the flame-retardant polyurethane foam.Its performance is seen the synthetic of fire resistant polymer polylol, performance B and flame retardant resistance column in performance and the application synopsis.
Synthetic, the performance of fire resistant polymer polylol and use synopsis
Annotate: the performance of performance A based polymer polyvalent alcohol, fire resistant polymer polylol.Annotate: performance B is a polyurathamc foamy performance.6# annotates: temperature of reaction is 90 ℃, can't foam because of viscosity is too high.TBPAE: be tetrabromophthalate allyl fat.
| Sample | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 # | ????7 | ????8 | ????9 | ???10 | |
| The still material | 3050/ part of 330/ part of 551c/ part | ?667 | ?667 | ?667 | ?667 | ?667 | ??667 | ????667 | ????667 | ????667 | ???667 |
| Reinforced | 3050/ part of dispersant of 330/ part of 551c/ part/part AIBN/ part TBPAE/ part styrene/part acrylonitrile/part | ?335 ?40.3 ?8 ?30.1 ?600 ?200 | ?330 ?28 ?5.5 ?30.1 ?430 ?107 | ?335 ?40.3 ?8 ?30.1 ?600 ?200 | ?335 ?40.3 ?8 ?30.1 ?600 ?200 | ?330 ?28 ?5.5 ?30.1 ?430 ?107 | ??335 ??28 ??5.5 ??30.1 ??430 ??107 | ????335 ????40.3 ????8 ????55 ????600 ????200 | ????335 ????40.3 ????8 ????90 ????600 ????200 | ????335 ????40.3 ????8 ????0 ????000 ????200 | ???335 ???40.3 ???8 ???0 ???600 ???200 |
| Performance A | Viscosity/mPa.s bromine content/% solid content/% | ?5200 ?0.98 ?43 | ?4240 ?1.33 ?34 | ?4960 ?0.97 ?42.5 | ?5146 ?0.96 ?41.5 | ?5900 ?1.4 ?33 | ??24055 ??1.34 ??33.5 | ????5310 ????1.79 ????42.7 | ????5410 ????3 ????43.5 | ????5160 ????0 ????43.5 | ???5230 ???0 ???42.5 |
| Performance B | 50% hardness/Kpa tensile strength/Kpa tear strength/Ncm -1 | ?14.6 ?115 ?6.8 | ?9.5 ?113 ?6.3 | ?13.5 ?116 ?6.9 | ?14 ?118 ?7.0 | ?10 ?110 ?6.5 | ??-- ??-- ??-- | ????14.7 ????115 ????7.1 | ????15 ????114 ????7.4 | ????14.2 ????117 ????7.15 | ???13.6 ???113 ???7.2 |
| Flame retardant resistance | Fire-retardant rank | ?SE/NB ?R602 | ?SE | ?SE/NB ?R602 | ?SE/NB ?R602 | ?SE | ??-- | ????SE | ????SE | Not fire-retardant | Not fire-retardant |
Claims (10)
1. a fire resistant polymer polylol is characterized in that, the stable polymer colloidal dispersion system that this fire resistant polymer polylol is made up of disperse phase flame-retardant polymer microballoon and external phase polyether glycol two-phase; The structural unit that wherein has following constitutional features on the flame-retardant polymer microballoon molecular chain structure:
In the formula: X=F, Cl, Br, I; N=1,2,3,4;
R
1=H, CH
3, CH
2-CH
3, CH
2-CH
2-CH
3, CH (CH
3)
2, CH
2-CH
2-O-CO-CH=CH
2, CH
2=CH-CONH, CH
2-CH (OH)-CH
2-O-CO-CH=CH
2, CH
2-CH (OH)-CH
2-O-CO-C (CH
3)=CH
2, CH
2-CH=CH
2, CH
2-CH
2-CH=CH
2, CH
2-C (CH
3)=CH
2, CH
2-CH
2-C (CH
3)=CH
2In a kind of;
R
2=H, CH
3, CH
2-CH
3, CH
2-CH
2-CH
3, CH (CH
3)
2, CH
2-CH
2-O-CO-CH=CH
2, CH
2=CH-CONH, CH
2-CH (OH)-CH
2-O-CO-CH=CH
2, CH
2-CH (OH)-CH
2-O-CO-C (CH
3)=CH
2, CH
2-CH=CH
2, CH
2-CH
2-CH=CH
2, CH
2-C (CH
3)=CH
2, CH
2-CH
2-C (CH
3)=CH
2In a kind of.
2. fire resistant polymer polylol according to claim 1, it is characterized in that, described flame-retardant polymer microballoon be by the polyether glycol of one or more vinyl monomer, vinyl modification, flame-retardant ethylene base monomer polyether glycol mutually in free-radical polymerized formation.
3. fire resistant polymer polylol according to claim 1, it is characterized in that, the polyether glycol of described external phase is homopolymer or the propylene oxide and the ethylene oxide copolymer of propylene oxide, its functionality is between 2～8, hydroxyl value is between 20mgKOH/g～700mgKOH/g, and proportion of primary OH groups is between 2%～95%.
4. fire resistant polymer polylol according to claim 1 is characterized in that, the viscosity of described polymeric colloid dispersion system is 1000mPa.s～5500mPa.s (25 ℃).
5. fire resistant polymer polylol according to claim 1 and 2, it is characterized in that, the weight (solid content) of the flame-retardant polymer microballoon of described disperse phase account for whole polymeric colloid dispersion system heavy 15%～45%, the particle diameter of flame-retardant polymer microballoon is between 0.05 μ m～10 μ m.
6. fire resistant polymer polylol according to claim 1 is characterized in that, described X=Br, n=4.
7. fire resistant polymer polylol according to claim 1 is characterized in that, described R
1, R
2Have at least one have can radical polymerization the carbon-carbon double bond group.
8. according to claim 1 or 7 described fire resistant polymer polylols, it is characterized in that described R
1, R
2Be respectively: CH
2-CH=CH
2, H, CH
2A kind of among the=CH-CONH.
9. fire resistant polymer polylol according to claim 2, it is characterized in that, described vinyl monomer can be vinylbenzene, alpha-methyl styrene, bromstyrol, methyl acrylate, ethyl propenoate, butyl methacrylate, vinyl cyanide, Alpha-Methyl vinyl cyanide, vinyl acetate, vinyl acetate between to for plastic, acrylamide etc. one or more have the monomer that carbon-carbon double bond can carry out radical polymerization.
10. according to any one the described fire resistant polymer polylol in the claim 1～9, it is characterized in that, this fire resistant polymer polylol can be mixed with any ratio with polyether glycol, polymer polyatomic alcohol, again with diisocyanate prepared in reaction resistance combustion polyurethane foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991120353A CN1133682C (en) | 1999-01-22 | 1999-01-22 | Fire resistant polymer polylol and its use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991120353A CN1133682C (en) | 1999-01-22 | 1999-01-22 | Fire resistant polymer polylol and its use |
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| Publication Number | Publication Date |
|---|---|
| CN1228446A true CN1228446A (en) | 1999-09-15 |
| CN1133682C CN1133682C (en) | 2004-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991120353A Expired - Fee Related CN1133682C (en) | 1999-01-22 | 1999-01-22 | Fire resistant polymer polylol and its use |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101704937B (en) * | 2009-11-10 | 2011-12-28 | 航天材料及工艺研究所 | Low-fluoride polyurethane foaming plastic for insulating heat at low temperature |
| CN102585140A (en) * | 2011-01-13 | 2012-07-18 | 嘉纳尔科技（北京）有限公司 | Flame retardant polyurethane composition, flame retardant polyurethane foam material and method for preparing same |
| CN102618054A (en) * | 2011-01-31 | 2012-08-01 | 韩财元 | Technology for increasing flame retardant performance of plastic by microbubbles |
| CN102659996A (en) * | 2012-04-17 | 2012-09-12 | 深圳市国志汇富高分子材料股份有限公司 | High-efficiency, no-molten droplet and flame-resistant reticulated polyurethane foam plastic and preparation technology thereof |
| CN106496437A (en) * | 2015-09-06 | 2017-03-15 | 万华化学集团股份有限公司 | A kind of fire resistant polymer polylol and its preparation method and application |
| WO2018010630A1 (en) * | 2016-07-12 | 2018-01-18 | 佳化化学科技发展（上海）有限公司 | Composition capable of substituting use of styrene-acrylonitrile copolymer pop |
| CN109762223A (en) * | 2016-12-07 | 2019-05-17 | 中广核高新核材科技（苏州）有限公司 | Manufacturing process for low smoke and non-toxic Flame-Retardant and Oil-Resistant type CABLE MATERIALS |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1295266C (en) * | 2004-09-30 | 2007-01-17 | 青岛科技大学 | Preparation method of fire retardant high activity polymer polyether polyol and method for preparing high elastic resilience fire retardant golyurethane soft foam material therefrom |
| CN1308373C (en) * | 2004-09-30 | 2007-04-04 | 青岛科技大学 | Preparation method of fire retardant polymer polyether polyol and method for preparing block fire retardant polyurethane foam mateial therefrom |
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1999
- 1999-01-22 CN CNB991120353A patent/CN1133682C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704937B (en) * | 2009-11-10 | 2011-12-28 | 航天材料及工艺研究所 | Low-fluoride polyurethane foaming plastic for insulating heat at low temperature |
| CN102585140A (en) * | 2011-01-13 | 2012-07-18 | 嘉纳尔科技（北京）有限公司 | Flame retardant polyurethane composition, flame retardant polyurethane foam material and method for preparing same |
| CN102618054A (en) * | 2011-01-31 | 2012-08-01 | 韩财元 | Technology for increasing flame retardant performance of plastic by microbubbles |
| CN102659996A (en) * | 2012-04-17 | 2012-09-12 | 深圳市国志汇富高分子材料股份有限公司 | High-efficiency, no-molten droplet and flame-resistant reticulated polyurethane foam plastic and preparation technology thereof |
| CN106496437A (en) * | 2015-09-06 | 2017-03-15 | 万华化学集团股份有限公司 | A kind of fire resistant polymer polylol and its preparation method and application |
| CN106496437B (en) * | 2015-09-06 | 2018-08-28 | 万华化学集团股份有限公司 | A kind of fire resistant polymer polylol and its preparation method and application |
| WO2018010630A1 (en) * | 2016-07-12 | 2018-01-18 | 佳化化学科技发展（上海）有限公司 | Composition capable of substituting use of styrene-acrylonitrile copolymer pop |
| US11261287B2 (en) | 2016-07-12 | 2022-03-01 | Jiahua Science & Technology Development (Shanghai) Ltd. | Composition capable of substituting use of styrene-acrylonitrile copolymer POP |
| CN109762223A (en) * | 2016-12-07 | 2019-05-17 | 中广核高新核材科技（苏州）有限公司 | Manufacturing process for low smoke and non-toxic Flame-Retardant and Oil-Resistant type CABLE MATERIALS |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1133682C (en) | 2004-01-07 |
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