CN102329408B - Flame-retardant rigid polyurethane foam prepared by taking ionic liquid as flame retardant agent - Google Patents
Flame-retardant rigid polyurethane foam prepared by taking ionic liquid as flame retardant agent Download PDFInfo
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Abstract
The invention discloses a flame-retardant rigid polyurethane foam prepared by taking an ionic liquid as a flame retardant agent, which mainly solves the technical problem that in the prior art, the physical properties of a rigid polyurethane foam are affected because of adding a flame retardant agent. The flame-retardant rigid polyurethane foam is prepared through the following steps of: firstly, after weighing a black material (diisocyanate) and a white material (comprising polyether polyol, water, a catalyst, a surfactant, and other additives), pouring the materials into different containers for later use, weighing a flame retardant agent and then adding the flame retardant agent into the white material, wherein the flame retardant agent accounts for 15%, 20%, 25% or 30% of the white material by mass; then, pouring the black material into the white material to mix uniformly, stirring the obtained mixture until the foaming reaction has started 10 seconds, then, immediately injecting the obtained object in a mold, and after carrying out a chemical reaction and foaming on the obtained object, obtaining a rigid polyurethane foam plastic; and finally, carrying out curing on the rigid polyurethane foam plastic for 24 hours at a temperature of 30-40 DEG C, and then carrying out a flame-retardant performance test on the obtained product. In the invention, the ionic liquid is taken as the flame retardant agent of the rigid polyurethane foam for the first time, and has good compatibility with polyurethane foaming materials. The flame-retardant rigid polyurethane foam disclosed by the invention is simple in foaming operation and high in thermal stability, and the occurrence of a core scorching phenomenon in the process of curing is avoided; and the flame-retardant rigid polyurethane foam has the characteristics of less smoke generation, small toxicity, good self-extinguishment, and prolonged service life. The polyurethane foam is a new environmentally-friendly material.
Description
Technical field
The present invention relates to a kind of flame retarded rigid polyurethane foams, particularly a kind of flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant belongs to fire retardant material manufacturing and applied technical field.
Background technology
Hard polyurethane foam is a kind of macromolecular material of superior performance, because polyurethane foam has advantages such as good heat insulating, easy processing, light weight, easy construction, so its range of application very extensively, almost is applied to national economy all departments.Because this thermal insulation of materials is effective; Physical strength is high; Electric property, resistance to chemical corrosion and soundproof effect are good, make it in many engineerings fields such as furniture, automotive trim, building heat preservation, household electrical appliances the irreplaceable effect of other materials arranged, particularly aspect building heat preservation; Because the requirement of world energy sources shortage and energy conservation object; Aspect building, not only be widely used in the Industrial buildings facility, but also be applied in the body of wall of covil construction facility more and more and roof heat insulation is heat insulation and the building air conditioning tubing system on, urethane foam is the unique New Building Materials of a kind of function.Because urethane foam has unrivaled advantage at aspects such as insulation, heat insulation, sound insulations, it is widely used in various large common facilities and luxurious hotel, restaurant.But as other macromolecular materials, be combustible in air without the urethane of fire-retardant finish, its limiting oxygen index(LOI) (LOI) has only about 18; Lighted easily having under the situation of burning things which may cause a fire disaster, propagation of flame is rapid, and follows the generation of a large amount of flue gases; Domestic many in recent years fire are all caused by urethane foam; And caused heavy losses, and the inflammableness of hard polyurethane foam has limited its use occasion, and the development of its flame-retarded technology has received increasing concern.Flame resistant method report about polyurethane material is a lot of at present, and fire retardant commonly used is divided into additive flame retardant and reactive flame retardant, and the research of additive flame retardant at present is more, and the additive flame retardant major part is to add the compound that contains halogen, phosphorus, antimony etc.
The full phosphorus fire retardant of employings such as Luo Zhenyang (DMMP, DEEP, V6), halogenated phosphate fire retardant (TCEP, TCPP, TDCP) and the two are composite carries out flame-retardant modified to rigid urethane foam; Test result proves that the flame retardant effect of full phosphorus fire retardant is superior to the halogenated phosphate based flame retardant, and phosphorus halogen compositional flame-retardant effect is superior to single fire retardant.Though phosplate and phosphonic acid ester have obtained widespread use in the PU industry, be the main fire retardant that uses in the domestic PU foam materials, because their relative molecular masses are little; Consumption is big; There is migration at material internal, has plastification simultaneously concurrently, can be to the material property deleterious impact.It is raw material that Peng Zhi etc. adopt polyvalent alcohol, isocyanic ester, catalyzer, whipping agent and fire retardant etc.; Prepared full water foamed flame retardant polyurethane rigid foam; Test result shows that polyester polyol can improve foam structure, but can reduce compressive strength and dimensional stability; The water foaming agent consumption is unsuitable too high; Isocyanate index was at 1.1～1.2 o'clock, and foamy compressive strength, dimensional stability etc. are better; Additive flame retardant three (2-chloro isopropyl) SULPHOSUCCINIC ACID ESTER (TCPP) can give material certain flame retardant resistance, but influential to foam structure, compressive strength and dimensional stability.Alkylhalide group phosphate flame retardant commonly used; Good, cheap like 3 (β-chloroethyl) SULPHOSUCCINIC ACID ESTERs and foaming component consistency, but because poor heat stability can cause the burning core in the foam maturing process; Foam there is plastification, influences the physicals of hard polyurethane foams.
Summary of the invention
The objective of the invention is deficiency, and a kind of flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant is provided to above-mentioned prior art.Ionic liquid has non-volatile or zero vp, wide boiling range, high heat capacity and thermal energy storage density; High thermal stability has characteristics such as selective dissolution power and designability, synthetic; Catalysis, biocatalysis, stripping technique; Electrochemistry, aspects such as analytical chemistry and nano science have obtained extensive studies.Ion liquid high thermal stability and self uninflammability ability make it have the good flame performance.But particular study is not also carried out in the application about high thermal stability, and the present invention utilizes ion liquid high thermal stability first, and it is applied in the hard polyurethane foam flame-retarded technology as fire retardant.Not only overcome the defective that the phosphorus flame retardant volatility is big, thermotolerance is not high relatively, also overcome the big shortcoming of the halogenated flame retardant amount of being fuming simultaneously.Ionic liquid self non-volatility, nontoxic is a kind of environmental friendliness, a flame retardant properties BACN preferably simultaneously.
The objective of the invention is to realize: a kind of flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant through following technical proposals; After will deceiving material and the accurate weighing of white material, be poured into different containers for future use, the fire retardant of the different mass per-cent of accurate weighing is joined in the white material; To deceive then and expect that being poured into white material mixes; After being stirred to foamable reaction and beginning 10s, inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam.The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last.
Above-mentioned black material is selected vulcabond for use.
The composition of above-mentioned white material (quality share): polyether glycol 70 ~ 100; Organic silicone oil suds-stabilizing agent 4 ~ 6; Catalyzer is that dipropylene glycol solution and the dibutyl tin laurate by 33% triethylene diamine mixes, and wherein the dipropylene glycol solution of tin class catalyzer 0.1 ~ 0.2,33% triethylene diamine is 0.2 ~ 0.4; Whipping agent adopts F11, and the quality share is 1.5 ~ 3.5; Water 4 ~ 7.
The usage ratio of above-mentioned white material and black material is 1:1 ~ 1.1.
Above-mentioned fire retardant is selected two substituted alkyl glyoxaline ion liquids for use, and wherein alkyl chain length is C
4~ C
16Alkyl, negatively charged ion is tetrafluoroborate or hexafluoro-phosphate radical (as: 1 monobutyl, one 3 monomethyl miaow a tetrafluoro borates, 1 one hexyls, one 3 monomethyl miaow hexafluorophosphates, l one octyl group one 3 monomethyl imidazoles hexafluorophosphates, l monobutyl one 3 monomethyl imidazoles hexafluorophosphates etc.).
The fire retardant of above-mentioned different mass per-cent is respectively 15%, 20%, 25%, 30% of white material quality.
The present invention compared with prior art has the following advantages:
(1) utilize the fire retardant of ionic liquid as hard polyurethane foams first, ionic liquid self is nontoxic, and flame retardant effect is better.
(2) ionic liquid among the present invention is the colourless transparent liquid shape, and density is low, and good with polyurethane foam material consistency, foaming operation is simple.
(3) the present invention self thermostability is high, can in the foam maturing process, not cause to burn the core phenomenon.
(4) do not have volatility, can from goods, not emanate, increase the working life of flame retarded rigid polyurethane foams as additive flame retardant.
(5) adopt the flame retarded rigid polyurethane foams of ionic liquid as fire retardant, its amount of being fuming reduces greatly, no fusion dropping in the combustion processes, and self-extinguishing time significantly reduces, and is a kind of eco-friendly novel flame-retardant hard polyurethane foams.
Description of drawings
Fig. 1 is a flame retarded rigid polyurethane foams TG curve of the present invention.
Fig. 2 is a flame retarded rigid polyurethane foams DTA curve of the present invention.
As shown in Figure 1, be 0% to the A flame retardant agent content; B fire retardant (l monobutyl one 3 monomethyl imidazoles hexafluorophosphates) content is that 25% hard polyurethane foams carries out thermogravimetric analysis, and data are shown in figure.To no fire retardant and flame retardant agent content is that 25% hard polyurethane foams carries out thermogravimetric analysis.
From thermogravimetric curve, can find out; The weightlessness of hard polyurethane foams is two stages; Do not have the tangible fire retardant zero-g period, can find out that the ionic liquid thermostability is fine, decomposition temperature is higher; L monobutyl one 3 monomethyl imidazoles hexafluorophosphates generally begin to decompose about 300 ℃, and are approaching with the temperature that hard polyurethane foams begins to decompose.The weightless fs of hard polyurethane foams of containing fire retardant is at 250 ℃ ~ 360 ℃, and rate of weight loss is about about 32.5%, has 25.1% decompose residues remaining during to 775 ℃; And the weightless fs of the hard polyurethane foams that does not add fire retardant is at 240 ℃ ~ 400 ℃; Rate of weight loss is about about 46.3%, has 11.25% decompose residues remaining during to 775 ℃, this shows ion liquid interpolation; Can improve temperature of initial decomposition; Can effectively stop the decomposition course of TDI in the urethane, reduce the rate of weight loss of fs effectively, and little to the decomposition influence of polyvalent alcohol.
As shown in Figure 2, be 0% to the A flame retardant agent content; B fire retardant (l monobutyl one 3 monomethyl imidazoles hexafluorophosphates) content is 25% hard polyurethane foams; Can find out by the DTA curve; The quantity of the exothermic peak of the hard polyurethane foams of interpolation fire retardant increases to some extent, shows that ionic liquid decomposes about 300 ℃ ~ 400 ℃, and is weightless corresponding each other with the fs in the TG curve; The peak area of exothermic peak that adds the hard polyurethane foams of fire retardant in addition is less than the exothermic peak peak area of the hard polyurethane foams of no fire retardant; Thermal discharge reduces greatly, this shows, has the ion liquid adding of high thermal stability; Effectively suppress the decomposition of rigid foam at foam inside, improved the thermostability of hard polyurethane foams.
Embodiment
Embodiment one: a kind of flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant; After 1.1 parts (weight quota) black material (vulcabond) and 1 part (weight quota) are expected accurate weighing in vain; Be poured into different containers for future use; The fire retardant that weighing is accounted for white material 15% (mass percent) joins in the white material, will deceive material then and pour in the white material and mix, after being stirred to foamable reaction and beginning 10s; Inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam.The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last.Said fire retardant is 1 monobutyl, one 3 monomethyl miaow a tetrafluoro borates.
Embodiment two: a kind of flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant; After 1 part (weight quota) black material (vulcabond) and 1 part (weight quota) expected accurate weighing in vain; Be poured into different containers for future use; The fire retardant that weighing is accounted for white material 20% (mass percent) joins in the white material, will deceive material then and pour in the white material and mix, after being stirred to foamable reaction and beginning 10s; Inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam.The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last.Said fire retardant is 1 one hexyls, one 3 monomethyl miaow hexafluorophosphates.
Embodiment three: a kind of flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant; After 1 part (weight quota) black material (vulcabond) and 1 part (weight quota) expected accurate weighing in vain; Be poured into different containers for future use; The fire retardant that weighing is accounted for white material 25% (mass percent) joins in the white material, will deceive material then and pour in the white material and mix, after being stirred to foamable reaction and beginning 10s; Inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam.The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last.Said fire retardant is l one octyl group one 3 monomethyl imidazoles hexafluorophosphates.
Embodiment four: a kind of flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant; After 1 part (weight quota) black material (vulcabond) and 1 part (weight quota) expected accurate weighing in vain; Be poured into different containers for future use; The fire retardant that weighing is accounted for white material 30% (mass percent) joins in the white material, will deceive material then and pour in the white material and mix, after being stirred to foamable reaction and beginning 10s; Inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam.The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last.Said fire retardant is l monobutyl one 3 monomethyl imidazoles hexafluorophosphates.
Embodiment five: a kind of flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant; After will deceiving material (vulcabond) and the accurate weighing of white material, be poured into different containers for future use, accurately the fire retardant gradation of weighing different mass per-cent joins in the white material at every turn; To deceive then and expect that being poured into white material mixes; After being stirred to foamable reaction and beginning 10s, inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam.The hard polyurethane foams that slaking made after 24 hours under 30 ℃ ~ 40 ℃ situation at last, preparation growth 150mm, wide 10mm; The sample of thick 10mm carries out the mensuration of oxygen index; Minimum 15 of sample size, nitrogen, oxygen pressure are 0.1 ± 0.01MPa in the mensuration process, nitrogen, oxygen mix flow are 10L ± 0.5L/min; Use the top to light method, the time of flame interaction is the longest to be 30S.The hard polyurethane foams that makes is prepared into preparation growth 130mm, wide 13mm, and the sample of thick 10mm carries out horizontal burning test, and it is 30S that sample is executed the flame time.The powdered sample that the hard polyurethane foams that makes prepares 8mg carries out heat analysis, and TR is: 22 ℃ ~ 800 ℃ temperature rise rates are: 20 ℃/min.The fire retardant of above-mentioned different mass per-cent is respectively 15%, 20%, 25%, 30% of white material quality.
Embodiment six: accurately measure black material of 30g (vulcabond) and 30g and expect in vain; Be poured into different containers for future use respectively; Distinguishing accurate weighing then expects in vain that the l monobutyl one 3 monomethyl imidazoles hexafluorophosphates of 15% (4.5g) of quality join in the white material as fire retardant and mixes; To deceive material then and be poured in the white material and stir, after being stirred to foamable reaction and beginning 10s, inject mould immediately; Through chemical reaction and foaming, the hard polyurethane foams that slaking made after 24 hours under 30 ℃ ~ 40 ℃ situation.And then the mass content that adopts l monobutyl one 3 monomethyl imidazoles hexafluorophosphates respectively is respectively 20% (6g), 25% (7.5g), 30% (9g) and repeats above-mentioned experimentation; The hard polyurethane foams that makes is carried out the combustionproperty test, and the limiting oxygen index determination data see the following form one:
Table one
The horizontal firing speed data is seen table two:
Table two
The composition of above-mentioned white material (quality share): polyether glycol 70 ~ 100; Organic silicone oil suds-stabilizing agent 4 ~ 6; Catalyzer is that dipropylene glycol solution and the dibutyl tin laurate by 33% triethylene diamine mixes, and wherein the dipropylene glycol solution of tin class catalyzer 0.1 ~ 0.2,33% triethylene diamine is 0.2 ~ 0.4; Whipping agent adopts F11, and the quality share is 1.5 ~ 3.5; Water 4 ~ 7.
The compound method of above-mentioned l monobutyl one 3 monomethyl imidazoles hexafluorophosphates: [BMIM] Br of 0.1mol is dissolved in the 200ml beaker that fills 100ml zero(ppm) water; Carry out magnetic agitation simultaneously; Slowly splash into the 16ml phosphofluoric acid; Leave standstill behind the stirring at room 2h to liquid and be divided into two phases; Take off a layer golden yellow oily liquids and be dissolved in a spot of methylene dichloride mutually, add zero(ppm) water and wash, the water after each washing splashes into silver sulfate solution and when not having generation of xanchromatic AgBr deposition and the test of PH test paper to show neutral, stops washing.Stop to get 125 ℃ of vacuum-drying 24h in the organic phase vacuum drying oven after the washing, obtaining weak yellow liquid promptly is [BMIM] PF
6
The JF-3 type limiting oxygen index determination appearance that the oxygen index of flame retardant polyurethane of the present invention is to use Nanjing Jiangning District analytical instrument factory to produce is tested.Horizontal firing speed is to adopt the CZF-3 horizontal vertical burning determinator of Nanjing Jiangning District analytical instrument factory to measure.Thermogravimetric analysis adopts the comprehensive thermal analyzer of HCT-1 of Beijing permanent scientific instrument factory to analyze.
Claims (8)
1. flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant; After will deceiving material and the accurate weighing of white material, be poured into different containers for future use, the fire retardant of accurate weighing is joined in the white material; To deceive then and expect that being poured into white material mixes; After being stirred to foamable reaction and beginning 10s, inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam; The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last, and the usage ratio of above-mentioned white material and black material is 1: 1-1.1; Above-mentioned black material adopts vulcabond; Above-mentioned white material is formed with the quality share: polyether glycol 70 ~ 100; Organic silicone oil suds-stabilizing agent 4 ~ 6; Catalyzer is that dipropylene glycol solution and the dibutyl tin laurate by 33% triethylene diamine mixes, and wherein the dipropylene glycol solution of tin class catalyzer 0.1 ~ 0.2,33% triethylene diamine is 0.2 ~ 0.4; Whipping agent adopts F11, and the quality share is 1.5 ~ 3.5; Water 4 ~ 7, its fire retardant are selected two substituted alkyl glyoxaline ion liquids for use, and wherein alkyl chain length is C
4~ C
16Alkyl, negatively charged ion is tetrafluoroborate or hexafluoro-phosphate radical, that is: 1-butyl-3-methyl miaow a tetrafluoro borate; 1-hexyl-3-methyl miaow hexafluorophosphate; L-octyl group-3-Methylimidazole hexafluorophosphate; L-butyl-3-Methylimidazole hexafluorophosphate.
2. the flame retarded rigid polyurethane foams that utilizes ionic liquid as fire retardant as claimed in claim 1, its fire retardant consumption accounts for 15%, 20%, 25% or 30% of white material quality respectively.
According to claim 1 or claim 2 utilize the flame retarded rigid polyurethane foams of ionic liquid as fire retardant; Weight share is poured into different containers for future use after deceiving material and the accurate weighing of 1 part of white material with 1.1 parts, and the fire retardant that weighing is accounted for white material quality 15% joins in the white material; To deceive then and expect to pour in the white material to mix; After being stirred to foamable reaction and beginning 10s, inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam; The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last, and said fire retardant is 1-butyl-3-methyl imidazolium tetrafluoroborate.
According to claim 1 or claim 2 utilize the flame retarded rigid polyurethane foams of ionic liquid as fire retardant; Weight share is poured into different containers for future use after deceiving material and the accurate weighing of 1 part of white material with 1 part, and the fire retardant that weighing is accounted for white material quality 20% joins in the white material; To deceive then and expect to pour in the white material to mix; After being stirred to foamable reaction and beginning 10s, inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam; The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last, and said fire retardant is 1-hexyl-3-Methylimidazole hexafluorophosphate.
According to claim 1 or claim 2 utilize the flame retarded rigid polyurethane foams of ionic liquid as fire retardant; Weight share is poured into different containers for future use after deceiving material and the accurate weighing of 1 part of white material with 1 part, and the fire retardant that weighing is accounted for white material quality 25% joins in the white material; To deceive then and expect to pour in the white material to mix; After being stirred to foamable reaction and beginning 10s, inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam; The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last, and said fire retardant is l-octyl group-3-Methylimidazole hexafluorophosphate.
According to claim 1 or claim 2 utilize the flame retarded rigid polyurethane foams of ionic liquid as fire retardant; Weight share is poured into different containers for future use after deceiving material and the accurate weighing of 1 part of white material with 1 part, and the fire retardant that weighing is accounted for white material quality 30% joins in the white material; To deceive then and expect to pour in the white material to mix; After being stirred to foamable reaction and beginning 10s, inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam; The flame retardant properties test is carried out in slaking after 24 hours under 30 ℃ ~ 40 ℃ situation at last, and said fire retardant is l-butyl-3-Methylimidazole hexafluorophosphate.
According to claim 1 or claim 2 utilize the flame retarded rigid polyurethane foams of ionic liquid as fire retardant, will deceive material and the accurate weighing of white material at every turn after, be poured into different containers for future use; Accurately the fire retardant gradation of weighing different mass per-cent joins in the white material, will deceive material then and be poured into white material and mix, after being stirred to foamable reaction and beginning 10s; Inject mould immediately, after chemical reaction and foaming, promptly obtain rigid urethane foam, the hard polyurethane foams that slaking made after 24 hours under 30 ℃ ~ 40 ℃ situation at last; Preparation growth 150mm, wide 10mm, the sample of thick 10mm carries out the mensuration of oxygen index; Minimum 15 of sample size, nitrogen, oxygen pressure are 0.1 ± 0.01MPa in the mensuration process, nitrogen, oxygen mix flow are 10L ± 0.5L/min; Use the top to light method, the time of flame interaction is the longest to be 30S, and the hard polyurethane foams that makes is prepared into preparation growth 130mm; Wide 13mm; The sample of thick 10mm carries out horizontal burning test, and it is 30S that sample is executed the flame time, and the powdered sample that the hard polyurethane foams that makes prepares 8mg carries out heat analysis; TR is: 22 ℃ of-800 ℃ of temperature rise rates are: 20 ℃/min, the fire retardant of above-mentioned different mass per-cent is respectively 15%, 20%, 25%, 30% of white material quality.
According to claim 1 or claim 2 utilize the flame retarded rigid polyurethane foams of ionic liquid as fire retardant; Accurately measuring black material of 30g and 30g expects in vain; Be poured into different containers for future use respectively, l-butyl-3-Methylimidazole hexafluorophosphate that accurate then weighing accounts for white material quality 15% joins in the white material as fire retardant and mixes, and will deceive then and expect to be poured in the white material to stir; After being stirred to foamable reaction and beginning 10s; Inject mould immediately, through chemical reaction and foaming, slaking made hard polyurethane foams after 24 hours under 30 ℃ ~ 40 ℃ situation; Adopt the l-butyl-3-Methylimidazole hexafluorophosphate that accounts for white material quality 20%, 25% or 30% respectively again, repeat above-mentioned foam process process.
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| CN105440652B (en) * | 2015-12-25 | 2018-12-04 | 青岛科技大学 | A kind of flame retardant thermoplastic polyurethane elastomer and preparation method thereof |
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| CN106751585A (en) * | 2016-12-28 | 2017-05-31 | 宁波优科泰科技发展有限公司 | A kind of flame retardant plastics using ionic liquid as fire retardant and preparation method thereof |
| CN106633702A (en) * | 2016-12-28 | 2017-05-10 | 宁波优科泰科技发展有限公司 | Flame-retardant plastic using ionic liquid as flame retardant and preparation method thereof |
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| CN111808256A (en) * | 2020-07-31 | 2020-10-23 | 湖南省普力达高分子新材料股份有限公司 | High-density conductive polyurethane foam, preparation method thereof and adhesive tape |
| CN116478527A (en) * | 2023-06-25 | 2023-07-25 | 潍坊潍星联合橡塑有限公司 | Flame-retardant polyurethane cable outer sheath material |
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| 李思源等.1-丁基-3-甲基咪唑甲磺酸盐离子液体对聚碳酸酯阻燃性能及热降解行为的影响.《高分子通报》.2010,(第11期),第76-82页. * |
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