CN107286316A - A kind of enhanced resistance combustion polyurethane foam and preparation method - Google Patents

A kind of enhanced resistance combustion polyurethane foam and preparation method Download PDF

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Publication number
CN107286316A
CN107286316A CN201710589015.XA CN201710589015A CN107286316A CN 107286316 A CN107286316 A CN 107286316A CN 201710589015 A CN201710589015 A CN 201710589015A CN 107286316 A CN107286316 A CN 107286316A
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polyurethane foam
preparation
resistance combustion
enhanced resistance
combustion polyurethane
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陈庆
曾军堂
陈兵
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Chengdu New Keli Chemical Science Co Ltd
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Chengdu New Keli Chemical Science Co Ltd
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    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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    • 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
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    • 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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    • 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
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
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    • C08J2203/00—Foams characterized by the expanding agent
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    • C08J2375/08—Polyurethanes from polyethers

Abstract

The present invention relates to macromolecule modified technical field, more particularly to a kind of enhanced resistance combustion polyurethane foam and preparation method, the preparation method of the enhanced resistance combustion polyurethane foam comprise the following steps：（1）The modification of epoxy resin；（2）The preparation of modified polyether；（3）After modified polyether, foaming agent, catalyst 2, chain extender 2, crosslinking agent 2 and surfactant are well mixed in organic solvent, mixed system is obtained, isocyanates is added into mixed system, after being well mixed, 1 ~ 6h is incubated at 70 ~ 95 DEG C, resistance combustion polyurethane foam is obtained.The present invention is in urethane raw is prepared, the use of halogen-containing epoxide monomer is that raw material carries out ring-opening polymerisation, add the blending of structural type polyethers and obtain admixtured polyether, rigid chain segment is introduced in polyethers, so that polyethers has excellent mechanical property so that the polyurethane foam prepared by the polyethers also has excellent mechanical property.

Description

A kind of enhanced resistance combustion polyurethane foam and preparation method
Technical field
The present invention relates to macromolecule modified technical field, more particularly to a kind of enhanced resistance combustion polyurethane foam and preparation Method.
Background technology
One of polyurethane (PU) foamed plastics system plastics variety the most frequently used at present, RPUF（Referred to as RPU）It is one of most important kind in polyurethane material system, with excellent physical and mechanical properties, acoustical behavior, electrical property Energy and acid-fast alkali-proof performance.The rate of closed hole of the material belongs to hydrophobic material, with preferable moistureproof and waterproof performance more than 90% And good thermal insulation, sound insulation, shockproof properties, with very strong cohesive force, be widely used as petrochemical pipe, refrigerating equipment, The heat-insulation material of transporting equipment and building etc..Global annual requirement is in 5,000,000 t or so according to estimates, wherein portion big absolutely Point it is soft polyurethane foam and hard bubbles.And PU foamed materials easily burn in atmosphere, and a large amount of toxic gases are produced during burning And flue dust.Therefore, foreign countries give great concern to the fire-retardant of PU foamed materials, and have promulgated many about fire-retardant regulation And flame-retardant standard.In China, although do not set up the regulation fire-retardant on PU foams also, but in fact, to for aircraft, wheel Ship, rolling stock, automobile, other important industry parts, equipment and the polyurethane foam in some places, are proposed resistance in recent years Combustion is required, and has much employed flame retardant grade PU foams.
There is family more than 50 in fire retardant manufacturer of China, and kind nearly more than 50 is planted, but combustion inhibitor special is few, and general types 20 ~ 30 kinds.Although the total productive capacity of China's fire retardant is up to 150,000 t, development and the foreign countries of current China fire retardant still have not small Gap, especially configuration aspects in flame retardant products, less varieties are of low grade, and the yield of manufacturing enterprise is small, not yet forms big Production scale and esbablished corporation.
The fire retardant that domestic polyurethane foam is used, single variety is more, and consumption is big, the research of external composite flame-retardant agent and Using very active, related kind also compares many.To comply with fire-retardant low smog, hypotoxicity, innoxious development trend, exploitation High-efficiency compound fire-proof agent, by with wide market prospects.
The enhancing of polyurethane is typically that polyurethane/glass fiber compound material is prepared using glass fibre etc., is come with this Improve the mechanical strength of polyurethane.Assign PU have two methods with anti-flammability, one is it is carried out it is structurally-modified, such as by isocyanide Urea acrylate structure is introduced into PU chains, and the charing to improve material is inclined to and reduces its combustibility, but the application of this method is current It is very limited, is typically appropriate only for preparing rigid foam.
Another most common method is to add response type or additive flame retardant in PU formulas.But add fire retardant method Often causing foam to collapse bubble, cracking, efflorescence or makes the physical and mechanical properties such as its resilience significantly decline, and loses itself and is had Some performance advantages.Reactive flame retardant method be production polyurethane soft foamed plastics formula in add phosphorous, chlorine, bromine, boron, The reactive flame retardants such as the polyol of the fire-retardant member of nitrogen, or introduce ignition-proof element in PPG structure and hindered Performance is fired, such a method has the advantages that fire resistance persistence is good, influence smaller to physical and mechanical properties.
The content of the invention
There are inflammable and intensity decreases defects for prior art polyurethane foam, the present invention proposes a kind of enhanced Resistance combustion polyurethane foam and preparation method.Can have polyurethane product by the method for introducing ignition-proof element in PPG Standby higher heat resistance, dimensional stability and intensity.
To solve the above problems, the present invention uses following technical scheme：
A kind of preparation method of enhanced resistance combustion polyurethane foam, comprises the following steps：
（1）The modification of epoxy resin：Compound containing halogen is well mixed in organic solvent with epoxide monomer Afterwards, regulation system temperature is 85 ~ 100 DEG C, is then added dropwise into system after catalyst 1,2 ~ 8h of reaction, obtains halogen-containing epoxy Compound monomer；
（2）The preparation of modified polyether：By halogen-containing epoxide monomer, polyethers, chain extender 1 and crosslinking agent 1 organic molten It is well mixed in agent, then radiation treatment, obtains modified polyether；
（3）Modified polyether, foaming agent, catalyst 2, chain extender 2, crosslinking agent 2 and surfactant are mixed in organic solvent After uniform, mixed system is obtained, isocyanates is added into mixed system, after being well mixed, be incubated 1 ~ 6h at 70 ~ 95 DEG C, obtain To resistance combustion polyurethane foam.
The present invention introduces a halogen into epoxy monomer by the way that the pre- epoxy monomer of the compound containing halogen is reacted In, so that epoxy resin has the effect of flame-retardant smoke inhibition, and the halogen-containing epoxide list being modified by this method In body, the adhesion of halogen and epoxy resin is strong, is not susceptible to the phenomenon decomposed, and not only reduces harm of the halogen to environment, also The characteristic of its flame-retardant smoke inhibition is can guarantee that, extends its service life.
It is preferred that, the compound containing halogen is at least one of POCl3, phosphorus pentachloride, phosphorus trichloride.
The monomer of the epoxy resin can be well known to the art personnel, and the present invention does not have special to it It is required that, the halogen-containing epoxide monomer is the compound with the formula of formula I：
（Formula I）
Wherein, R1 and R2 are independently each at least one of C1 ~ C4 chlorohydrocarbon of alkyl, nitro, C1 ~ C4.
Organic solvent can improve the uniformity of material mixing, and the present invention does not have special want to the species of organic solvent Ask, can be well known to the art personnel as long as can play a part of and dissolve ultra-violet absorber, example Such as, the organic solvent is acetone, DMF, 1-METHYLPYRROLIDONE, DMA, dimethyl Acetamide, dichloromethane, triethyl phosphate, acetone, chloroform, toluene, ethanol, acetic acid, ethyl acetate, formic acid, chloroform, four At least one of hydrogen furans and dimethyl sulfoxide (DMSO).
Catalyst can promote epoxy resin to occur ring-opening reaction, can not only improve the production rate of reaction product, moreover it is possible to Improve reaction rate, it is preferred that in step（1）In, the catalyst 1 is triethyl benzyl ammonia chloride, triethylbenzyl bromination At least one of ammonium and N, N- dimethyl Bian amine.
Polyurethane foam is obtained by polyethers and isocyanates reaction, according to the difference of raw material type, obtained bullet The performance of property polyurethane is also different.The species of polyethers of the present invention does not have special limitation, is given birth to as long as can be reacted with isocyanates Generating polyurethane, can be well known to the art personnel, and polyethers is polyether Glycols and/or polyethers ternary as described Alcohol, specially polytetrahydrofuran diol, polyoxypropyleneglycol, tetrahydrofuran-propylene oxide copolymer glycols, PPOX three At least one of alcohol etc..
The present invention does not have special limitation to the species of isocyanates, as long as can be with the poly- ammonia of PEPA reaction generation Ester, can be well known to the art personnel, and isocyanates is IPDI, four methylenes as described Group diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI), 1,5- naphthalene diisocyanates, diphenyl methane two At least one of isocyanates or XDI.
Catalyst can promote polyethers and isocyanates to react, it is preferred that the catalyst 2 is triethylene diamine, diformazan At least one of amino-ethyl ether and N,N-Dibenzylamine；
Foaming agent is one of indispensable raw material in synthesis of polyurethane foam, it is preferred that the foaming agent is HCFC-141 hairs Any one in infusion, HCFC-141b foaming agents, CFC-11 foaming agents.
Surfactant can reduce the surface free energy of material, and the surfactant is nonionic surfactant. It is further preferred that the nonionic surfactant is ester type surfactant, ether type surfactant, amine type surface-active At least one of agent, acid amide type surfactant and ester-ether type surfactant.It is specific as follows：Ester type surfactant can be with For at least one of sorbitan fatty acid ester and polyoxyethylene fatty acid ester etc..Ether type surfactant can be polyoxy At least one of vinyl alkyl alcohol ether and polyethenoxy alkylphenols etc..Amine surfactant can be Polyoxyethylene fatty Amine etc..Acidamide surfactant can be such as polyoxyethylate amide.Ester ether surface active agent can be sorbitan esters of fatty Acid ester polyoxyethylene ether type (tween type) etc..It is preferred that sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene fat Fat amine, polyoxyethylate amide or APEO, more preferred polyoxyethylene fatty amine, polyoxyethylate amide or polyoxyethylene Ether.Fat in wherein described fatty acid ester, fatty amine refers to C2-C4 straight-chain hydrocarbons.In alkyl alcohol ether, alkylbenzene phenolic ether Alkyl is C2-C4 straight-chain hydrocarbons.
Chain extender refers to the compound that can promote molecule chain extension, extend, and chain extender can make polyurethane reaction system rapid Ground carries out chain extension and crosslinking, and they have the characteristic group that can be chemically reacted with reaction system, and molecular weight is low, and reaction is lived Sprinkle, stronger response competition probability is constituted to isocyanates and polyalcohols system, they can extremely efficient adjust reaction system Reaction speed；The crosslinking agent and consumption of different cultivars can be used, the technological parameters such as reactant viscosity growth is adjusted, is allowed to adapt to The requirement of processing.Participate in reacting and enter in main polymer chain using chain extender, can be by some of chain extension agent molecule characteristic Unit structure is introduced into polyurethane backbone, can influence some performances of polyurethane.It is preferred that, the chain extender 1 and chain extender 2 are each From being independently ethylene glycol, propane diols, BDO, diglycol, glycerine, trimethylolpropane, Isosorbide-5-Nitrae-hexamethylene At least one in glycol, hydrogenated bisphenol A, α-allylin, glycidol allyl ether, cumyl peroxide, sulphur Kind.
The crosslinking agent 1 and crosslinking agent 2 are organic peroxide crosslinking agent.
A kind of enhanced resistance combustion polyurethane foam, it is characterised in that the enhanced resistance combustion polyurethane foam is by above-mentioned institute The preparation method stated is prepared.
Compared with prior art, the characteristics of it is protruded and excellent effect are：
The present invention is that raw material carries out ring-opening polymerisation using halogen-containing epoxide monomer in urethane raw is prepared, then Add the blending of structural type polyethers and obtain admixtured polyether, rigid chain segment is introduced in polyethers, so that polyethers has excellent mechanics Performance so that the polyurethane foam prepared by the polyethers also has excellent mechanical property.Introduce a halogen into epoxy monomer In, so that epoxy resin has the effect of flame-retardant smoke inhibition, and the halogen-containing epoxide list being modified by this method In body, the adhesion of halogen and epoxy resin is strong, is not susceptible to the phenomenon decomposed, and not only reduces harm of the halogen to environment, also The characteristic of its flame-retardant smoke inhibition is can guarantee that, extends its service life.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method of enhanced resistance combustion polyurethane foam, comprises the following steps：
（1）The modification of epoxy resin：By POCl3 and nitro epoxide monomer in DMA and diformazan After being well mixed in the mixed solution of yl acetamide, regulation system temperature is 90 DEG C, and triethylbenzyl is then added dropwise into system After ammonium chloride, reaction 3h, washing, extraction obtain chlorine modified epoxy compound monomer；
（2）The preparation of modified polyether：By chlorine modified epoxy compound monomer, PPOX triol, trimethylolpropane and mistake Aoxidize isopropylbenzene to be well mixed in DMA and the mixed solution of dimethyl acetamide, then in radiation, obtain To modified polyether；
（3）By modified polyether, HCFC-141b foaming agents, triethylene diamine, ethylene glycol, benzoyl peroxide and sorbitan After fatty acid ester APEO is well mixed in DMA and the mixed solution of dimethyl acetamide, obtain Mixed system, IPDI is added into mixed system, after being well mixed, and is incubated 4h at 90 DEG C, is obtained fire-retardant Polyurethane foam.
Embodiment 2
A kind of preparation method of enhanced resistance combustion polyurethane foam, comprises the following steps：
（1）The modification of epoxy resin：Phosphorus pentachloride is well mixed with bisphenol A type epoxy resin monomer in triethyl phosphate Afterwards, regulation system temperature is 95 DEG C, is then added dropwise into system after triethyl benzyl ammonia chloride, reaction 4h, and washing, extraction are obtained To chlorine modified epoxy compound monomer；
（2）The preparation of modified polyether：By chlorine modified epoxy compound monomer, tetrahydrofuran-propylene oxide copolymer glycols, three hydroxyl first Base propane and two (4,2 toluyl) peroxide are well mixed in triethyl phosphate, then in radiation, obtain modified poly- Ether；
（3）By modified polyether, CFC-11 foaming agents, dimethylaminoethyl ether, glycidol the allyl ether, (uncle of normal-butyl 4,4 2 Butyl peroxy) after valerate and polyoxyethylene fatty acid ester be well mixed in triethyl phosphate, mixed system is obtained, to mixed Tetramethylene diisocyanate is added in zoarium system, after being well mixed, 3h is incubated at 85 DEG C, obtains resistance combustion polyurethane foam.
Embodiment 3
A kind of preparation method of enhanced resistance combustion polyurethane foam, comprises the following steps：
（1）The modification of epoxy resin：Phosphorus trichloride and fluorine substituted epoxy compound monomer are mixed in DMF After conjunction uniformly, regulation system temperature is 90 DEG C, is then added dropwise into system after triethylbenzyl ammonium bromide, reaction 6h, washs, extracts Take, obtain chlorine modified epoxy compound monomer；
（2）The preparation of modified polyether：By chlorine modified epoxy compound monomer, polyoxypropyleneglycol, cumyl peroxide and Benzoyl peroxide is well mixed in DMF, then in radiation, obtains modified polyether；
（3）By modified polyether, HCFC-141b foaming agents, N,N-Dibenzylamine, α-allylin, 2,5- dimethyl -2, After (tert-butyl hydroperoxide) hexanes of 5- bis- and polyoxyethylene fatty amine are well mixed in DMF, mixed System, hexamethylene diisocyanate is added into mixed system, after being well mixed, and is incubated 2h at 80 DEG C, is obtained fire-retardant poly- ammonia Ester foam.
Embodiment 4
A kind of preparation method of enhanced resistance combustion polyurethane foam, comprises the following steps：
（1）The modification of epoxy resin：Phosphorus trichloride is mixed with siliceous epoxy monomer in DMA After even, regulation system temperature is 100 DEG C, is then added dropwise into system after triethylbenzyl ammonium bromide, reaction 8h, washing, extraction, Obtain chlorine modified epoxy compound monomer；
（2）The preparation of modified polyether：Chlorine modified epoxy compound monomer, erythritan, hydrogenated bisphenol A and peroxidating is different Propyl benzene is well mixed in DMA, then in radiation, obtains modified polyether；
（3）By modified polyether, HCFC-141 foaming agents, dimethylaminoethyl ether, hydrogenated bisphenol A, two (4,2 toluyl) mistakes After oxide and polyoxyethylate amide are well mixed in DMA, mixed system is obtained, into mixed system Toluene di-isocyanate(TDI) is added, after being well mixed, 1h is incubated at 95 DEG C, obtains resistance combustion polyurethane foam.
Embodiment 5
A kind of preparation method of enhanced resistance combustion polyurethane foam, comprises the following steps：
（1）The modification of epoxy resin：After POCl3 is well mixed with nitro epoxide monomer in tetrahydrofuran, adjust It is 85 DEG C to save system temperature, is then added dropwise into system after N, N- dimethyl Bian amine, reaction 2h, and washing, extraction obtain chlorine modification Epoxide monomer；
（2）The preparation of modified polyether：By chlorine modified epoxy compound monomer, PPOX triol, Isosorbide-5-Nitrae-cyclohexanediol and 2, 5- dimethyl -2,5- bis- (tert-butyl hydroperoxide) hexane is well mixed in tetrahydrofuran, then in radiation, obtains modified poly- Ether；
（3）By modified polyether, HCFC-141 foaming agents, N,N-Dibenzylamine, diglycol, dicumyl peroxide and poly- After oxygen vinyl alkyl alcohol ether is well mixed in tetrahydrofuran, mixed system is obtained, 1,5- naphthalenes two are added into mixed system different Cyanate, after being well mixed, is incubated 6h at 70 DEG C, obtains resistance combustion polyurethane foam.
Comparative example 1
A kind of preparation method of enhanced resistance combustion polyurethane foam, comprises the following steps：
The preparation of modified polyether：By chlorine modified epoxy compound monomer, PPOX triol, trimethylolpropane and peroxidating Isopropylbenzene is well mixed in DMA and the mixed solution of dimethyl acetamide, then in radiation, is changed Property polyethers；
By modified polyether, HCFC-141b foaming agents, triethylene diamine, ethylene glycol, benzoyl peroxide and sorbitan esters of fatty After acid ester polyoxyethylene ether is well mixed in DMA and the mixed solution of dimethyl acetamide, mixed System, IPDI is added into mixed system, after being well mixed, and is incubated 4h at 90 DEG C, is obtained fire-retardant poly- ammonia Ester foam.
Comparative example 2
（1）The modification of epoxy resin：By POCl3 and nitro epoxide monomer in DMA and diformazan After being well mixed in the mixed solution of yl acetamide, regulation system temperature is 90 DEG C, and triethylbenzyl is then added dropwise into system After ammonium chloride, reaction 3h, washing, extraction obtain chlorine modified epoxy compound monomer；
（2）By modified polyether, HCFC-141b foaming agents, triethylene diamine, ethylene glycol, benzoyl peroxide and sorbitan After fatty acid ester APEO is well mixed in DMA and the mixed solution of dimethyl acetamide, obtain Mixed system, IPDI is added into mixed system, after being well mixed, and is incubated 4h at 90 DEG C, is obtained fire-retardant Polyurethane foam.
Experiment test
Polyurethane foam obtained by embodiment 1 ~ 5 and comparative example 1 ~ 2, by following method measurement performances：
Compressive strength is determined to be carried out by GB 8813-2008.
Limited oxygen index is determined with reference to GB/T 2406.1-2008《Plastics Combustion method for testing performance》Carry out.
Experimental result is as shown in table 1.
Table 1：

Claims (8)

1. a kind of preparation method of enhanced resistance combustion polyurethane foam, it is characterised in that comprise the following steps：
（1）The modification of epoxy resin：Compound containing halogen is well mixed in organic solvent with epoxide monomer Afterwards, regulation system temperature is 85 ~ 100 DEG C, is then added dropwise into system after catalyst 1,2 ~ 8h of reaction, obtains halogen-containing epoxy Compound monomer；
（2）The preparation of modified polyether：By halogen-containing epoxide monomer, polyethers, chain extender 1 and crosslinking agent 1 organic molten It is well mixed in agent, then in radiation, obtains modified polyether；
（3）Modified polyether, foaming agent, catalyst 2, chain extender 2, crosslinking agent 2 and surfactant are mixed in organic solvent After uniform, mixed system is obtained, isocyanates is added into mixed system, after being well mixed, be incubated 1 ~ 6h at 70 ~ 95 DEG C, obtain To resistance combustion polyurethane foam；
The compound containing halogen is at least one of POCl3, phosphorus pentachloride, phosphorus trichloride；
The epoxide monomer is the compound with the formula of formula I：
（Formula I）
Wherein, R1 and R2 are independently each at least one of C1 ~ C4 chlorohydrocarbon of alkyl, nitro, C1 ~ C4.
2. the preparation method of enhanced resistance combustion polyurethane foam according to claim 1, it is characterised in that described organic molten Agent is acetone, DMF, 1-METHYLPYRROLIDONE, DMA, dimethyl acetamide, dichloromethane Alkane, triethyl phosphate, acetone, chloroform, toluene, ethanol, acetic acid, ethyl acetate, formic acid, chloroform, tetrahydrofuran and diformazan At least one of base sulfoxide.
3. the preparation method of enhanced resistance combustion polyurethane foam according to claim 1, it is characterised in that in step（1） In, the catalyst 1 is at least one in triethyl benzyl ammonia chloride, triethylbenzyl ammonium bromide and N, N- dimethyl Bian amine Kind.
4. the preparation method of enhanced resistance combustion polyurethane foam according to claim 1, it is characterised in that in step（2） In, the polyethers is polyether Glycols and/or polyether-tribasic alcohol.
5. the preparation method of enhanced resistance combustion polyurethane foam according to claim 1, it is characterised in that in step（3） In, the isocyanates is IPDI, tetramethylene diisocyanate, hexamethylene diisocyanate, first In phenylene diisocyanate, 1,5- naphthalene diisocyanates, methyl diphenylene diisocyanate or XDI It is at least one；The catalyst 2 is at least one of triethylene diamine, dimethylaminoethyl ether and N,N-Dibenzylamine； The foaming agent is any one in HCFC-141 foaming agents, HCFC-141b foaming agents, CFC-11 foaming agents.
6. the preparation method of enhanced resistance combustion polyurethane foam according to claim 1, it is characterised in that the chain extender 1 and chain extender 2 each be independently ethylene glycol, propane diols, BDO, diglycol, glycerine, trihydroxy methyl third Alkane, Isosorbide-5-Nitrae-cyclohexanediol, hydrogenated bisphenol A, α-allylin, glycidol allyl ether, cumyl peroxide, sulphur At least one of.
7. the preparation method of enhanced resistance combustion polyurethane foam according to claim 1, it is characterised in that the crosslinking agent 1 and crosslinking agent 2 be organic peroxide crosslinking agent.
8. a kind of enhanced resistance combustion polyurethane foam, it is characterised in that the enhanced resistance combustion polyurethane foam is by claim 1 Preparation method described in ~ 9 any one is prepared.
CN201710589015.XA 2017-07-19 2017-07-19 A kind of enhanced resistance combustion polyurethane foam and preparation method Pending CN107286316A (en)

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Publication number Priority date Publication date Assignee Title
CN108652127A (en) * 2018-05-22 2018-10-16 东莞市顺风运动器材有限公司 A kind of basketball movement insole
CN108840842A (en) * 2018-06-01 2018-11-20 万华化学集团股份有限公司 A kind of epoxy resin foaming agent, composition epoxy resin and its preparation and application
CN108892924A (en) * 2018-04-16 2018-11-27 安徽昊森新材料科技有限公司 A kind of automotive upholstery and preparation method thereof
CN111363463A (en) * 2018-12-26 2020-07-03 财团法人工业技术研究院 Polymers and coatings
CN111499786A (en) * 2020-06-04 2020-08-07 周玉 High-strength flame-retardant polyphenyl resin and application thereof in preparation of insulation board

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CN103183806A (en) * 2013-04-17 2013-07-03 北京东方雨虹防水技术股份有限公司 High-flame-retardant hard polyurethane foam material and preparation method thereof
CN103554467A (en) * 2013-10-31 2014-02-05 淄博德信联邦化学工业有限公司 Preparation method of phosphorus and chlorine containing flame retardant polyether polyol

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CN103183806A (en) * 2013-04-17 2013-07-03 北京东方雨虹防水技术股份有限公司 High-flame-retardant hard polyurethane foam material and preparation method thereof
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108892924A (en) * 2018-04-16 2018-11-27 安徽昊森新材料科技有限公司 A kind of automotive upholstery and preparation method thereof
CN108652127A (en) * 2018-05-22 2018-10-16 东莞市顺风运动器材有限公司 A kind of basketball movement insole
CN108840842A (en) * 2018-06-01 2018-11-20 万华化学集团股份有限公司 A kind of epoxy resin foaming agent, composition epoxy resin and its preparation and application
CN111363463A (en) * 2018-12-26 2020-07-03 财团法人工业技术研究院 Polymers and coatings
CN111499786A (en) * 2020-06-04 2020-08-07 周玉 High-strength flame-retardant polyphenyl resin and application thereof in preparation of insulation board
CN111499786B (en) * 2020-06-04 2022-01-14 南通杰西卡新型材料有限公司 High-strength flame-retardant polyphenyl resin and application thereof in preparation of insulation board

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