CN112812473A - 一种低导热系数硬质交联聚氯乙烯泡沫材料及其制备方法 - Google Patents
一种低导热系数硬质交联聚氯乙烯泡沫材料及其制备方法 Download PDFInfo
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- CN112812473A CN112812473A CN202110173491.XA CN202110173491A CN112812473A CN 112812473 A CN112812473 A CN 112812473A CN 202110173491 A CN202110173491 A CN 202110173491A CN 112812473 A CN112812473 A CN 112812473A
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- polyvinyl chloride
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 42
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 42
- 239000006261 foam material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 3
- 239000012948 isocyanate Substances 0.000 claims abstract description 3
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 3
- 239000004094 surface-active agent Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 21
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- -1 polymethylene Polymers 0.000 claims description 16
- 238000005187 foaming Methods 0.000 claims description 15
- 229920001400 block copolymer Polymers 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 235000012424 soybean oil Nutrition 0.000 claims description 10
- 239000003549 soybean oil Substances 0.000 claims description 10
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- NVSXSBBVEDNGPY-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical compound CCC(F)(F)C(F)(F)F NVSXSBBVEDNGPY-UHFFFAOYSA-N 0.000 claims description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- NVFYKZBOLSIHEI-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.O=C1OC(=O)C=C1 NVFYKZBOLSIHEI-UHFFFAOYSA-N 0.000 claims description 2
- OSIMQZHJCXQJDX-UHFFFAOYSA-N furan-2,5-dione;prop-2-enenitrile Chemical compound C=CC#N.O=C1OC(=O)C=C1 OSIMQZHJCXQJDX-UHFFFAOYSA-N 0.000 claims description 2
- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims 1
- 239000011112 polyethylene naphthalate Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000006260 foam Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 8
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 8
- 239000004246 zinc acetate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012774 insulation material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NXFJXKDZEKNNRK-UHFFFAOYSA-N furan-2,5-dione;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.O=C1OC(=O)C=C1 NXFJXKDZEKNNRK-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- RCXHRHWRRACBTK-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propane-1,2-diol Chemical compound OCC(O)COCC1CO1 RCXHRHWRRACBTK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VNZYHVPAPZNCBZ-UHFFFAOYSA-N furan-2,5-dione;methyl prop-2-enoate Chemical compound COC(=O)C=C.O=C1OC(=O)C=C1 VNZYHVPAPZNCBZ-UHFFFAOYSA-N 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
本发明属于泡沫材料技术领域,具体涉及一种低导热系数硬质交联聚氯乙烯泡沫材料及其制备方法,解决了现有技术中,交联聚氯乙烯泡沫材料生产周期长、导热系数高、导热系数随时间大幅增加的问题。本发明的泡沫材料配方包括,100份聚氯乙烯、20‑50份异氰酸酯、0‑30份环氧树脂、10‑50份活性稀释剂、5‑50份改性树脂、5‑50份发泡剂、5‑20份热稳定剂、1‑5份表面活性剂、0.1‑5份硫化剂、0.1‑5份促进剂。该泡沫具有生产周期短、并且在‑170—40℃环境下满足高强度、高韧性、高阻燃、高闭孔率、低密度等性能要求的同时,导热系数≤30mW/mk,长期满足低导热系数使用需求。
Description
技术领域
本发明属于泡沫材料技术领域,具体涉及一种低导热系数硬质交联聚氯乙烯泡沫材料及其制备方法。
背景技术
特殊船用保温材料要求能够长期在-170-40℃环境温度下保持高强度、高韧性、高阻燃、低密度、低导热系数。传统保温材料如PU泡沫、PIR泡沫仅导热系数满足要求,力学性能无法满足使用要求。满足性能要求且价格较低的泡沫材料仅有交联聚氯乙烯泡沫材料。
目前,世界上仅瑞典DIAB公司一家能够提供特殊船用硬质交联聚氯乙烯泡沫产品。原因主要有二:一是高强度、高韧性、高阻燃、高闭孔率、低密度硬质交联聚氯乙烯泡沫材生产技术难度较大,生产周期长,生产周期约为15-30d,且仅瑞典DIAB、意大利Maricell等少数几家公司能够生产;二是现有硬质交联聚氯乙烯泡沫为水发泡工艺,泡沫材料泡孔中的气体为CO2,CO2导热系数高、容易从泡沫中渗透出去,导致保温材料初始导热系数高、导热系数短时间内大幅增加、失去保温能力,保温材料使用寿命极短。无法满足特殊船用保温材料的使用要求。
专利CN106867140A所公开的技术,虽然初始导热系数较低,但是经过对比试验验证,泡沫材料无法长期保持低导热系数,保温性能丧失较快,且发泡工艺采用传统水发泡工艺,生产周期长。本发明既保持了硬质交联聚氯乙烯泡沫产品优异的力学性能、阻燃性能,又大幅降低了泡沫材料生产周期、降低了导热系数、延长了保温寿命、有望打破国外技术垄断。
发明内容
本发明的目的:本发明旨在提供一种低导热系数硬质交联聚氯乙烯泡沫材料及其制备方法,能够有效缩短硬质交联聚氯乙烯泡沫材料的生产周期;并且在-170—40℃环境下满足高强度、高韧性、高阻燃、高闭孔率、低密度等性能要求的同时,导热系数≤30mW/mk,长期满足低导热系数使用需求。
本发明的技术方案:根据本发明的第一方面,提供一种低导热系数硬质交联聚氯乙烯泡沫材料,其原料按质量份数的构成为:
优选的是,所述的聚氯乙烯为粒径小于100μm、分子量在2000-20000的PVC糊树脂。
优选的是,所述的异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯三聚体、多亚甲基多苯基多异氰酸酯中的至少一种。
优选的是,所述的环氧树脂为双酚A型、双酚F型、双酚S型环氧树脂中的至少一种。
优选的是,所述活性稀释剂为粘度小于500mPas的缩水甘油醚或缩水甘油酯中的至少一种。
优选的是,所述的改性树脂为马来酸酐苯乙烯嵌段共聚物、马来酸酐丙烯酸酯嵌段共聚物、马来酸酐甲基丙烯酸酯嵌段共聚物、聚偏氯乙烯、聚萘二甲酸丙二醇酯中的至少一种。
优选的是,所述的发泡剂为环戊烷、正戊烷、环己烷、五氟丙烷、五氟丁烷中的至少一种。
优选的是,所述的热稳定剂为环氧豆油、硬脂酸锌、硬脂酸钙、硬脂酸钡、硬脂酸镁、十二烷基磺酸钠中的至少一种。
优选的是,所述的表面活性剂为聚醚聚-硅氧烷嵌段共聚物。
优选的是,所述硫化剂为有机过氧化合物。
优选的是,所述促进剂为2,4,6—三(二甲胺基甲基)苯酚及其羧酸盐和羧酸酯或锰、钙、钴、锌的羧酸盐中的至少一种。
根据本发明的第二方面,提供一种低导热系数硬质交联聚氯乙烯泡沫材料的制备方法,用于制备上述的低导热系数交联聚氯乙烯泡沫材料,按以下步骤操作:
S1:将液体原料使用计量泵导入到行星搅拌釜中,在20-30℃混合20min;
S2:将固体粉料加入搅拌釜中,在20-30℃混合20min,保温、静置30min除去气泡;
S3:将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
S4:将模具放置在平板硫化机上,加压25-35MPa,温度升高至150-200℃,保持温度压力10-40min;
S5:将平板硫化机冷却到40-80℃,泄压后开模取出生胚;
S6:将生胚放入80-130℃烘箱中发泡1-4h,再在40-80℃烘箱中固化4-10天得到发泡制品。
与现有技术相比,本发明的有益效果为:
1)通过采用本发明的发泡-固化体系和制备工艺,在保留泡沫材料高强度、高韧性、高闭孔率、低密度等良好力学性能的同时,比现有技术生产周期缩短一半以上,极大地提升了生产效率;
2)为了满足-170—40℃环境下的长期使用需求,通过采用低导热系数的物理发泡剂,大幅降低泡沫材料初始导热系数;同时通过使用抗渗透改性树脂,产生复杂的协同效应,使得泡沫材料能够长时间保持低导热系数,从而大幅提高保温材料使用寿命。
具体实施方式
为了进一步了解本发明,下面结合实施例对本发明的优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点而不是对本发明专利要求的限制。实施例中所用原料均可商购获得。
实施例1
配方为100份PVC糊树脂,35份万华PM200,28份环氧树脂E51,10份烯丙基缩水甘油醚,25份丁基缩水甘油醚,46份马来酸酐甲基丙烯酸甲酯嵌段共聚物,46份环戊烷,15份环氧大豆油,5份AK8805,5份过氧化二异丙苯,3份DMP-30羧酸酯,2份醋酸锌。工艺为:
1)将液体原料使用计量泵导入到行星搅拌釜中,在30℃混合20min;
2)将固体粉料加入搅拌釜中,在30℃混合20min,保温、静置30min除去气泡;
3)将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
4)将模具放置在平板硫化机上,加压30MPa,温度升高至170℃,保持温度压力10min。
5)将平板硫化机冷却到60℃,泄压后开模取出生胚。
6)将生胚放入115℃烘箱中发泡2h,再在80℃烘箱中固化6天得到发泡制品。
实施例2
配方为100份PVC糊树脂,35份万华PM200,28份环氧树脂E51,10份烯丙基缩水甘油醚,25份丁基缩水甘油醚,46份马来酸酐丙烯酸甲酯嵌段共聚物,46份环戊烷,15份环氧大豆油,5份AK8805,5份过氧化二异丙苯,3份DMP-30羧酸酯,2份醋酸锌。工艺为:
1)将液体原料使用计量泵导入到行星搅拌釜中,在30℃混合20min;
2)将固体粉料加入搅拌釜中,在30℃混合20min,保温、静置30min除去气泡;
3)将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
4)将模具放置在平板硫化机上,加压30MPa,温度升高至170℃,保持温度压力10min。
5)将平板硫化机冷却到60℃,泄压后开模取出生胚。
6)将生胚放入115℃烘箱中发泡2h,再在80℃烘箱中固化6天得到发泡制品。
实施例3
配方为100份PVC糊树脂,35份万华PM200,28份环氧树脂E51,10份烯丙基缩水甘油醚,25份丁基缩水甘油醚,46份马来酸酐丙烯腈嵌段共聚物,46份环戊烷,15份环氧大豆油,5份AK8805,5份过氧化二异丙苯,3份DMP-30羧酸酯,2份醋酸锌。工艺为:
1)将液体原料使用计量泵导入到行星搅拌釜中,在30℃混合20min;
2)将固体粉料加入搅拌釜中,在30℃混合20min,保温、静置30min除去气泡;
3)将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
4)将模具放置在平板硫化机上,加压30MPa,温度升高至170℃,保持温度压力10min。
5)将平板硫化机冷却到60℃,泄压后开模取出生胚。
6)将生胚放入115℃烘箱中发泡2h,再在80℃烘箱中固化6天得到发泡制品。
实施例4
配方为100份PVC糊树脂,35份万华PM200,28份环氧树脂E51,10份烯丙基缩水甘油醚,25份丁基缩水甘油醚,46份聚偏氯乙烯,46份环戊烷,15份环氧大豆油,5份AK8805,5份过氧化二异丙苯,3份DMP-30羧酸酯,2份醋酸锌。工艺为:
1)将液体原料使用计量泵导入到行星搅拌釜中,在30℃混合20min;
2)将固体粉料加入搅拌釜中,在30℃混合20min,保温、静置30min除去气泡;
3)将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
4)将模具放置在平板硫化机上,加压30MPa,温度升高至170℃,保持温度压力10min。
5)将平板硫化机冷却到60℃,泄压后开模取出生胚。
6)将生胚放入115℃烘箱中发泡2h,再在80℃烘箱中固化6天得到发泡制品。
实施例5
配方为100份PVC糊树脂,35份万华PM200,28份环氧树脂E51,10份烯丙基缩水甘油醚,25份丁基缩水甘油醚,46份聚萘二甲酸丙二醇酯,46份环戊烷,15份环氧大豆油,5份AK8805,5份过氧化二异丙苯,3份DMP-30羧酸酯,2份醋酸锌。工艺为:
1)将液体原料使用计量泵导入到行星搅拌釜中,在30℃混合20min;
2)将固体粉料加入搅拌釜中,在30℃混合20min,保温、静置30min除去气泡;
3)将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
4)将模具放置在平板硫化机上,加压30MPa,温度升高至170℃,保持温度压力10min。
5)将平板硫化机冷却到60℃,泄压后开模取出生胚。
6)将生胚放入115℃烘箱中发泡2h,再在80℃烘箱中固化6天得到发泡制品。
实施例6
配方为100份PVC糊树脂,35份万华PM200,28份环氧树脂E51,10份烯丙基缩水甘油醚,25份丁基缩水甘油醚,26份马来酸酐甲基丙烯酸甲酯嵌段共聚物,20份聚偏氯乙烯,46份环戊烷,15份环氧大豆油,5份AK8805,5份过氧化二异丙苯,3份DMP-30羧酸酯,2份醋酸锌。工艺为:
1)将液体原料使用计量泵导入到行星搅拌釜中,在30℃混合20min;
2)将固体粉料加入搅拌釜中,在30℃混合20min,保温、静置30min除去气泡;
3)将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
4)将模具放置在平板硫化机上,加压30MPa,温度升高至170℃,保持温度压力10min。
5)将平板硫化机冷却到60℃,泄压后开模取出生胚。
6)将生胚放入115℃烘箱中发泡2h,再在80℃烘箱中固化6天得到发泡制品。
对比例1
配方为100份PVC糊树脂,35份万华PM200,28份环氧树脂E51,10份烯丙基缩水甘油醚,25份丁基缩水甘油醚,46份环戊烷,15份环氧大豆油,5份AK8805,5份过氧化二异丙苯,3份DMP-30羧酸酯,2份醋酸锌。工艺为:
1)将液体原料使用计量泵导入到行星搅拌釜中,在30℃混合20min;
2)将固体粉料加入搅拌釜中,在30℃混合20min,保温、静置30min除去气泡;
3)将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
4)将模具放置在平板硫化机上,加压30MPa,温度升高至170℃,保持温度压力10min。
5)将平板硫化机冷却到60℃,泄压后开模取出生胚。
6)将生胚放入115℃烘箱中发泡2h,再在80℃烘箱中固化6天得到发泡制品。
对比例2
配方为100份PVC糊树脂,35份万华PM200,28份环氧树脂E51,10份烯丙基缩水甘油醚,25份丁基缩水甘油醚,26份马来酸酐,20份甲基丙烯酸甲酯,46份环戊烷,15份环氧大豆油,5份AK8805,5份过氧化二异丙苯,3份DMP-30羧酸酯,2份醋酸锌。工艺为:
1)将液体原料使用计量泵导入到行星搅拌釜中,在30℃混合20min;
2)将固体粉料加入搅拌釜中,在30℃混合20min,保温、静置30min除去气泡;
3)将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
4)将模具放置在平板硫化机上,加压30MPa,温度升高至170℃,保持温度压力10min。
5)将平板硫化机冷却到60℃,泄压后开模取出生胚。
6)将生胚放入115℃烘箱中发泡2h,再在80℃烘箱中固化6天得到发泡制品。
对比例3
按照专利CN106867140A中实施例3进行试验,配方为100份PVC糊树脂,50份琥珀酸酐,10份四氢苯酐,10份丙三醇缩水甘油醚,60份多亚甲基多苯基多异氰酸酯(PAPI),10份N,N-二亚硝基五亚甲基四胺,3份吐温80,5份三氧化二锑,0.1份石墨粉(400目)。
制备工艺为:将原料混合均匀加入模具,先在90℃预热20min,升压至15MPa、升温至180℃,模压时间为40s/mm,冷却至110℃开模,在水中100℃发泡2h,样品3-1在70℃水中固化6天,样品3-2在70℃水中固化10天,样品3-3在70℃水中固化10天,在70℃烘箱中干燥5天。
性能测试与结果说明
为了进一步说明本发明的增益效果,将实施例1-6、对比例1-3进行性能测试,测试方法为:
压缩强度ASTM D 1621,压缩模量ASTM D 1621-B-73,导热系数ASTM D C 581,加速老化为70℃0d、7d、14d、21d、28d,表观密度ASTM D 1622,闭孔率ASTM D 6226,孔径通过切片后带刻尺的光学显微镜测量。测量结果如表1所示。
对比表1强度模量测试结果可知,采用本发明发泡-固化体系的泡沫材料实施例1-6、对比例1-2力学性能远超现有技术对比例3。
对比实施例1~6、对比例1~3的0d导热系数可知,引入低导热系数物理发泡剂可以有效降低泡沫初始导热系数。对比实施例1~6、对比例1~3加速老化后的导热系数结果可知,本发明通过引入抗渗透改性树脂,大幅延长了泡沫材料的保温寿命,且这种抗渗透树脂必须具有特定结构,将这种树脂的单体直接加入配方中,不能起到延长泡沫材料的保温寿命的效果。对比实施例1和对比例3-1~3-3测试结果可知,传统水发泡工艺需要长时间固化和干燥,而本发明大幅缩减了生产周期、提高了生产效率、降低了生产成本。
表1样品性能测试结果
Claims (12)
2.根据权利要求1所述的一种低导热系数硬质交联聚氯乙烯泡沫材料,其特征在于:所述的聚氯乙烯为粒径小于100μm、分子量在2000-20000的PVC糊树脂。
3.根据权利要求1所述的一种低导热系数硬质交联聚氯乙烯泡沫材料,其特征在于:所述的异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯三聚体、多亚甲基多苯基多异氰酸酯中的至少一种。
4.根据权利要求1所述的一种低导热系数硬质交联聚氯乙烯泡沫材料,其特征在于:所述的环氧树脂为双酚A型、双酚F型、双酚S型环氧树脂中的至少一种。
5.根据权利要求1所述的一种低导热系数硬质交联聚氯乙烯泡沫材料,其特征在于:所述活性稀释剂为粘度小于500mPas的缩水甘油醚或缩水甘油酯中的至少一种。
6.根据权利要求1所述的一种低导热系数硬质交联聚氯乙烯泡沫材料,其特征在于:所述的改性树脂为马来酸酐丙烯酸酯嵌段共聚物、马来酸酐甲基丙烯酸酯嵌段共聚物、马来酸酐丙烯腈嵌段共聚物、聚偏氯乙烯、聚萘二甲酸丙二醇酯中的至少一种。
7.根据权利要求1所述的一种低导热系数硬质交联聚氯乙烯泡沫材料,其特征在于:所述的发泡剂为环戊烷、正戊烷、五氟丙烷、五氟丁烷中的至少一种。
8.根据权利要求1所述的一种低导热系数硬质交联聚氯乙烯泡沫材料,其特征在于:所述的热稳定剂为环氧豆油、硬脂酸锌、硬脂酸钙、硬脂酸钡、硬脂酸镁、十二烷基磺酸钠中的至少一种。
9.根据权利要求1所述的一种低导热系数交联聚氯乙烯泡沫材料,其特征在于:所述的表面活性剂为聚醚聚-硅氧烷嵌段共聚物。
10.根据权利要求1所述的一种低导热系数交联聚氯乙烯泡沫材料,其特征在于:所述硫化剂为有机过氧化合物。
11.根据权利要求1所述的一种低导热系数交联聚氯乙烯泡沫材料,其特征在于:所述促进剂为2,4,6—三(二甲胺基甲基)苯酚及其羧酸盐和羧酸酯或锰、钙、钴、锌的羧酸盐中的至少一种。
12.一种低导热系数硬质交联聚氯乙烯泡沫材料的制备方法,用于制备权利要求1~11中任意一项所述的低导热系数交联聚氯乙烯泡沫材料,其特征在于,按以下步骤操作:
S1:将液体原料使用计量泵导入到行星搅拌釜中,在20-30℃混合20min;
S2:将固体粉料加入搅拌釜中,在20-30℃混合20min,保温、静置30min除去气泡;
S3:将搅拌釜用干燥空气加压至0.1-0.2MPa,并通过底部放料阀将物料放入模具中;
S4:将模具放置在平板硫化机上,加压25-35MPa,温度升高至150-200℃,保持温度压力10-40min;
S5:将平板硫化机冷却到40-80℃,泄压后开模取出生胚;
S6:将生胚放入80-130℃烘箱中发泡1-4h,再在40-80℃烘箱中固化4-10天得到发泡制品。
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