CN102585341A - Preparation method for anti-radiation ethylene-vinyl acetate copolymer composite material - Google Patents
Preparation method for anti-radiation ethylene-vinyl acetate copolymer composite material Download PDFInfo
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- CN102585341A CN102585341A CN201210027893XA CN201210027893A CN102585341A CN 102585341 A CN102585341 A CN 102585341A CN 201210027893X A CN201210027893X A CN 201210027893XA CN 201210027893 A CN201210027893 A CN 201210027893A CN 102585341 A CN102585341 A CN 102585341A
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- Prior art keywords
- vinyl acetate
- ethylene
- acetate copolymer
- preparation
- radioprotective
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 53
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 230000003471 anti-radiation Effects 0.000 title abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims description 35
- 230000004223 radioprotective effect Effects 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 zirconium ester Chemical class 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 4
- 229910052981 lead sulfide Inorganic materials 0.000 claims description 4
- 229940056932 lead sulfide Drugs 0.000 claims description 4
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 3
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 3
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 claims description 3
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 claims description 3
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 241001062472 Stokellia anisodon Species 0.000 claims description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000001069 triethyl citrate Substances 0.000 claims description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013769 triethyl citrate Nutrition 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 8
- 239000004744 fabric Substances 0.000 abstract description 7
- 239000004753 textile Substances 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 108010025899 gelatin film Proteins 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- QLFSGJVBZCESND-UHFFFAOYSA-N lead;prop-1-ene Chemical compound [Pb].CC=C QLFSGJVBZCESND-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-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
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- IBKNSIPMTGYUNZ-UHFFFAOYSA-N ethenyl(methoxy)silane Chemical compound CO[SiH2]C=C IBKNSIPMTGYUNZ-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000000718 radiation-protective agent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention relates to a preparation method for an anti-radiation ethylene-vinyl acetate copolymer composite material. The steps comprises: weighing 100 parts of lead salt, 1-5 parts of coupling agent and 15-50 parts of solvent by weight, wherein the solvent is one or more of water and ester organic solvents, dissolving the coupling agent into the solvent, then adding the solution into the lead salt, stirring and evenly mixing the solution, activating the solution at constant temperature to obtain surface modified lead salt; and weighing 100 parts of ethylene-vinyl acetate copolymer, 50-250 parts of surface modified lead salt, 0-10 parts of polar monomer, 0-1 parts of initiator, 0.1-2 parts of antioxygen and 0-15 parts of lubricating agent, stirring and evenly mixing the mixture, fusing and compositing the mixture to obtain the composite material. The anti-radiation ethylene-vinyl acetate copolymer composite material prepared through the method of fusing forming processing can serve as an anti-radiation coating or gel film to be used in textile and to be formed into clothes and cord fabric and the like with the anti-radiation function, and has wide application prospects.
Description
Technical field
Technical field of composite materials of the present invention relates in particular to a kind of preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material.
Background technology
Ethylene-vinyl acetate copolymer is because of having good processing characteristics; Viscosifying power is strong, good snappiness, impact strength, resisting environmental stress and cracking and good optical performance etc. are arranged in the awide temperature range and be widely used in industries such as machinery, chemical industry, electrical equipment, communications and transportation and building along with progress of science and technology; People are more and more to the research of antiradiation material, and the range of application of antiradiation material is more and more wider.Antiradiation material is except that as the personal protection clothing, also in medical clinic, fields such as Nuclear power plants, building and detector instrument instrument have obtained using widely.Ethylene-vinyl acetate copolymer processing is simple, flexibly, cost is low and excellent performance etc., if can give its radiation proof function, can in personal protection and construction safety, be applied.At present, improve on its flame retardant properties, seldom it is prepared antiradiation material as resin matrix the research of ethylene-vinyl acetate copolymer is mainly concentrated.
Lead metal is because of having good anti-radiation, and is widely used in traditional radioprotective matrix material, but Toxicity of Lead is bigger, gradually by replacements such as leaded Nano compound such as its compound such as propylene lead plumbate, lead sulfide, plumbous oxide.Receive much concern about the research that changes the shielding property of synthetic resins through doping lead metal compound both at home and abroad always.People such as Zhang Yu (preparation and the performance study of Vestolen PP 7052 lead plumbate/epoxy resin radiation protection material; The polymer journal; 2010; 23 (5), 582-587) studied methyltrimethoxy silane, propylene lead plumbate and be doped in the epoxy resin and adopt gamma-radiation graft polymerization method to make the nanometer propylene lead plumbate/epoxy resin radiation protection material that has the high quality uptake factor to gamma-ray; People such as An Jun (preparation and the research of the resin/nanometer lead composite material of anti-high-energy radiation, engineering plastics, 2004,32 (12), 14-17) studied to have reactive group-SO
3-crosslinked polystyrene sulfonic acid sodium cation exchange resin be template, add lead nitrate, maturation process makes sigmatron and Beta-ray shielding rate is reached resin/nanometer lead composite material of 30%.
The above-mentioned existing method for preparing the radioprotective polymer composites more or less all exists the synthesis technique complicacy, and the defective that severe reaction conditions, shielding efficiency are not high had not been reported the adhesive property of radioprotective polymer composites and textiles yet.
Summary of the invention
The objective of the invention is to provides a kind of preparation method that the radioprotective ethylene-vinyl acetate copolymer matrix material of well-shielded effect can be arranged X ray to the deficiency on the prior art.The preparation method of this ethylene-vinyl acetate copolymer matrix material; Technology is simple; Be convenient to produce; The matrix material of processing has radioprotective characteristic and strong with the viscosifying power of textiles, has given ethylene-vinyl acetate copolymer new function, and has expanded the Application Areas of ethylene-vinyl acetate copolymer.
For realizing such purpose; The present invention proposes in ethylene-vinyl acetate copolymer, to add lead salt as antiradiation agent, in order to improve the interface problem of ethylene-vinyl acetate copolymer and lead salt, at first with the surface treatment of coupling agent to lead salt; Afterwards; For the interface bonding is further improved, in compound system, add polar monomer and initiator situ-formed graft and improve ethylene-vinyl acetate copolymer and lead salt interface dispersiveness, to improve the cementability of matrix material; Add oxidation inhibitor simultaneously, that lubricant makes shielding property through the melt molding method for processing is good; Viscosifying power is strong; Softish ethylene-vinyl acetate copolymer matrix material; It can be used as antiradiation coating or glued membrane and is used for textiles and processes clothes with radiation proof function and cord etc., is with a wide range of applications.
The objective of the invention is to realize through following technical scheme:
The present invention relates to a kind of preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material, comprise the steps:
Step 1, the preparation of surface-treated lead salt:
(a), in weight part, take by weighing 100 parts of lead salts, 1～5 part of coupling agent and 15～50 parts of solvents, said solvent is one or more in water and the alcohol organic solvent;
(b), said coupling agent is dissolved in the said solvent, join then in the said lead salt, mix back constant temperature activation (mixed material is placed the thermostat container activation), promptly get the surface-treated lead salt;
Step 2; In weight part, take by weighing following feed composition: 50～250 parts of the surface-treated lead salts that 100 parts of ethylene-vinyl acetate copolymers, the first step make, 0～10 part of polar monomer, 0～1 part of initiator, 0.1～2 part in oxidation inhibitor, 0～15 part of lubricant; It is compound to mix the back fusion afterwards, promptly gets said radioprotective ethylene-vinyl acetate copolymer matrix material.
Preferably, the lead salt described in the step 1 (a) is one or more the mixture in yellow lead oxide, plumbic oxide, lead sulfide, plumbic acetate, lead oxalate, lead stearate, the tri-lead tetroxide.
Preferably, the coupling agent described in the step 1 (a) is one or more the mixture in silane coupling agent, titanate coupling agent, zirconium ester coupling agent, the aluminate coupling agent.
Preferably, the alcohol organic solvent described in the step 1 (a) is ethanol, methyl alcohol and Virahol.
Preferably, mixing described in the step 1 (b) is specially: on impeller, mix with 300～3000r/min, mixing time is 3～20min.
Preferably, the constant temperature activation described in the step 1 (b) is specially: activation temperature is 100～140 ℃, and soak time is 1～4 hour.
Preferably, vinyl acetate between to for plastic in the ethylene-vinyl acetate copolymer described in the step 2 (VA) content is 12%～33%, and promptly softening temperature is 50～80 ℃.
Preferably, the polar monomer described in the step 2 is a kind of or several kinds the mixture in maleic anhydride, vinylformic acid, acrylic amide, vinyl cyanide, 3-butene-1-alcohol, the SY-Monomer G.
Preferably, the initiator described in the step 2 is a kind of or several kinds the mixture in Di Cumyl Peroxide 99, Diisopropyl azodicarboxylate, Lucidol, tert-butyl peroxy acetate, peroxidized t-butyl perbenzoate, two (tert-butyl hydroperoxide sec.-propyl) benzene.
Preferably, the oxidation inhibitor described in the step 2 is N, and [3-(3 for N '-two; The 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, Tyox B, tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester, two (2,2; 6,6-tetramethyl--4-piperidyl) sebate, 2,2 '-methylene bis (4-methyl-6-tert butyl phenol), 2; 6-di-tert-butyl-4-methy phenol, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 4; 4 '-(β, β '-dihydroxyl dipropyl oxygen phenyl)-2, the mixture of one or more in the 2-propane.
Preferably, the lubricant described in the step 2 is a kind of or several kinds the mixture in whiteruss, Triple Pressed Stearic Acid, phthalic ester, terephthalate, isophthalic acid ester, tributyl citrate, dibutyl maleate, dioctyl maleate, adipic acid ester, triethyl citrate, the glycol ether benzoic ether.
Preferably, the mixing described in the step 2 is specially: the rotating speed with 600～2400r/min on impeller mixes, and mixing time is 5～30min.
Preferably, the fusion composite methods described in the step 2 is to open one or more of the type of being smelt, compression molding, extrusion moulding, injection moulding etc.
Preferably, the fusion compound temperature described in the step 2 is 70～150 ℃.
Compared with prior art, the present invention has following beneficial effect:
1, the ethylene-vinyl acetate copolymer matrix material that contains lead salt with the textiles agglutinating is a thermoplastic elastomer, thus can reclaim, and reuse and avoided the pollution of lead salt to environment;
2, add the liquid coupling agent in the mixed at high speed stage and can avoid lead salt powder dust from flying, improve processing environment;
3, adding polar monomer and initiator is in the mixed at high speed stage, so the moulding of graft reaction and matrix material is carried out synchronously, has not only simplified production process, and the effect of handling the interface is also better;
4, compare with the traditional method of the interface problem of polymkeric substance with simple use coupling agent treatment inorganics, when introducing polar monomer, its interface is better, and the viscosifying power of ethylene-vinyl acetate superpolymer and textiles is also stronger.
Embodiment
Below through concrete embodiment technical scheme of the present invention is further described.Following examples are to further specify of the present invention, rather than limit scope of the present invention.
Embodiment 1
The first step; 1g γ-methacryloxypropyl trimethoxy silane is dissolved in the 15g water, adds the 100g yellow lead oxide then, under 1800r/min on the impeller, fully stir 10min; Mixed material is put into 100 ℃ of baking ovens; Placed 4 hours, and took out naturally cooling, obtain the lead salt of surface-treated.
Second step; With 50g lead salt, ethylene-vinyl acetate copolymer (VA content is 30%) 100g, the oxidation inhibitor N of above-mentioned surface-treated, N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine 0.1g adds in the high speed mixing roll; Under mixing speed 2400r/min, mixed 5 minutes.The mixing masterbatch that obtains is extruded granulating at 130 ℃, and injection moulding in 150 ℃ injection moulding machine then obtains the ethylene-vinyl acetate copolymer matrix material of shielding property.Its shielding efficiency to X ray is 40%, and tensile strength is 18.7MPa, and elongation at break is 760%, Shao Shi D hardness 71, with the stripping strength of cloth be 1.2N/mm.
Embodiment 2
The first step; The 5g butyl(tetra)titanate is dissolved in 25g water and the 25g alcoholic acid mixed solution, adds the 100g plumbic oxide then, under 300r/min on the impeller, fully stir 20min; Mixed material is put into 140 ℃ of baking ovens; Placed 1 hour, and took out naturally cooling, obtain the lead salt of surface-treated.
Second step is with 100g lead salt, ethylene-vinyl acetate copolymer (VA content is 25%) 100g, whiteruss 15g, oxidation inhibitor tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) the ester 1g and two (2 of above-mentioned surface-treated; 2; 6,6-tetramethyl--4-piperidyl) sebate 1g, add in the high speed mixing roll; Under mixing speed 600r/min, mixed 30 minutes.The mixing masterbatch that obtains joined in 70 ℃ the mill and mix in flakes,, obtain the ethylene-vinyl acetate copolymer matrix material of shielding property then 120 ℃ of following compression moldings.Its shielding efficiency to X ray is 64%, and tensile strength is 16MPa, and elongation at break is 720%, Shao Shi D hardness 45, with the stripping strength of cloth be 1.0N/mm.
Embodiment 3
The first step is dissolved in the 9.0g zirconium iso-propoxide in 90.0g Virahol and the 45.0g ethanol, adds the 300g lead oxalate then; Under 3000r/min on the impeller, fully stir 3min; Mixed material is put into 120 ℃ of baking ovens, placed 2 hours, take out the lead salt that naturally cooling obtains surface-treated.
Second step; 250g lead salt, 100g ethylene-vinyl acetate copolymer (VA content is 15%), 10g tributyl citrate, 10g maleic anhydride, 1g Di Cumyl Peroxide 99,1g 2 with above-mentioned surface-treated; 2 '-methylene bis (4-methyl-6-tert butyl phenol) adds in the high speed mixing roll; Under mixing speed 1000r/min, mixed 30 minutes.The mixing masterbatch that obtains joined in 70 ℃ the mill, mix,, obtain the ethylene-vinyl acetate copolymer matrix material of shielding property then 110 ℃ of following mold pressings 300 seconds.Its shielding efficiency to X ray is 75%, and tensile strength is 14MPa, and elongation at break is 600%, Shao Shi D hardness 45, with the stripping strength of cloth be 1.5N/mm.
Embodiment 4
The first step is dissolved in 4g vinyl methoxy silane in 40g ethanol and the 20g methyl alcohol, adds the 200g plumbic acetate then; Under 2400r/min on the impeller, fully stir 8min; Mixed material is put into 120 ℃ of baking ovens, placed 2 hours, take out the lead salt that naturally cooling obtains surface-treated.
Second step; 150g lead salt, 100g ethylene-vinyl acetate copolymer (VA content is 20%), 10g Triple Pressed Stearic Acid, 5g vinylformic acid, 0.5g peroxidized t-butyl perbenzoate, 1g 2 with above-mentioned surface-treated; 2 '-methylene bis (4-methyl-6-tert butyl phenol) adds in the high speed mixing roll; Under mixing speed 1200r/min, mix 20min.The mixing masterbatch that obtains is added injection moulding machine, and 150 ℃ of injection mouldings obtain the ethylene-vinyl acetate copolymer matrix material of shielding property.Its shielding efficiency to X ray is 55%, and tensile strength is 11MPa, and elongation at break is 570%, Shao Shi D hardness 43, with the stripping strength of cloth be 1.4N/mm.
Embodiment 5
The first step; 7.0g aluminate coupling agent UP-AL 801 is dissolved in the 50g Virahol; Add 200g lead sulfide then, under 1500r/min on the impeller, fully stir 12min, mixed material is put into 130 ℃ of baking ovens; Placed 1.5 hours, and took out the lead salt that naturally cooling obtains surface-treated.
Second step; 200g lead salt, 100g ethylene-vinyl acetate copolymer (VA content is 12%), 10g tributyl citrate, 2g dioctyl maleate, 3g3-butene-1-alcohol, 0.5g Diisopropyl azodicarboxylate, 1g 4 with above-mentioned surface-treated; 4 '-(β, β '-dihydroxyl dipropyl oxygen phenyl)-2,2-propane add in the high speed mixing roll; Under mixing speed 900r/min, mix 25min.At 120 ℃ of forcing machine extruding pelletizations, then with the particle injection moulding, 135 ℃ of injection temperatures obtain the ethylene-vinyl acetate copolymer matrix material of shielding property with the mixing masterbatch that obtains.Its shielding efficiency to X ray is 65%, and tensile strength is 9.8MPa, and elongation at break is 500%, Shao Shi D hardness 60, with the stripping strength of cloth be 1.8N/mm.
Embodiment 6
The first step; 1g γ-glycidyl ether oxygen propyl trimethoxy silicane and 2g butyl(tetra)titanate are dissolved in the 150g ethanol; Add 200g lead stearate and 100g tri-lead tetroxide then, under 2700r/min on the impeller, fully stir 5min, mixed material is put into 110 ℃ of baking ovens; Placed 2.5 hours, and took out the lead salt that naturally cooling obtains surface-treated.
Second step; Two (tert-butyl hydroperoxide sec.-propyl) benzene of lead salt, 100g ethylene-vinyl acetate superpolymer (VA content is 33%), 3g phthalic ester, 1g acrylic amide, 1g vinyl cyanide, 0.1g tert-butyl peroxy acetate, 0.2g, 0.5g four [β-(3 with the 250g surface-treated; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 0.5g Tyox B add in the high speed mixing roll; Under mixing speed 2100r/min, mix 10min.The mixing masterbatch that obtains joined in 90 ℃ the mill, mix,, obtain the ethylene-vinyl acetate copolymer matrix material of shielding property then 110 ℃ of following compression moldings.Its shielding efficiency to X ray is 72%, and tensile strength is 14MPa, and elongation at break is 700%, Shao Shi D hardness 41, with the stripping strength of cloth be 1.6N/mm.
Can know by the foregoing description; It is good that method of the present invention can make shielding property; Viscosifying power is strong; Softish ethylene-vinyl acetate copolymer matrix material, it can be used as antiradiation coating or glued membrane and is used for textiles and processes clothes with radiation proof function and cord etc., is with a wide range of applications.
Claims (14)
1. the preparation method of a radioprotective ethylene-vinyl acetate copolymer matrix material is characterized in that, comprises the steps:
Step 1, the preparation of surface-treated lead salt:
(a), in weight part, take by weighing 100 parts of lead salts, 1～5 part of coupling agent and 15～50 parts of solvents, said solvent is one or more in water and the alcohol organic solvent;
(b), said coupling agent is dissolved in the said solvent, join then in the said lead salt, mix back constant temperature activation, promptly get the surface-treated lead salt;
Step 2 in weight part, takes by weighing 100 parts of ethylene-vinyl acetate copolymers, 50～250 parts of surface-treated lead salts, 0～10 part of polar monomer, 0～1 part of initiator, 0.1～2 part of oxidation inhibitor, 0～15 part of lubricant; It is compound to mix the back fusion afterwards, promptly gets said radioprotective ethylene-vinyl acetate copolymer matrix material.
2. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1; It is characterized in that the lead salt described in the step 1 (a) is one or more the mixture in yellow lead oxide, plumbic oxide, lead sulfide, plumbic acetate, lead oxalate, lead stearate, the tri-lead tetroxide.
3. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1; It is characterized in that the coupling agent described in the step 1 (a) is one or more the mixture in silane coupling agent, titanate coupling agent, zirconium ester coupling agent, the aluminate coupling agent.
4. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1 is characterized in that, the alcohol organic solvent described in the step 1 (a) is ethanol, methyl alcohol and Virahol.
5. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1; It is characterized in that; Mixing described in the step 1 (b) is specially: on impeller, mix with 300～3000r/min, mixing time is 3～20min.
6. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1 is characterized in that, the constant temperature activation described in the step 1 (b) is specially: activation temperature is 100～140 ℃, and soak time is 1～4 hour.
7. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1 is characterized in that, vinyl acetate content is 12%～33% in the ethylene-vinyl acetate copolymer described in the step 2.
8. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1; It is characterized in that the polar monomer described in the step 2 is one or more the mixture in maleic anhydride, vinylformic acid, acrylic amide, vinyl cyanide, 3-butene-1-alcohol, the SY-Monomer G.
9. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1; It is characterized in that the initiator described in the step 2 is one or more the mixture in Di Cumyl Peroxide 99, Diisopropyl azodicarboxylate, Lucidol, tert-butyl peroxy acetate, the different monooctyl ester tert-butyl ester of peroxo-, peroxidized t-butyl perbenzoate, two (tert-butyl hydroperoxide sec.-propyl) benzene.
10. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1 is characterized in that, the oxidation inhibitor described in the step 2 is N; N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, Tyox B, tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester, two (2; 2,6,6-tetramethyl--4-piperidyl) sebate, 2; 2 '-methylene bis (4-methyl-6-tert butyl phenol), 2,6 di tert butyl 4 methyl phenol, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 4; 4 '-(β, β '-dihydroxyl dipropyl oxygen phenyl)-2, the mixture of one or more in the 2-propane.
11. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1; It is characterized in that the lubricant described in the step 2 is one or more the mixture in whiteruss, Triple Pressed Stearic Acid, phthalic ester, terephthalate, isophthalic acid ester, tributyl citrate, dibutyl maleate, dioctyl maleate, adipic acid ester, triethyl citrate, the glycol ether benzoic ether.
12. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1; It is characterized in that; Mixing described in the step 2 is specially: on impeller, mix with 600～2400r/min, mixing time is 5～30min.
13. the preparation method of radioprotective ethylene-vinyl acetate copolymer matrix material according to claim 1; It is characterized in that the fusion composite methods described in the step 2 is to open in the type of being smelt, compression molding, extrusion moulding, the injection moulding one or more.
14. the preparation method according to claim 1 or 13 described radioprotective ethylene-vinyl acetate copolymer matrix materials is characterized in that, the fusion compound temperature described in the step 2 is 70～150 ℃.
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| CN106633350A (en) * | 2016-12-12 | 2017-05-10 | 天津新霁科技有限公司 | Anti-radiation novel material and preparation method thereof |
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