NO150516B - PROCEDURE FOR POLYMERIZATION OF VINYL CHLORIDE - Google Patents
PROCEDURE FOR POLYMERIZATION OF VINYL CHLORIDE Download PDFInfo
- Publication number
- NO150516B NO150516B NO762508A NO762508A NO150516B NO 150516 B NO150516 B NO 150516B NO 762508 A NO762508 A NO 762508A NO 762508 A NO762508 A NO 762508A NO 150516 B NO150516 B NO 150516B
- Authority
- NO
- Norway
- Prior art keywords
- polymerization
- vinyl chloride
- solvent
- black
- acid
- Prior art date
Links
- 238000006116 polymerization reaction Methods 0.000 title claims description 60
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 24
- 239000000178 monomer Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 9
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000003505 polymerization initiator Substances 0.000 claims description 5
- YCUVUDODLRLVIC-UHFFFAOYSA-N Sudan black B Chemical compound C1=CC(=C23)NC(C)(C)NC2=CC=CC3=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 YCUVUDODLRLVIC-UHFFFAOYSA-N 0.000 claims description 4
- AOMZHDJXSYHPKS-UHFFFAOYSA-L disodium 4-amino-5-hydroxy-3-[(4-nitrophenyl)diazenyl]-6-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(N=NC=3C=CC=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 AOMZHDJXSYHPKS-UHFFFAOYSA-L 0.000 claims description 4
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 claims description 3
- NRWMZRAFXGWHLA-UHFFFAOYSA-N 4-[(4-phenyldiazenylphenyl)diazenyl]naphthalen-1-amine Chemical compound C12=CC=CC=C2C(N)=CC=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 NRWMZRAFXGWHLA-UHFFFAOYSA-N 0.000 claims description 3
- ZMWAXVAETNTVAT-UHFFFAOYSA-N 7-n,8-n,5-triphenylphenazin-5-ium-2,3,7,8-tetramine;chloride Chemical compound [Cl-].C=1C=CC=CC=1NC=1C=C2[N+](C=3C=CC=CC=3)=C3C=C(N)C(N)=CC3=NC2=CC=1NC1=CC=CC=C1 ZMWAXVAETNTVAT-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- ALLOLPOYFRLCCX-UHFFFAOYSA-N chembl1986529 Chemical compound COC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ALLOLPOYFRLCCX-UHFFFAOYSA-N 0.000 claims description 3
- AMMWFYKTZVIRFN-UHFFFAOYSA-M chembl2028442 Chemical compound [Na+].C1=CC=CC2=C(O)C(N=NC3=C4C=CC(=CC4=C(C=C3O)S([O-])(=O)=O)[N+]([O-])=O)=CC=C21 AMMWFYKTZVIRFN-UHFFFAOYSA-M 0.000 claims description 3
- UTIACSXEVKXHPT-YIDQSHOPSA-L disodium;4-[(2z)-2-[(5z)-4,6-dioxo-5-[(4-sulfonatonaphthalen-1-yl)hydrazinylidene]cyclohex-2-en-1-ylidene]hydrazinyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].C12=CC=CC=C2C(S(=O)(=O)[O-])=CC=C1N\N=C(\C=CC\1=O)C(=O)C/1=N\NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 UTIACSXEVKXHPT-YIDQSHOPSA-L 0.000 claims description 3
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- NRBKWAQSLYBVSG-UHFFFAOYSA-N solvent red 26 Chemical compound CC1=CC=CC=C1N=NC1=CC(C)=C(N=NC=2C3=CC=CC=C3C=CC=2O)C=C1C NRBKWAQSLYBVSG-UHFFFAOYSA-N 0.000 claims description 3
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 claims description 2
- WLDHEUZGFKACJH-ZRUFZDNISA-K Amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1\N=N\C1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-ZRUFZDNISA-K 0.000 claims description 2
- 235000012735 amaranth Nutrition 0.000 claims description 2
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 23
- 230000008021 deposition Effects 0.000 description 14
- 238000013019 agitation Methods 0.000 description 10
- -1 amine compound Chemical class 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 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 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- ISCIXAIEDTZJCQ-UHFFFAOYSA-M [4-[[4-(dimethylamino)phenyl]-phenylmethylidene]cyclohexa-2,5-dien-1-ylidene]-dimethylazanium;2-hydroxy-2-oxoacetate;oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C([O-])=O.C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 ISCIXAIEDTZJCQ-UHFFFAOYSA-M 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 229940035044 sorbitan monolaurate Drugs 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- CACRRXGTWZXOAU-UHFFFAOYSA-N octadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCS(O)(=O)=O CACRRXGTWZXOAU-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Nærværende oppfinnelse vedrører en forbedret fremgangsmåte for polymerisasjon av vinylklorid eller.en blanding av The present invention relates to an improved method for the polymerization of vinyl chloride or a mixture of
monomerer, som består hovedsakelig av vinylklorid, i nærvær av en polymerisasjonsinitiator i en polymerisasjonsreaktor, og hvorved avsetningen av polymerskall på innerveggene til polymerisasjonsreaktor og overflatene til en agitator samt andre deler, hvilke kommer i kontakt med monomeren eller monomerene, effektivt kan forhindres. monomers, consisting mainly of vinyl chloride, in the presence of a polymerization initiator in a polymerization reactor, and whereby the deposition of polymer shell on the inner walls of the polymerization reactor and the surfaces of an agitator as well as other parts, which come into contact with the monomer or monomers, can be effectively prevented.
Kjente fremgangsmåter for produksjon av vinylkloridpolymer omfatter suspensjonspolymerisasjon, emulsjonspolymerisasjon, løs-ningspolymerisasjon, gassfasepolymerisasjon og massepolymerisasjon. Disse'konvensjonelle polymerisasjdnsmetodene har den ulem- Known methods for the production of vinyl chloride polymer include suspension polymerization, emulsion polymerization, solution polymerization, gas phase polymerization and bulk polymerization. These conventional polymerization methods have the disadvantage of
pe at polymerisasjonsskall avsettes på overflatene og veggene til polymerisasjonsreaktoren og andre deler omfattende agitator-blader, hvilke deler kommer i kontakt med monomeren> og dette resulterer , i redusert utbytte av polymerprodukt samt redusert kjø-leeffekt når det gjelder polymerisasjonsreaktoren. Videre har skallavsetningen på overflatene en tendens til å løsne og så- pe that polymerization scale is deposited on the surfaces and walls of the polymerization reactor and other parts including agitator blades, which parts come into contact with the monomer> and this results in a reduced yield of polymer product as well as a reduced cooling effect in the case of the polymerization reactor. Furthermore, the shell deposit on the surfaces tends to loosen and so-
ledes komme inn i polymerproduktet, og dette resulterer i en lav-ere produktkvalitet. Videre må all skallavsetning fjernes etter hver polymerisasjoriskjøring, og dette krever meget arbeidstid, is led to enter the polymer product, and this results in a lower product quality. Furthermore, all scale deposits must be removed after each polymerization run, and this requires a lot of work time,
som igjen resulterer i redusert produktivitet. Dessuten innebærer arbeidet med skallfjerning et helsemessig problem p.g.a.at det monomere vinylklorid har kreftfremkallende egenskaper. which in turn results in reduced productivity. In addition, the work with shell removal involves a health problem because the monomeric vinyl chloride has cancer-causing properties.
I den hensikt å hindre en slik uønsket polymerskallavsetning på innerveggene- og øvrige overflater i polymerisasjonreaktoren, har det blitt foreslått å overtrekke disse overflater med en amin-forbindelse, en kinonforbindelse, én aldehydforbindelse eller en annen polar organisk forbindelse (jfr. U.S. patent 3.669946). In order to prevent such unwanted polymer shell deposition on the inner walls and other surfaces of the polymerization reactor, it has been proposed to coat these surfaces with an amine compound, a quinone compound, an aldehyde compound or another polar organic compound (cf. U.S. patent 3.669946) .
Denne fremgangsmåte er imidlertid anvendbar når det gjelder sus-pens jonspolymerisas jon, men den.er ikke egnet når det gjelder andre typer av polymerisasjon. Likevel er den anvendte fremgangsmåten ved suspensjonspolymerisasjon bare effektiv i forbindelse med homopolymerisasjon av vinylklorid, hvorved man kan. unngå dannelse av polymerskall selv etter et betydelig antall polymerisas jonskjøringer. Generelt er imidlerid den tidligere kjente This method is, however, applicable when it comes to suspension ion polymerization, but it is not suitable when it comes to other types of polymerization. Nevertheless, the method used in suspension polymerization is only effective in connection with homopolymerization of vinyl chloride, whereby one can. avoid polymer shell formation even after a significant number of polymerization runs. In general, however, the former is known
fremgangsmåte ufordelaktig når: procedure disadvantageous when:
(1) en kopolymerisasJon av vinylklorid med en kopolymériserbar monomer eller flere kopolymeriserbare monomerer skal foretas; (2) et emulgeringsmiddel tilsettes polymerisasjonsblandingen for å understøtte dispergeringen; (3) et acylperoksyd såsom benzoylperoksyd eller lauroylperoksyd anvendes som polymerisasjonsinitiator; og (4) polymerisasjonen utføres i nærvær av visse prosess-additiver såsom- smøremidler og stabilisatorer, f.eks. laurinsyre, stearinsyre, laurylsulfonat, stearylsulfonat og salter derav. (1) a copolymerization of vinyl chloride with a copolymerizable monomer or copolymerizable monomers shall be carried out; (2) an emulsifier is added to the polymerization mixture to aid dispersion; (3) an acyl peroxide such as benzoyl peroxide or lauroyl peroxide is used as the polymerization initiator; and (4) the polymerization is carried out in the presence of certain process additives such as lubricants and stabilizers, e.g. lauric acid, stearic acid, lauryl sulphonate, stearyl sulphonate and salts thereof.
Det har derfor vært et primært formål med nærværende oppfinnelse å fremskaffe en fremgangsmåte for polymerisasjon av vinylklorid elTer en blanding av monomerer som består i alt vesent- It has therefore been a primary purpose of the present invention to provide a method for the polymerization of vinyl chloride or a mixture of monomers consisting essentially of
lig av vinylklorid i nærvær av en polymerisasjonsinitiator i en polymerisasjonsreaktor, og hvorved avsetningen av polymerskall på innerveggene til polymerisasjonsreaktoren og øvrige overflater, hvilke kommer i kontakt med monomeren eller monomerene, i alt vesentlig kan. forhindres uansett polymerisasjonstype. lig of vinyl chloride in the presence of a polymerization initiator in a polymerization reactor, and whereby the deposition of polymer shell on the inner walls of the polymerization reactor and other surfaces, which come into contact with the monomer or monomers, essentially can. is prevented regardless of the type of polymerization.
Et annet formål med nærværende oppfinnelse har vært å fremskaffe en fremgangsmåte for polymerisasjon av vinylklorid eller en blanding av monomerer.som i- alt vesentlig består av vinylklorid, og hvorved man- lett kan fremstille vinylkloridpolymer av høy kvalitet. Another purpose of the present invention has been to provide a method for the polymerization of vinyl chloride or a mixture of monomers, which essentially consists of vinyl chloride, and by which vinyl chloride polymer of high quality can easily be produced.
Et ytterligere formål med nærværende oppfinnelse har vært å fremskaffe en fremgangsmåte for fremstilling av en polyvinylklorid-harpiks eller en kopolymer harpiks bestående i alt vesentlig av vinylklorid, og hvorved produksjonseffektiviteten til polymerisas jons-fremgangsmåten kan forbedres. A further object of the present invention has been to provide a method for the production of a polyvinyl chloride resin or a copolymer resin consisting essentially of vinyl chloride, and whereby the production efficiency of the polymerization process can be improved.
Med fremgangsmåten ifølge nærværende oppfinnelse har de ovenfor nevnte formål kunnet oppnås ved at man før polymerisasjonen, og eventuelt etter vasking med vann, overtrekker innerveggene til den nevnte polymerisasjonsreaktor og øvrige overflater, som kommer i kontakt med monomeren eller monomerene, med beleggmateriale som inneholder i det minste en elektrodonator-forbindelse valgt blant "Solvent Black-. 7", diaminonaftalen,, "Solvent Orange 14"., etylendiamin, "Basic Green 4", "Solvent Black 5", indulin, azulen, tiofenol, "Solvent Black 3", etanolamin og morfolin og i det minste en elektronakseptor-forbindelse valgt blant "Solvent Red 1", • Solvent Red 49", "Acid Black 2"", "Acid Brown 14", "Mordant Black 11", p-benzokinon, "Acid Red 27", "Solvent Red 26", difenokinon, fenol og difénylsyre dg p-benzoxinon. With the method according to the present invention, the above-mentioned objectives have been achieved by coating the inner walls of the aforementioned polymerization reactor and other surfaces, which come into contact with the monomer or monomers, with a coating material that contains in the at least one electron donor compound selected from "Solvent Black-. 7", diaminonaphthalene,, "Solvent Orange 14", ethylenediamine, "Basic Green 4", "Solvent Black 5", indulin, azulene, thiophenol, "Solvent Black 3" , ethanolamine and morpholine and at least one electron acceptor compound selected from "Solvent Red 1", • Solvent Red 49", "Acid Black 2"", "Acid Brown 14", "Mordant Black 11", p-benzoquinone, " Acid Red 27", "Solvent Red 26", diphenoquinone, phenol and diphenyl acid dg p-benzoxinone.
Ved fremgangsmåten ifølge nærværende oppfinnelse kan avsetningen In the method according to the present invention, the deposition can
av polymerskall på innerveggene til polymerisasjonsreaktoren, ågi-tatorbladene og andre deler, som kommer i kontakt med monomer eller monomerer., i alt vesentlig elimineres. Videre, er nærværende fremgangsmåte fordelaktig da den.er effektiv i forbindelse med en hvilken som helst type av polymerisasjon, d.v.s. , suspensjons-polymerisas jon, emulsjonspolymerisasjon, løsningspolymerisasjon eller massepolymerisasjon, ja også når det gjelder kopolymérisa-sjon av en monomerblanding bestående i ålt vesentlig av vinylklorid såvel som ved homdpolymerisasjbh av vinylklorid. of polymer shell on the inner walls of the polymerization reactor, the agitator blades and other parts, which come into contact with monomer or monomers., are essentially eliminated. Furthermore, the present method is advantageous as it is effective in connection with any type of polymerization, i.e. , suspension polymerization, emulsion polymerization, solution polymerization or mass polymerization, yes also when it comes to copolymerization of a monomer mixture consisting essentially of vinyl chloride as well as in homopolymerization of vinyl chloride.
Årsaken til at polymerskallavsetning unngås ved nærværende•fremgangs-måte, antas å bero på den mekanisme at en blanding av en av de nevnte «lektronavgivende forbindelser og-en åv de nevnte elektronmottag-ende forbindelser danner e-t - ladnings-overf ørihgsrkompleks , som er effektiv- for formålet , ■pg som skiller.seg fra de vanligvis anvendte beleggforbindelser såsom aminer, kinoner og aldehyder.. Overflaten på hvilken det således dannede ladnings-overførings-komplekset er påført vil, nærmere forklart, være i en tilstand, slik at den samme overflaten ikke absorberer skalldarinende mole-kyler som forekommer i polymerisasjonsblandingen. The reason why polymer shell deposition is avoided by the present method is believed to be due to the mechanism that a mixture of one of the aforementioned electron-donating compounds and one of the aforementioned electron-accepting compounds forms an e-t charge transfer complex, which is effective - for the purpose, ■pg which differs from the usually used coating compounds such as amines, quinones and aldehydes. the surface does not absorb shell-forming molecules that occur in the polymerization mixture.
De anvendbare elektrondonator-forbindelsene ved fremgangsmåten ifølge nærværende oppfinnelse omfatter "Solvent Black 7", diamino-' naftalen, ;"Solvent Orange 14", etylendiamin, "Basic Green 4", "Solvent Black 5", indulin, azulen, tiofenol, "Solvent Black 3", etanolamin og morfolin. The usable electron donor compounds in the method according to the present invention include Solvent Black 7, diamino-naphthalene, Solvent Orange 14, ethylenediamine, Basic Green 4, Solvent Black 5, indulin, azulene, thiophenol, Solvent Black 3", ethanolamine and morpholine.
De anvendbare elektronakseptor-forbindelsene ved fremgangsmåten ifølge nærværende oppfinnelse omfatter "Solvent Red 1", "Solvent Red 49", "Acid Black 2", "Acid Brown 14", "Mordant Black 11", p-benzokinon, "Aeid Red 27", "Solvent Red 26", difenokinorr, fenol og difenylsyre og p-benzokinon^ The useful electron acceptor compounds in the method of the present invention include "Solvent Red 1", "Solvent Red 49", "Acid Black 2", "Acid Brown 14", "Mordant Black 11", p-benzoquinone, "Aeid Red 27" , "Solvent Red 26", diphenoquinorr, phenol and diphenyl acid and p-benzoquinone^
Ved nærværende fremgangsmåte blandes minst en av de nevnte elektrondonatorforbindelser og i det minste en av de nevnte elek-tronakseptorforbindelser på enkel måte ved å oppløse eller dispergere disse sammen i et egnet medium..Det er også mulig å opp-løse eller dispergere disse hver for seg, slik at de erholdte to oppløsningene eller dispersjonene blandes. En slik oppløsning eller dispergering utføres vanligvis ved romtemperatur, eller også enkelte ganger under 0°C eller over 50°C, og, hvis ønsket, under bestråling med lys. Det anvendte lyset er vanligvis synlig eller ultraviolett lys, som kommer fra en fluoriscerende lampe eller kvikksølvlampe. In the present method, at least one of the mentioned electron donor compounds and at least one of the mentioned electron acceptor compounds are mixed in a simple way by dissolving or dispersing them together in a suitable medium. It is also possible to dissolve or disperse these separately themselves, so that the two solutions or dispersions obtained are mixed. Such a dissolution or dispersion is usually carried out at room temperature, or sometimes below 0°C or above 50°C, and, if desired, under irradiation with light. The light used is usually visible or ultraviolet light, which comes from a fluorescent lamp or mercury lamp.
Eksempler på media hvori nevnte elektronavgivende og elektronmottag ende forbindelser kan oppløses eller dispergeres er vann; etere såsom tetrahydrofuran og diisopropyleter; alkohler såsom metanol, etanol og propanol; estere såsom metylacetat og etylacetat; ketoner såsom aceton og metyletylketon; hydrokarboner såsom benzen-, toluen, xylen og heksan; klorerte hydrokarboner såsom metylen-klorid, karbontetraklorid og trikloretylen; og aprotiske løsnings-midler såsom dimetylformamid, dimetylacetamid, dimetylsulfoksyd og acetonitril. Disse nevnte media anvendes hver for seg eller i kombinasjon. Examples of media in which said electron-donating and electron-accepting compounds can be dissolved or dispersed are water; ethers such as tetrahydrofuran and diisopropyl ether; alcohols such as methanol, ethanol and propanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; hydrocarbons such as benzene, toluene, xylene and hexane; chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride and trichlorethylene; and aprotic solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and acetonitrile. These mentioned media are used separately or in combination.
Ifølge nærværende oppfinnelse oppnås en god effekt med hensyn til å hindre avsetning av polymerskall når blandingsforholdet av elextrondonator-forbindelsen og elektronakseptor-forbindelsen er mellom 1:5 og 5:1 (vektsforholdj. According to the present invention, a good effect is achieved with regard to preventing the deposition of polymer shells when the mixing ratio of the electron donor compound and the electron acceptor compound is between 1:5 and 5:1 (weight ratioj.
Mengdeforholdene i blandingen av elektrondonator- og elektronakseptor-f orbindelsene som påføres innerveggene til polymerisassjons-reaktoren og øvrige deler, som kommer i kontakt med monomeren eller monomerene, er uforandret i forhold til de mengder som anvendes ved tidligere kjente fremgangsmåter, og hvorved konven-sjonelle beleggmaterialer anvendes. D.v.s. at man oppnår en til-fredsstillende effekt med herrsyn til å hindre polymerskallavsetning .nar blandinge appliseres. på overflatene i et mengdef orhold--som tilsvarer . minst 0,001 g/m 2 overtrukket flate,,Dét anbefales imidlertid at de således overtrukkede overflatene vaskes med vann for å fjerne.eventuelle overskudd av beleggmateriale, som eventuelt vil kunne løsne og komme inn i polymerproduktet. The quantity ratios in the mixture of the electron donor and electron acceptor compounds that are applied to the inner walls of the polymerization reactor and other parts that come into contact with the monomer or monomers are unchanged in relation to the quantities used in previously known methods, and whereby conventional coating materials are used. I.e. that a satisfactory effect is achieved with regard to preventing polymer shell deposition when the mixtures are applied. on the surfaces in a quantitative ratio--which corresponds to . at least 0.001 g/m 2 coated surface,, However, it is recommended that the thus coated surfaces be washed with water to remove any excess of coating material, which could eventually come loose and enter the polymer product.
Videre kan effekten med hensyn til å hindre avsetning av polymerskall forsterkes ved .å tilsette ett eller flere alkaliske stoffér såsom oksyder, hydroksyder, karbonater, fosfater, bikarbonater,. ■' silikater og karboksylater av alkalimetaller, jordalkalimetaller og ammonium til polymerisasjonblandingen. I dette tilfelle fore-trekkes imidlertid at mengden av slike additiver er mindre enn 1 vekt-%, beregnet på monomeren eller monomerene, slik at kvali-teten til den erholdte polymer ikke skal bli forringet, og slik at polymerisasjonsreaksjonen ikke forstyrres. Furthermore, the effect with regard to preventing the deposition of polymer shell can be enhanced by adding one or more alkaline substances such as oxides, hydroxides, carbonates, phosphates, bicarbonates. ■' silicates and carboxylates of alkali metals, alkaline earth metals and ammonium to the polymerization mixture. In this case, however, it is preferred that the amount of such additives is less than 1% by weight, calculated on the monomer or monomers, so that the quality of the polymer obtained will not be impaired, and so that the polymerization reaction is not disturbed.
Fremgangsmåten ifølge nærværende oppfinnelse er effektiv når det gjelder alle typer av polymerisasjon av vinylklorid, d.v.s. sus-pens jonspolymerisas jon, løsnings- og massepolymerisasjon. Fremgangsmåten ifølge nærværende oppfinnelse er dessuten ikke begren-set av polymerisasjonsbetingelser såsom polymerisasjonstempera-turer og agiteringsbetingelse eller av typen av additiver som tilsettes polymerisasjonsblandingen, f.eks. suspensjonsmidler såsom partielt forsåpet polyvinylalkohol og metylcellulose, anioniske emulgeringsmidler såsom natriumlaurylsulfat, natriumdodecylbenzen-sulfonat og natriumdioktylsulfosuccinat, ikke-ioniske emulgeringsmidler såsom sorbitanmonolaurat og polyoksyetylenalkyleter, kjede-overføringsmidler såsom trikloretylen og merkaptaner og initia-torer såsom diidopropylperoksydikarbonat, lauroylperoksyd og dimetylvaleronitril. Effekten av fremgangsmåten ifølge nærværende oppfinnelse påvirkes ikke av nærvær av visse additiver såsom fyll-stoffer, (f.eks. kalsiumkarbonat og titandioksyd), stabilisatorer (f.eks. tribasisk blysulfat, kalsiumstearat og dibutyltinnlaurat), smøremidler (f.eks. risvoks og stearinsyre) og myknere (f.eks. dioktylftalat og dibutylftalat). The method according to the present invention is effective in all types of polymerization of vinyl chloride, i.e. suspension polymerisation, solution and mass polymerisation. The method according to the present invention is also not limited by polymerization conditions such as polymerization temperatures and agitation conditions or by the type of additives that are added to the polymerization mixture, e.g. suspending agents such as partially saponified polyvinyl alcohol and methyl cellulose, anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate and sodium dioctyl sulfosuccinate, nonionic emulsifiers such as sorbitan monolaurate and polyoxyethylene alkyl ether, chain transfer agents such as trichloroethylene and mercaptans and initiators such as diidopropyl peroxydicarbonate, lauroyl peroxide and dimethylvaleronitrile. The effect of the method according to the present invention is not affected by the presence of certain additives such as fillers (e.g. calcium carbonate and titanium dioxide), stabilizers (e.g. tribasic lead sulphate, calcium stearate and dibutyltin laurate), lubricants (e.g. rice wax and stearic acid) and plasticizers (e.g. dioctyl phthalate and dibutyl phthalate).
Videre kan man med nærværende oppfinnelse oppnå en utmerket effekt ikke bare ved homopolymerisasjon av vinylklorid, men også ved kopolymerisasjon av vinylklorid med en eller flere monomerer som er kopolymeriserbare med vinylklorid, f.eks. vinylestere, vinyl-etere, akrylonitril^ akrylsyre, akrylsyreestere, metakrylsyre, metakrylsyreestere, maleinsyre, maleinsyreestere, maleinsyrean-hydrid, furmarsyre, furmarsyreestere, aromatiske vinylmonomrer, vinylhalogenider med unntakelse av vinylklorid, vinylidenhaloge-nider og olefiner. Furthermore, with the present invention, an excellent effect can be achieved not only by homopolymerization of vinyl chloride, but also by copolymerization of vinyl chloride with one or more monomers that are copolymerizable with vinyl chloride, e.g. vinyl esters, vinyl ethers, acrylonitrile, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, maleic acid, maleic acid esters, maleic anhydride, furmaric acid, furmaric acid esters, aromatic vinyl monomers, vinyl halides with the exception of vinyl chloride, vinylidene halides and olefins.
Nærværende oppfinnelse skal ytterligere illustreres ved hjelp av følgende eksempler. The present invention shall be further illustrated by means of the following examples.
Eksempel . 1 Example . 1
•Forskjellige beleggløsninger ble fremstilt ved å blande eléktron-donator-forbindelsene og elektro'nakseptor-f orbindelsene i løs-ningsmidlene, slik som vist i tabell I, ved romtemperatur under agitering i 3 timer, hvoretter man foretok filtrering for derved, å få en konsentrasjon på 1 vekt-% beregnet på løsningsmid-let. •Different coating solutions were prepared by mixing the electron-donor compounds and the electron-acceptor compounds in the solvents, as shown in Table I, at room temperature under agitation for 3 hours, after which filtration was carried out in order to obtain a concentration of 1% by weight calculated on the solvent.
Hver belegg-løsning, som man således erholdt, ble. applisert på overflatene til innerveggene til en 1.000-liter stor rustfri stålpolymerisasjonsreaktor i et mengdeforhold som tilsvarte 0,1 g/m 2(beregnet som tørrstoff). De således behandlede overflatene ble deretter tørket og vasket med vann. Each coating solution, which was thus obtained, was applied to the surfaces of the inner walls of a 1,000-liter stainless steel polymerization reactor in a quantity ratio that corresponded to 0.1 g/m 2 (calculated as dry matter). The thus treated surfaces were then dried and washed with water.
Deretter ble 50 0 kg avionisert vann, 0,5 kg hydroksypropylmetyl-cellulose, 0,5 kg sorbitanmonolaurat, 2 00 g dimetylvaleronitril og 200 kg vinylklorid chargert i polymerisasjonsreaktoren, hvoretter polymerisasjonen ble utført ved 57°C i 10 timer. Etter fullføring av polymerisasjonen ble mengden av polymerskallavsetning på overflatene bestemt med de i den samme tabell an-gitte resultater. Then, 500 kg of deionized water, 0.5 kg of hydroxypropyl methyl cellulose, 0.5 kg of sorbitan monolaurate, 200 g of dimethylvaleronitrile and 200 kg of vinyl chloride were charged into the polymerization reactor, after which the polymerization was carried out at 57°C for 10 hours. After completion of the polymerization, the amount of polymer shell deposition on the surfaces was determined with the results given in the same table.
Eksempel 2 Example 2
Beleggløsning ble fremstilt ved å blande "Solvent Black 3" som elektrondonator og "Acid Black 2" som elektronakseptor i for-skjellige mengdeforhold (vektsforhold) i visse løsningsmidler under spesielle betingelser, slik som angitt i tabell II, hvoretter man foretok filtrering for således å få en konsentrasjon på 1 vekt-% beregnet på løsningsmidlet. Coating solution was prepared by mixing "Solvent Black 3" as electron donor and "Acid Black 2" as electron acceptor in different proportions (weight ratio) in certain solvents under special conditions, as indicated in Table II, after which filtration was carried out in order to obtain a concentration of 1% by weight calculated on the solvent.
Hver beleggløsning, som man således erholdt, ble appliasert på overflatene til innerveggene til en 1.000-liter stor rustfri stålpolymerisasjonsreaktor samt på agitatorbladene i et merrgde-forhold som tilsvarte 0,1 g/m 2 (som tørrstoff). De således behandlede overflatene ble deretter tørket og vasket med vann. Deretter ble 500 kg avionisert vann, 0,5 kg partielt forsåpet polyvinylalkohol, 100 g diisopropylperoksydikarbonat og 200 kg vinylklorid chargert i polymerisasjonsreaktoren, hvoretter polymerisasjonen ble utført ved 57°C i 10 timer under agitering ved en hastighet på 100 o.p.iru Etter fullført polymerisas jon ble mengden av polymerskallavsetning på overflatene bestemt, og resultatene angis i tabelt II. Each coating solution thus obtained was applied to the surfaces of the inner walls of a 1,000-liter stainless steel polymerization reactor as well as to the agitator blades in a density ratio corresponding to 0.1 g/m 2 (as dry matter). The thus treated surfaces were then dried and washed with water. Next, 500 kg of deionized water, 0.5 kg of partially saponified polyvinyl alcohol, 100 g of diisopropyl peroxydicarbonate and 200 kg of vinyl chloride were charged into the polymerization reactor, after which the polymerization was carried out at 57°C for 10 hours under agitation at a speed of 100 rpm. After completion of polymerization the amount of polymer shell deposition on the surfaces was determined, and the results are given in Table II.
Betingelser (a): Begge forbindelser befant seg sammen i løsnings-midlet under agitering i 3 timer ved romtemp. Conditions (a): Both compounds were together in the solvent under agitation for 3 hours at room temperature.
(b) : Samme betingelser som (a) med unntakelse for (b) : Same conditions as (a) except for
at temperaturen var 0°C. that the temperature was 0°C.
(c) : Samme betingelser som (a) med unntakelse for (c) : Same conditions as (a) except for
at temperaturen var 90°C. that the temperature was 90°C.
(d) : Av hver forbindelse ble det dannet en løsning ved hjelp av løsningsmidlet under agitering i 3 timer ved romtemp., og de erholdte 2 løsninger ble bla-det sammen. (e) : Samme betingelser som (a) med unntakelse for at (d) : Of each compound, a solution was formed using the solvent under agitation for 3 hours at room temperature, and the 2 solutions obtained were combined. (e) : Same conditions as (a) with the exception that
bestrålning med UV-lvs kom i tillegg. irradiation with UV-lvs was added.
(f) : Samme betingelser som (a) med unntakelse for at agiteringsperioden varte 1 time. (f): Same conditions as (a) with the exception that the agitation period lasted 1 hour.
Eksempel 3 Example 3
Ved å anvende beleggløsningen fra forsøk nr. 28 i eksempel 2 ble overflaten til innerveggene til et 1000-liter stort rust-fritt stål-polymerisasjonskar samt agitatoren, som hadde blad av skovl-type, og som var 6 00. mm i ..diameter ^overtrukket med en mengde som tilsvarte 0,1 g/m 2, regnet som tørrstoff. De således behandlede overflatene ble deretter tørket og vasket med vann. By using the coating solution from trial No. 28 in Example 2, the surface of the inner walls of a 1000-liter stainless steel polymerization vessel as well as the agitator, which had paddle-type blades, and which was 600 mm in diameter ^coated with an amount corresponding to 0.1 g/m 2, calculated as dry matter. The thus treated surfaces were then dried and washed with water.
Deretter ble 100 kg vinylklorid, 200 kg avionisert vann og visse mengder additiver sammen med visse mengder polymerisas jonsinitiator og dispergeringsmiddel, som angitt i tabell III, tilsatt til polymerisasjonsreaktoren, hvoretter polymerisas jonen ble foretatt ved 57°C i 10 timer under en agiterings-hastighet på 100 omdreininger pr. minutt. Etter fullføring av polymerisasjonen ble mengden avsatt polymerskall på overflatene bestemt. Resultatene fremgår av tabell III under rubrikken "Nærværende oppfinnelse". Then, 100 kg of vinyl chloride, 200 kg of deionized water and certain amounts of additives together with certain amounts of polymerization initiator and dispersant, as indicated in Table III, were added to the polymerization reactor, after which the polymerization was carried out at 57°C for 10 hours under an agitation speed at 100 revolutions per minute. After completion of the polymerization, the amount of polymer shell deposited on the surfaces was determined. The results appear in table III under the heading "Present invention".
For sammenligning ble samme arbeidsoperasjoner som angitt ovenfor gjentatt med unntakelse for at beleggløsningen var en oppløsning av "Solvent Black. 7" alene. Mengden av polymerskall ble bestemt, og resultatene angis i samme tabell under rubrikken "Sammenligning". For comparison, the same work operations as indicated above were repeated with the exception that the coating solution was a solution of "Solvent Black. 7" alone. The amount of polymer shell was determined and the results are given in the same table under the heading "Comparison".
For ytterligere sammenligning ble forsøk nr. 52, som vises i For further comparison, trial No. 52, shown in
tabellen, utført på lignende måte med unntakelse for at ingen beleggløsning ble anvendt. Resultatet,d.v.s. mengden, av polymerskallavsetning ved dette forsøk angis i samme tabell. the table, carried out in a similar way with the exception that no coating solution was used. The result, i.e. the amount of polymer shell deposition in this experiment is given in the same table.
Merknader: Notes:
(1) I forsøk nr.43 ble det anvendt en monomerblanding bestående av 85 kg vinylklorid og 15 kg vinylacetat istedenfor vinylklorid som ble anvendt i øvrige forsøk. (2) I forsøk nr. 44 ble det anvendt en monomerblanding bestående av 95 kg vinylklorid og 5 kg vinylacetat. (1) In experiment no. 43, a monomer mixture consisting of 85 kg of vinyl chloride and 15 kg of vinyl acetate was used instead of the vinyl chloride that was used in the other experiments. (2) In experiment no. 44, a monomer mixture consisting of 95 kg of vinyl chloride and 5 kg of vinyl acetate was used.
(3) I forsøk nr. 51 var turtallet ved agitering 30. (3) In experiment no. 51, the speed during agitation was 30.
(4) I tabellen betyr DVN dimetylvaleronitril; LPO (4) In the table, DVN means dimethylvaleronitrile; LPO
betyr lauroylperoksyd; BPO betyr benzoylperoksyd; means lauroyl peroxide; BPO means benzoyl peroxide;
IPP betyr diisopropylperoksydikarbonat; PVA betyr partielt forsåpet polyvinylalkohol; HPMC betyr hydroksypropylmetylcelluloser S.L.S, betyr natriumlaurylsulfat; CA. betyr cetylalkohol og DOP betyr dioktylftalat. IPP means diisopropyl peroxydicarbonate; PVA means partially saponified polyvinyl alcohol; HPMC means hydroxypropyl methyl cellulose S.L.S means sodium lauryl sulfate; ABOUT. means cetyl alcohol and DOP means dioctyl phthalate.
Eksempel 4-Beleggløsningen fra forsøk nr. 28,eksempel 2, ble applisert på overflatene til innerveggene til en 5-Iiter stor rustfri stål-polymerisas jonsreaktor samt agitatorbladene i et mengdeforhold som tilsvarte 0,1 g/m 2. De således behandlede overflatene ble deretter tørket og vasket med vann. Deretter ble 1800 g vinylklorid, 2700 g avionisert vann, 0,1 g partielt forsåpet polyvinylalkohol, 0,1 g natriumstearat og 0,03 g dimetylvaleronitril tilsatt til polymerisasjonsreaktoren, hvoretter man foretok polymerisasjon ved 57°C i nærvær av et bestemt alkalisk stoff som ble tilsatt i mengder og ved tider som angis i tabell IV. Polymerisasjonskjøringer ble gjentatt med samme polymerisasjonsreaktor inntil polymerskallavsetning på de overtrukkede overflater ble funnet å overstige 1 g/m eller observert med det blotte øye. Antall polymerisasjonskjøringer, før nettopp en slik polymerisasjonskjøring hvor polymerskallavsetning- ble observert, ble registrert. Resultatene fremgår av tabell IV. Example 4 - The coating solution from experiment no. 28, example 2, was applied to the surfaces of the inner walls of a 5-litre stainless steel polymerisation ion reactor as well as the agitator blades in a quantity ratio corresponding to 0.1 g/m 2. The thus treated surfaces were then dried and washed with water. Next, 1800 g of vinyl chloride, 2700 g of deionized water, 0.1 g of partially saponified polyvinyl alcohol, 0.1 g of sodium stearate and 0.03 g of dimethylvaleronitrile were added to the polymerization reactor, after which polymerization was carried out at 57°C in the presence of a specific alkaline substance which were added in amounts and at times indicated in Table IV. Polymerization runs were repeated with the same polymerization reactor until polymer scale deposition on the coated surfaces was found to exceed 1 g/m or observed with the naked eye. The number of polymerization runs, before just such a polymerization run where polymer shell deposition was observed, was recorded. The results appear in Table IV.
Eksempel 5 Example 5
Beleggløsning fra forsøk nr. 28 i eksempel 2 ble applisert på overflaten til innerveggene til 2 polymerisasjonsreaktorer, hvorved den ene var en 2-liter stor rustfri stålreaktor av vertikal-type og den andre var.en 4-liter stor rustfri stålreaktor av horisontal-type, samt andre deler som kommer i kontakt med monomeren, og da i et mengdeforhold som tilsvarte 0,1 g/m . De overtrukkede overflater ble tørket og deretter vasket med vann. Deretter ble 800 g vinylklorid og 0,4 g dimetylvaleronitril tilsatt til den første 2-liter store polymerisasjonsreaktoren, etterfulgt av polymerisasjon ved 60°C i 2 timer med et turtall på .9.00 ved agiteringen. Den erholdte reaksjonsblandingen ble overført til den andre 4-liter store polymerisasjonsreaktoren, hvor det var tilsatt 800 g vinylklorid og 0,4 g dimetylvaleronitril, for derved å utføre en ytterligere polymerisasjon ved 57°C i 10 timer og med et turtall på 100 ved agiteringen. Coating solution from test no. 28 in example 2 was applied to the surface of the inner walls of 2 polymerization reactors, whereby one was a 2-liter stainless steel vertical-type reactor and the other was a 4-liter horizontal-type stainless steel reactor , as well as other parts that come into contact with the monomer, and then in a quantity ratio that corresponded to 0.1 g/m . The coated surfaces were dried and then washed with water. Next, 800 g of vinyl chloride and 0.4 g of dimethylvaleronitrile were added to the first 2-liter polymerization reactor, followed by polymerization at 60° C. for 2 hours with an agitation speed of .9.00. The resulting reaction mixture was transferred to the second 4-liter polymerization reactor, where 800 g of vinyl chloride and 0.4 g of dimethylvaleronitrile were added, in order to carry out a further polymerization at 57°C for 10 hours and with a speed of 100 during the agitation .
Polymerskallavsetningen på overflaten til hvér polymerisasjonsreaktor ble bestemt som angitt i tabell V. The polymer shell deposition on the surface of each polymerization reactor was determined as indicated in Table V.
For sammenligning ble et lignende forsøk utført uten anvendelse av beleggløsningen eller ved anvendelse av en beleggløsning bestående av "Solvent Black" alene. Resultatene vises i samme tabell. For comparison, a similar experiment was carried out without using the coating solution or using a coating solution consisting of "Solvent Black" alone. The results are shown in the same table.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP50089827A JPS5213592A (en) | 1975-07-23 | 1975-07-23 | Polymerization of vinyl chloride |
Publications (3)
Publication Number | Publication Date |
---|---|
NO762508L NO762508L (en) | 1977-01-25 |
NO150516B true NO150516B (en) | 1984-07-23 |
NO150516C NO150516C (en) | 1984-10-31 |
Family
ID=13981576
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO762508A NO150516C (en) | 1975-07-23 | 1976-07-19 | PROCEDURE FOR POLYMERIZATION OF VINYL CHLORIDE |
Country Status (20)
Country | Link |
---|---|
JP (1) | JPS5213592A (en) |
BE (1) | BE844215A (en) |
BR (1) | BR7604729A (en) |
CA (1) | CA1057896A (en) |
CH (1) | CH634856A5 (en) |
CU (1) | CU34543A (en) |
DE (1) | DE2632468A1 (en) |
DK (1) | DK152217C (en) |
ES (1) | ES449800A1 (en) |
FR (1) | FR2318883A1 (en) |
GB (1) | GB1559334A (en) |
HU (1) | HU174223B (en) |
IT (1) | IT1064851B (en) |
NL (1) | NL181581C (en) |
NO (1) | NO150516C (en) |
PL (1) | PL107283B1 (en) |
PT (1) | PT65399B (en) |
SE (1) | SE7608240L (en) |
TR (1) | TR19309A (en) |
YU (1) | YU39177B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4220743A (en) * | 1977-03-08 | 1980-09-02 | Ici Australia Limited | Process for aqueous dispersion polymerization of vinyl halide monomers in coated reactor |
EP0003875B1 (en) * | 1978-02-24 | 1981-06-24 | Imperial Chemical Industries Plc | Coating product for use in a reactor for vinyl halide polymerisation process, the reactor and the process |
DE2912571A1 (en) * | 1979-03-29 | 1980-10-09 | Basf Ag | METHOD FOR POLYMERIZING VINYL CHLORIDE |
IT1190641B (en) * | 1986-05-16 | 1988-02-16 | Enichem Polimeri | PROCESS FOR WATER SUSPENSION POLYMERIZATION OF VINYL MONOMERS CONTAINING HALOGEN |
CA2053827A1 (en) * | 1990-10-23 | 1992-04-24 | Toshihide Shimizu | Polymer scale preventive composition |
TWI238106B (en) | 2002-12-20 | 2005-08-21 | Miyanaga Kk | Blade edge structure for core drill |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE94210C (en) * | 1970-05-07 | |||
DE2044259C2 (en) * | 1970-09-07 | 1985-08-22 | Shinetsu Chemical Co., Tokio/Tokyo | Process for the suspension polymerization of vinyl chloride |
US3778423A (en) * | 1971-06-28 | 1973-12-11 | Universal Pvc Resins | Method for reducing polymer deposit in polymerization of vinyl chloride |
GB1439339A (en) * | 1972-11-20 | 1976-06-16 | Ici Ltd | Vinyl chloride polymerisation process |
JPS50157A (en) * | 1973-05-15 | 1975-01-06 | ||
US3849179A (en) * | 1973-08-27 | 1974-11-19 | Goodrich Co B F | Internally coated reaction vessel and process for coating the same |
JPS5224953B2 (en) * | 1974-12-27 | 1977-07-05 | Shinetsu Chemical Co |
-
1975
- 1975-07-23 JP JP50089827A patent/JPS5213592A/en active Granted
-
1976
- 1976-06-19 CU CU34543A patent/CU34543A/en unknown
- 1976-07-13 CA CA256,812A patent/CA1057896A/en not_active Expired
- 1976-07-13 ES ES449800A patent/ES449800A1/en not_active Expired
- 1976-07-16 BE BE168975A patent/BE844215A/en unknown
- 1976-07-19 NO NO762508A patent/NO150516C/en unknown
- 1976-07-19 GB GB29921/76A patent/GB1559334A/en not_active Expired
- 1976-07-19 DE DE2632468A patent/DE2632468A1/en active Granted
- 1976-07-19 YU YU01777/76A patent/YU39177B/en unknown
- 1976-07-19 CH CH923476A patent/CH634856A5/en not_active IP Right Cessation
- 1976-07-19 NL NLAANVRAGE7607969,A patent/NL181581C/en not_active IP Right Cessation
- 1976-07-20 SE SE7608240A patent/SE7608240L/en not_active Application Discontinuation
- 1976-07-21 BR BR7604729A patent/BR7604729A/en unknown
- 1976-07-21 HU HU76SI1526A patent/HU174223B/en unknown
- 1976-07-21 PL PL1976191341A patent/PL107283B1/en unknown
- 1976-07-22 PT PT65399A patent/PT65399B/en unknown
- 1976-07-22 TR TR19309A patent/TR19309A/en unknown
- 1976-07-22 DK DK329776A patent/DK152217C/en not_active IP Right Cessation
- 1976-07-23 IT IT25638/76A patent/IT1064851B/en active
- 1976-07-23 FR FR7622483A patent/FR2318883A1/en active Granted
Also Published As
Publication number | Publication date |
---|---|
PT65399B (en) | 1978-01-27 |
PL107283B1 (en) | 1980-02-29 |
CA1057896A (en) | 1979-07-03 |
CH634856A5 (en) | 1983-02-28 |
YU39177B (en) | 1984-08-31 |
DE2632468A1 (en) | 1977-02-10 |
HU174223B (en) | 1979-11-28 |
DK152217C (en) | 1988-08-29 |
IT1064851B (en) | 1985-02-25 |
BR7604729A (en) | 1977-08-02 |
CU34543A (en) | 1979-07-16 |
NO762508L (en) | 1977-01-25 |
TR19309A (en) | 1978-11-28 |
DK152217B (en) | 1988-02-08 |
NO150516C (en) | 1984-10-31 |
DK329776A (en) | 1977-01-24 |
PT65399A (en) | 1976-08-01 |
FR2318883A1 (en) | 1977-02-18 |
JPS5213592A (en) | 1977-02-01 |
BE844215A (en) | 1976-11-16 |
NL7607969A (en) | 1977-01-25 |
NL181581B (en) | 1987-04-16 |
ES449800A1 (en) | 1977-12-01 |
FR2318883B1 (en) | 1979-03-23 |
JPS5328347B2 (en) | 1978-08-14 |
SE7608240L (en) | 1977-01-24 |
YU177776A (en) | 1982-05-31 |
DE2632468C2 (en) | 1989-04-20 |
GB1559334A (en) | 1980-01-16 |
NL181581C (en) | 1987-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0906345B1 (en) | Brominated polystyrene having improved thermal stability and color and process for the preparation thereof | |
NO151414B (en) | PROCEDURE FOR POLYMERIZATION OF ETHYLENIC Saturated MONOMERS | |
NO150516B (en) | PROCEDURE FOR POLYMERIZATION OF VINYL CHLORIDE | |
NO155886B (en) | PROCEDURE FOR POLYMERIZATION OF VINYL MONOMERS. | |
US5789499A (en) | Polymerization process of vinyl chloride in the presence of oxygen | |
NO790432L (en) | PROCEDURE FOR POLYMERIZATION OF VINYL HALOGENIDE MONOMERS IN WATER DISPERSION | |
US5321104A (en) | Deposit suppressant composition for the internal surfaces of a polymerization reactor and a method of polymerizing vinyl monomers with use of said deposit suppressant composition | |
NO172988B (en) | PROCEDURE FOR AA PREVENTING POLYMER SURFACES IN A CONTAINER UNDER POLYMERIZATION OF MONOMERS WHICH HAVE AN ETHYLENIC DOUBLE BOND | |
US3544539A (en) | Process for the suspension polymerization of vinyl chloride | |
EP0051945B1 (en) | Improved suspension process for the polymerization of vinyl chloride monomer | |
EP0138660A1 (en) | Method for preventing polymer scale deposition in the polymerization of an ethylenically unsaturated monomer | |
CN100434446C (en) | Method for preparing latex | |
NO163860B (en) | PROCEDURE FOR AA PREVENTED POLYMER SHELL PROPOSAL BY POLYMERIZATION OF ETHYLENIC Saturated MONOMERS. | |
NO162726B (en) | PROCEDURE FOR SUSPENSION POLYMERIZATION OF VINYL CHLORIDE MONOMES AND EVENTS. | |
EP0027466A4 (en) | Coating polymerization reactors with the reaction products of thiodiphenols and a bleach. | |
JP3110600B2 (en) | Polymer scale adhesion inhibitor, and method for producing polymer using the same | |
KR810001533B1 (en) | Method for the polymerization of vinyl monomers | |
SU359831A1 (en) | METHOD OF OBTAINING POLYMERS BASED ON VINYL CHLORIDE | |
US6156853A (en) | Deposit suppressant composition for a polmerization reactor and a method of polymerizing vinyl monomers with use of said deposit suppressant composition | |
JPS63108004A (en) | Production of chlorinated vinyl chloride resin for forming lowly viscous and transparent solution | |
NO791683L (en) | PROCEDURE FOR AA PREVENT POLYMER BUILDING | |
JPH08109202A (en) | Production of polymer | |
KR810001490B1 (en) | Method for the preparation of vinyl chloride | |
JPH04170406A (en) | Production of vinyl chloride polymer | |
NO853949L (en) | PROCEDURE FOR THE PREPARATION OF POLYVINYL CHLORIDE RESIN. |