CS205496B1 - Manufacturing process of copolimer vinylchloride/olefin and/or vinylchloride/olefins with increased thermal stability - Google Patents
Manufacturing process of copolimer vinylchloride/olefin and/or vinylchloride/olefins with increased thermal stability Download PDFInfo
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- CS205496B1 CS205496B1 CS655579A CS655579A CS205496B1 CS 205496 B1 CS205496 B1 CS 205496B1 CS 655579 A CS655579 A CS 655579A CS 655579 A CS655579 A CS 655579A CS 205496 B1 CS205496 B1 CS 205496B1
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- temperature
- copolymer
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- vinyl chloride
- thermal stability
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 33
- 150000001336 alkenes Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 46
- 238000007334 copolymerization reaction Methods 0.000 claims description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- -1 perpendiculars Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 239000003017 thermal stabilizer Substances 0.000 claims description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 235000006708 antioxidants Nutrition 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 238000004061 bleaching Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 claims 1
- 239000003507 refrigerant Substances 0.000 claims 1
- 238000010079 rubber tapping Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 3
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical class CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- GNSPWPOHVBPSDX-UHFFFAOYSA-N 4-ethylphenol Chemical compound [CH2]CC1=CC=C(O)C=C1 GNSPWPOHVBPSDX-UHFFFAOYSA-N 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 1
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N para-ethyl phenol Natural products CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Vynález se týká spfisobu výroby kopolyeáru vinylchloridu β olefinom alebo zeeeou olefinov Cz až Cj^, zvlášť β propénom a 1-elkánmi až C^, pri ktoroe ea zabezpečuje Jednak poaerne vysokými koncentráciaei iniciátorov volnoradikálovej kopolymerizácie, zvlášť peroxidických zlúčenín, dostatečné vysoká rýchloeť kopolymerizácie, jednak Salšimi, technicky jednoduchýei opatrenlaml, aj zvýšená tepelná stabilita vyrobeného kopolyeáru·The present invention relates to processes for the preparation registration kopolyeáru chloride β olefin or Zeee olefin C of up to C ^, particularly β propene and 1-Elkan to C ^, in which was converted into the EA is obtained from the poaerne high koncentráciaei initiators of free-radical copolymerization, in particular a peroxide compound, a sufficient high rýchloeť copolymerization. on the one hand, Salshimi, a technically simple precaution, and the increased thermal stability of the produced copolyye ·
Oobre znána je výrobě kopolynárov vinylchloridu hlavně e 1-alkánmi, zvlášť kopolymáru vinylchloridu e eténom, propénom, izobutánom a 1-butánom. Mdže sa uekutočšovať spfieobom kontinuálnej, ale hlavně diskontlnuálnej emulznej a zvlášť suspenznaj kopolymerizácie. Vzhladom ne značná rozdiely v kopolymerizačných parametroch vinylchloridu a alkánov, zvlášť v procesech diskontlnuálnej kopolymerizácie, sa dostávajú produkty značné nehomogánne. Nevýše, celková reekčná rýchloeť volnoradikálovej kopolymerizácie vinylchloridu s alkénmi, v porovnáni e rýchlosťou homopolymerizácie vinylchloridu, je niekolkonáeobne nižšla . To má nepriaznivý vplyv jednak na homogenitu kopolyeáru, jednak na technické i ekonomická parametre procesu výroby kopolymárov vinylchloridu s elkánml.It is well known to produce vinyl chloride copolymers mainly with 1-alkanes, especially vinyl chloride copolymers with ethene, propene, isobutane and 1-butane. It can be carried out by means of continuous but mainly discontinuous emulsion and especially suspension copolymerization. Because of the considerable differences in the copolymerization parameters of vinyl chloride and alkanes, especially in the processes of discontinuous copolymerization, the products are substantially inhomogeneous. However, the overall reaction rate of the free-radical copolymerization of vinyl chloride with alkenes, compared to the homopolymerization rate of vinyl chloride, is several times lower. This has an adverse effect on the homogeneity of the copolyye and on the technical and economic parameters of the process of producing copolymers of vinyl chloride with alkane.
Ne odetránenie týchto nedostatkov ea v technickaj praxi využívá viac spfieobov. Najbežnejši spočívá v používaní troj- až pšťnásebne vyšších množetiev iniciátorov v porovnaní a homopolymerizáciou vinylchloridu za podobných teplotných a Salšich podoianok. Avšak zvýšená množstvo iniciátorov při kopolymerizácii vinylchloridu β elkánml, napr. vinylchloridu s propénom, má na strana druhej nepriaznivá dfialadky na technická parametre produktu, predovšetkým ne tepelná stabilitu kopolyeáru. Podobná a z hladiska technického ešte kritickajšla, je eituácia aj pri použiti lónových katalyzátorov, či iniciátorov kopolymerizácie vinylchloridu e 1-alkánmi.Not eliminating these shortcomings ea in technical practice makes use of more uses. The most common is the use of three to four times higher amounts of initiators compared to the homopolymerization of vinyl chloride at similar temperature and salichian pads. However, an increased amount of initiators in the copolymerization of vinyl chloride β-alkane, e.g. vinyl chloride with propene, on the other hand, has unfavorable control over the technical parameters of the product, in particular the thermal stability of the copolyye. Similar, and even more critical from the technical point of view, is the eituation also with the use of ion catalysts or initiators of copolymerization of vinyl chloride with 1-alkanes.
Prato příprava kopolymárov vinylchloridu e alkénmi 8 vyhovujúcou či zlepšenou tepelnou stabilitou je predmetom intenzivneho výekumu. Tak R. Bůning e R. Minke /Angew. Mekromol. Chemie 25. 27 (1972)/ pri kopolymerizácii vinylchloridu β propénom (rA » 2,45, r2 0,09 pri 60 °C) zistlli, že ea predneetne zabudovává do kopolyeáru vinylohlorid, ktorý ee tek so etúpajúcou konverziou aj rýchlejšie spotřebovává. Molekulová hmotnost i polymer izačná rýchloeť kleeejú eo etúpajúcou konverziou; propén ee obohacuje v kopolymére. A proto kopolymáry získaná pri nižších reakčných čaeoch eú tepelne etabilnejšle, než pri vyšších polymerlzačných čaeoch. Tento epfisob však naráže ne technické (potřeba značnej regenerácle monomerev ap.) 1 ekonomická problémy. VýhodnéJSie ee tak jeví vieeť kopolymerizáclu do vyšších konvbrzil, pri súčasnom zvyšovaní kopolymerizačných rýchlosti vplyvem zvýšených množetiev iniciátorov a úpravu teplotnej stability kopolymárov robit bu3 priamo v kopolymerizačnom procese alebo dodatočné. Tak je známa emulzná kopolymerizácie vinyl· chloridu e propénom e použitím hydrouhličltanu sodného ako pufru /Kasahara M.s Oaponský pat. 71-35 374 (197i)^»ričótt dá vzniknutý kopolymár Sálej neupravuje. Avšak ej vzhladom na emulzný spdsob kopolymerizácie je kopolymár teplotně málo etabilný. lný spfisob /Oaponský pat. 75-38 745 (1975)/ využívá pri výrobě suepenznáhe kopolyméru vinylchloridu e propylánoo eko modifikátory soli alkalických zemin kyeelíny ekrylovej epolusanorganickými solemiTherefore, the preparation of vinyl chloride copolymers with suitable or improved thermal stability is the subject of intensive research. So R. Bonning e R. Minke / Angew. Mekromol. Chemie 25. 27 (1972) / in copolymerization of vinyl chloride with β propene (r A »2.45, r 2 0.09 at 60 ° C) found that ea initially incorporated vinyl chloride into the copolyye, which also consumed more rapidly with increasing conversion . Both the molecular weight and the polymerization rate accelerate by increasing conversion; propene ee enriches in the copolymer. Thus, the copolymers obtained at lower reaction times are more thermally labile than at higher polymerization times. However, this epphisob encounters non-technical (need for considerable regeneration monomerev etc.) 1 economic problems. Thus, it is preferable to allow the copolymerization to rise to higher conversions, while increasing the copolymerization rate due to increased amounts of initiators and adjusting the thermal stability of the copolymers, either directly in the copolymerization process or additionally. Thus, emulsion copolymerization of vinyl chloride with propene is known using sodium bicarbonate buffer / Kasahara Ms Oapon Pat. 71-35, 374 (197i). However, with respect to the emulsion method of copolymerization, the copolymer is poorly temperature-labile. flax spfisob / Oapon Pat. 75-38 745 (1975) / utilizes, in the production of the copolymer of vinyl chloride and propylanoo eco copolymers, alkaline earth salt modifiers of ecrylic cyeelines with epo-organic salts
205 490 zinku. Okrem toho, že množstvo přidávaných soli Je značné, mvléšť přítomnost anorganických soli vo vlaetnom kopolymére je na závadu pri opracovaní a niektorých apllkáoáeh kepolymérov. Podle óalšieho postupu (pst, prihl. NSR 2 006 775} možno připravit tepelná stály kopolymér vlnylchlorid/propylán při použiti slyláterov, obsahujúcich hydroxylová skupiny alifatických alebo cykloalitetických alkoholov. Nevýhodou tohto postupu ja<hlavně dalšia retardácia přidávanými přísadami beztak dosí pomalej kopolyaerizácle vinylchloridu s propylónom. Ďalšie východisko aa hladá (V. Brit, pat. 1 234 365} v inlciácii kopolymerizácio vinylchloridu s alkánmi súčasne radikálovými i aniónovými, resp. komplexnými katalyzátormi, pričom sa však zvlášť ťažko odstraňujú zvyšky zlúčenín hliníka a titánu z kopolyméru, ktorá nepriaznivo ovplyvňujú technická vlastnosti produktu.205 490 zinc. In addition to the fact that the amount of salt added is considerable, in particular the presence of inorganic salts in the airborne copolymer is a defect in the processing and some application of the cepolymers. According to a further process (pst, U.S. Patent 2,006,775), a thermally stable wool / chloride / propylene copolymer can be prepared using hydroxyl groups of aliphatic or cycloalithetic alcohols. The disadvantage of this process is mainly the slow retardation of the propyl copolymer with slow addition of propyl copolymer. A further starting point and a smooth (V. Brit., U.S. Pat. No. 1,234,365) in the inclusion of copolymerization of vinyl chloride with alkanes at the same time with both radical and anionic or complex catalysts, but particularly difficult to remove residues of aluminum and titanium compounds from the copolymer, Product features
Uvedená a dalšia problémy výroby kopolymérov vinylchloridu a alkánmi a zvýšenie kvality produktov rieši spfiaob podlá tohto vynálezu.Said and other problems of producing vinyl chloride copolymers and alkanes and improving the quality of the products are solved by the process according to the invention.
Podle tohto vynálezu aa spfiaob výroby kopolyméru vinylchlorid/olofin a/alebo vinylchlorid/olefiny ao zvýšenou tepelnou stabilitou, suspenznou alebo amulznou volnoradlkélovou, a výhodou organickými peroxidml iniciovanou kopolymerlzéciou vinylchloridu a olaflnom alebo zmatou olafinev a 2 až 14 atómami uhlíka, a výhodou a propšnoa a 1-alkénmi ao 4 až 14 atómami uhlíka, pri teplota 10 až 90 °C, za apolupfiaobania ochranných koloidov, ako diapergétorov, emulgétorov, modifikétorov, připadne tiež regulétorov pH prostředía a molekulovej hmotnosti, uskutečňuje tak, ža kopolymerlzécla vinylchloridu aa vedlo do konverzie minimálně 60 % a potom do vzniknutej auapenzie alebo emulzie kopolyméru aa před odplynenlm a/alebo po odplynani nezreagovaných monomérov přidá jednorázová alebo po čaatiach termický stabilizátor v množstvo 0,005 až 0,5 % hmot·, počítané na monoméry a emulzia a/alebo auepenzia kopolyméru aa vystaví dalšiemu pfieobsniu teploty priamym a/alebo nepriamym ohrsvom, pričom teplota auapenzie alebo emulzie kopolyméru jo 50 až 100 °C a potom aa vadle na aeparáciu a sušenia.According to the present invention, and for the manufacture of a vinyl chloride / olophin and / or vinyl chloride / olefin copolymer and having increased thermal stability, suspension or amulous free-alkali, and preferably organic peroxide-initiated copolymerization of vinyl chloride and olafine or confused olafin and 2 to 14 carbon atoms, and preferably 1-alkenes having from 4 to 14 carbon atoms, at a temperature of 10 to 90 [deg.] C., under the influence of protective colloids, such as diapergers, emulsifiers, modifiers, and optionally pH and environmental regulators, by carrying out at least a conversion of vinyl chloride 60% and then to the resulting auapension or emulsion of the copolymer aa before and after the ungassing of the unreacted monomers, add a one-time or after-time thermal stabilizer in an amount of 0.005 to 0.5% by weight, calculated on the monomers and emulsion and / or temperature overload by direct and / or indirect heating, wherein the temperature of the auapension or emulsion of the copolymer is 50 to 100 ° C and then the aeparation and drying oven.
Výhodou epfieobu podlá tohto vynálezu je možnost uskutečňovat kopolymerizéciu vinylchloridu β alkánmi a poměrně vysokou výrobnoatou polymerlzačných zariadení limitovanou v podstatě možnostaml bezpečného odvodu kopolymerlzečného teple, tede blizkeu rýchlosti homopolymerlzácle, alebo pochopitelné, a vlacnéaobna vyššou koncentréclou lniclétorov. Zvlášť významnou výhodou je vyšila termická stabilita kopolyméru, a tým aj jeho Iahšia opracovatelnost a širšie aplikačně možnosti. Ďalšou výhodou ja skutečnost, ža redukčně člnidlé, resp. antloxydanty ako termická stabilizátory, aa pridévajú do reakčného systému v podetata ež po ukončeni kopolyaerizácle, tekže túto nemůžu retardovat elebo Inek nepriaznivo ovplyvniť, ale zaea dostatočne skoro, aby ee eohli dokonale hoaogenlzoveť, a tek čo najdůkladnejile odatréniť zvyšky lniclétorov a volných radlkélov.The advantage of the present invention is that it is possible to carry out copolymerization of vinyl chloride with β alkanes and relatively high productive polymerization devices, limited substantially by the ability to safely dissipate the copolymerization heat, i.e. near the homopolymerization rate, or understandably, and with high concentration. A particularly important advantage is the improved thermal stability of the copolymer and hence its easier workability and wider application possibilities. A further advantage is the fact that the reduction boats, respectively. antioxidants such as thermal stabilizers, and are added to the reaction system at a rate even after completion of the copolyaerization, since this cannot retard or inek adversely affect it, but early enough to be able to completely haloogenize, and as far as possible to resist the radial residues.
V napoelednom rado ja výhodeu aj technická nenáročnost zariadení, možnost využívat bažné polymerizačné autoklévy a delšie zariadenia prakticky a maximélnym využitím.In the midst of the series I also benefit from the technical demands of the devices, the possibility of using conventional polymerization autoclaves and longer devices with practical and maximum utilization.
Vhodná ja uskutečňovat kopolymerizéciu vinylchloridu a jedným alebo eúčasne viacerými elkénmi C4 až C^4, hlavně a eténom, propénom, 1-buténom, izobuténom a vyššími 1-alkén205 49β mi čo najrýohlejšie, a čo najvyššou konverziou monomérov, pri použiti najúčinnejšlch lniciátorov, resp. inioiačných eyetémov. K takým nesporná patria organické peroxidy, ako sú dialkylperoxydikarbonéty, diacylperoxidy, zmeená peroxidy i zmieéené organické i anorganické peroxidy, peroxypivaléty, všetky - či už vopred připravené (komerčně) alebo vytvářené in šitu“, acetylcyklohexylsulfonylperoxid, hydroperoxidy spolu s redukčnými činidlami, podobné peroxid vodíka e redukčnými činidlami ap. Množstvo týchto iniciétorov je najvhodnejšie volit tak, aby kopolymerizácia prebiehala podobné alebo evojou rýchlosťou čo najbližéie rýchlosti polymerizáeie samotného vinylchloridu. Zvyikové množetvá iniciétorov (organických a připadne aj anorganických peroxidov) je třeba po skončeni kopolymerizácie tepelná rozložit a/alebo ich účinok eliminovat redukčnými činidlami, resp. antioxidantami, ako technickými stabilizátoru!. Vhodnejšie je po skončeni kepolymerizécie při dat do suspenzie, či emulzie kopolyméru určité množstvo termického stabilizátore, čo v závislosti od typu e anožstva iniciátora, teploty a doby kopolymerizácie méže postačit, alebo navyěe ešte euspenziu kopolyméru podrobit tepelnému epraemvaniu, napr. priamou nesýtenou vodnou parou pri teplotách do 100 °C, najčastejšie 80 až 95 °C, obvykle na vhodnom deeorpčnom či odplyňovacom zariadení, napr. za pomoci prebublávacej kolony alebo kotlá, eitovej kolony ap. Teplotné namáhanie však ako z hlediska energetického, tak aj kvality produktu nie je vhodné predimenzovévať ani výšku teploty a ani kontaktnú dobu, ktorá by nemala byt pri uvedených teplotách dlhšia ako 90 min, resp. male by byť pod 60 min.A suitable I make kopolymerizéciu vinyl chloride with one or EUPart more ELKEN C 4 to C-4, the barrel and ethene, propene, 1-butene, isobutene, and higher 1-alkén205 49β like the najrýohlejšie, and as high monomer conversion, the use najúčinnejšlch lniciátorov, respectively. iniocative eyetems. Such indisputable include organic peroxides such as dialkyl peroxydicarbonates, diacyl peroxides, altered peroxides and mixed organic and inorganic peroxides, peroxivalents, all - whether prepared (commercially) or formed in situ ', acetylcyclohexylsulfonyl peroxide, hydroperoxides together with reducing agents, e reducing agents and the like. The amount of such initiators is most preferably chosen such that the copolymerization proceeds at a similar or evolution rate as close to the rate of polymerization of vinyl chloride alone. The customary amounts of initiators (organic and possibly inorganic peroxides) must be thermally decomposed after the copolymerization and / or their effect eliminated by reducing agents or reducing agents. antioxidants such as technical stabilizer !. Preferably, upon completion of the cepolymerization, a certain amount of thermal stabilizer is added to the suspension or emulsion of the copolymer, which may be sufficient, depending on the type of initiator, the temperature and the time of copolymerization, or additionally subjected to copolymer euspension. by direct unsaturated water vapor at temperatures up to 100 ° C, most commonly 80 to 95 ° C, usually on a suitable de-absorption or degassing device, e.g. using a bubbling column or boiler, an eit column, and the like. However, it is not suitable to over-dimension the temperature and the contact time, which should not be longer than 90 min. should be under 60 min.
Ako termické stabilizátory prichádzajú do úvahy predovšetkým známe antioxidanty, ako eú slkýlfenoly, alkoxyfenoly, zvlášť orto-aubetituované butylfenoly, napr. 2,6-di-tero-butyl-4-metylfenol, difenoly β metylánovým alebo eirnym mdetikom, ako napr. 4,4*-metylén-bi8-2,2'-dimetyl-6,6*-di-terc-butylfenol a analogické tio-bie-alkylfenoly, alkylované arylfosfity, zmesi fenolov a organických fosforitanov a připadne tiež zinkových soli organických kyselin ap. Menej vhodné, aj ke3 použitelné, sú diarylaminy, aminofenoly i diel kylamíny. Z redukčných činidiel (aj ke3 značná čaať známých antioxidantov eú redukčnými činidlemi)sú to hlavně organické a anorganické tiozlúčenlny, ako napr. dilauryltiodipropionét, hydrosiričitany alkalických kovov a zvlášť hydroairičitany alkalických zemin, naj mé technicky lahko dostupný hydroeiričitan vápenatý spolu e volným kysličníkem siřičitým, samotný kysličník siřičitý, dusitany alkalických kovov i zemin, kyselina eekorbová ap.Suitable thermal stabilizers are, in particular, the known antioxidants, such as polyphenols, alkoxyphenols, in particular ortho-substituted butylphenols, e.g. 2,6-di-tert-butyl-4-methylphenol, diphenols with a β methylan or an organic reagent, such as e.g. 4,4'-methylene-bi8-2,2'-dimethyl-6,6 * -di-tert-butylphenol and analogous thio-bie-alkylphenols, alkylated arylphosphites, mixtures of phenols and organic phosphonates and optionally also zinc salts of organic acids and . Less suitable, although useful, are diarylamines, aminophenols, and some cylamines. Among the reducing agents (although much of the known antioxidants are eu reducing agents), they are mainly organic and inorganic thiocompounds, such as e.g. dilauryl thiodipropionate, alkali metal hydrosulfites and especially alkaline earth metal hydrites, especially the readily available calcium hydrogen sulfite together with free sulfur dioxide, sulfur dioxide itself, alkali metal and earth nitrites, eecorbic acid and the like.
Ďalšie podrobnosti epčeobu výroby kopolýmérov vinylchloridu e olefínmi so zvýšenou tepelnou stabilitou, ako aj 3alšie výhody eú zřejmé z prikladov.Further details of the process for producing vinyl chloride copolymers and olefins with enhanced thermal stability, as well as other advantages of the EU, are evident from the examples.
Přiklad 1 oExample 1 o
Do autoklávu o objeme 50 dm z nehrdzavejúcej ocele sa nadávkuje 25 kg destilovanej vody, 14 g aetylhydroxypropylcelulózy, 28,2 g bie-4-terc-butylcyklehexylperoxydikarbonétu (Perkadox 16), 14,1 g dllauraylperoxidu a 0,7 g 2,6-di-terc-butyl-4-matylfenolu. Po uzavreti ea autokláv vypláchne dusíkom a vinylchloridom za účelom odatránania kyalika. Potom sa do autoklávu nadávkuje vinylchlorid v množstva 13 kg a nakoniec propylén v množstva25 kg of distilled water, 14 g of ethylhydroxypropylcellulose, 28.2 g of bie-4-tert-butylcyclohexylperoxydicarbonate (Perkadox 16), 14.1 g of dllauraylperoxide and 0.7 g of 2,6- are added to a 50dm stainless steel autoclave. di-tert-butyl-4-matylfenolu. After closing, the autoclave was flushed with nitrogen and vinyl chloride to remove the alkali. 13 kg of vinyl chloride is then metered into the autoclave and propylene is added
205 498205 498
1,1 kg. AutAkláv ea vyhraje ne teplotu 48 °C a táto teplota ea udržuje počas 12 h. Po tej to době ea nezreagované aonosáry odplynla. Produkt ea po echladenl autoklávu vypustí, odfiltruje a vyeuil. Zleka ea 9.7 kg kopolyaáru. čo odpovedá konverzll 69 %. Kopolyaár aá K hodnotu 58,1 a obsah chlóru 54,8 % haot. Vzorka ee analyzuje na tepelná stabilitu. Ne eutoaatickoa etabiliaetri pri 150 °C ee zleka hodnota tepelnej stability vyjádřená hodnotou celkovej bieloby 64,3 %.1,1 kg. The autoclave ea wins at 48 ° C and maintains this temperature ea for 12 h. After that time ea unreacted aonosars went away. After cooling the product, the autoclave is drained, filtered and dried. Zleka ea 9.7 kg copolyyaru. which corresponds to a conversion of 69%. Copolymer and K value 58.1 and chlorine content 54.8% haot. Sample ee is analyzed for thermal stability. Not eutoaatically and etabiliaetri at 150 ° C ee the thermal stability value expressed as a total white value of 64.3%.
Přiklad 2Example 2
Podobnýa postupoa ako v přiklade 1 ea urobí Selil pokus, len e týa rozdielom, že ea vynechá v receptáře termický etebilizátor 2,6-di-terc-butyl<,4-aetylfenol. Vznikne kopclyaár o K hodnotě 57,4 β obeehoa chlóru 54,7 % hmot. a e tepelnou stabilitou vyjádřenou ako celková bieloba,54,5 %.A procedure similar to that of Example 1 e and Selil will attempt, except that ea omits the thermal etebilizer 2,6-di-tert-butyl-1,4-ethylphenol in the recipe. A copolymer having a K value of 57.4 β by volume of chlorine of 54.7% by weight is formed. and e thermal stability expressed as total white, 54.5%.
Přiklad 3Example 3
Podobnýa postupoa ako v přiklade 2 pe uplynuti polyaerlzačnej doby 12 h ea do autoklávu bez odplynenia nezreegovaných aonoaárov prldejú roztoky antioxidentov o konc.A procedure similar to that of Example 2 for the expiration of the 12 h polyaerosion time e.
% haot. v anožetve po 5 ca a to 2,6-di-terc-4-aetylfenolu a dilauryltiodipropionátu a pri teplote okolo 60 ®C ea nechá za aleianla etáť. Suspenzie ee po ochládáni odfiltruje a kopolymer vyeuil. Získaný kopolyaár aá K hodnotu 58,1, obsah chlóru 53,8 % haot. e tepelná stabilitu vyjádřená ako celková bioloba 61,3 %.% haot. in an amount of 5 ca of 2,6-di-tert-4-ethylphenol and dilauryl thiodipropionate and at a temperature of about 60 ° C e, it is allowed to stand for an additional amount. After cooling, the suspension is filtered and the copolymer is filtered off. The copolymer obtained was 58.1, the chlorine content was 53.8% haot. e thermal stability expressed as a total bioloba of 61.3%.
Přiklad 4Example 4
Podobnýa postupoa ako v přiklade 1, ala baz 2,4-dl-terc-butyl-4-aetylfenolu, teda ako v přiklade 2, ea po ukončeni kopolyaerlzácle eutokláv za teple odplyni. Obsah eutoklávu ea přečerpá poaocou duaika do zásobníka suspenzie o obsahu 100 dm . Tento je opatřený duplikátoroa, aleiadloa a privodoa priaaej naeýtenej vodnej pery, Oo suspenzie ea přidá 100 ca vodného roztoku hydroalrlčltanu vápenatého o konc. 10 % haot. Potom za stálého aiečania ea privádza do suspenzie naeýtená vodná pata počas 30 ain v celkovoa anožetve 50 kg. Teplota prltoa vyetúpl na 70 °C. Nato oa auepanzia odfiltruje za tepla a kopolyaár ea vysuli. Zlaka aa produkt v anožatva 9,9 kg, čo odpovedá konvorzli 70,2 %. Kopolyaár aá K hodnotu 58,0, obsah chlóru 63,9 % haot. a tepelná stabilitu vyjádřená ako čolkové bleloba 65,6 %·A procedure similar to that of Example 1, but based on 2,4-dl-tert-butyl-4-ethylphenol, i.e. in Example 2, and e, after completion of the copolymers, is degassed by heat. The contents of the eutoclave ea are pumped through the duaica into a 100 dm suspension reservoir. The latter is provided with a duplicator, aleiadloa and privodoa for the saturated aqueous lips, 10o of the suspension e, and add 100 cc of an aqueous solution of calcium hydrogen phosphate with conc. 10% haot. Thereafter, while still eager ea, the saturated aqueous heel is suspended in the suspension for 30 ain in a total weight of 50 kg. The flow temperature rises to 70 ° C. The oa auepanzia was then filtered hot and copolyyaar e dried. The product was 9.9 kg, which corresponds to 70.2%. Copolymer and a K value of 58.0, a chlorine content of 63.9% haot. and thermal stability expressed as crib blub 65,6% ·
Přiklad 5Example 5
Oo autoklávu o objaaa 50 da z nehrdzavejácej ocele ea nadávkuje 25 kg deetilovenej vody, 14 g aetylhydroxypropylcelulózy, 28,2 g bie-4-terc-butylcyklohexylperoxýdlkarboná205 496 tu (Perkadox 16) a 14.1 g dilauroylperoxidu. Autokláv aa inertizuje duaikom a vinylchloridom, Potom aa do autoklávu nadávkuje 13 kg vinylchloridu a 1,1 kg propónu. Nato ea autokláv vyhraje na teplotu 48 °C a táto teplota ea udržiava počas 15 h. Po tejto doba aa nezreagované monoséry odplynia pri teplota 50 °C. Suapenzia aa přečerpá do záaobníka o objene 100 dm , přidá aa 10 cm roztoku 2,6-di-terc-butyl-4-metylfanolu v dichlóretáne o konc, 10 % hmot. a za atáleho mieěenia sa privádza naaýtená vodná para priamo do suspenzia v množstva 60 kg počae 40 min, čím teplota dosiahne 80 °C. Nato aa suspenzia bez chladenia přefiltruje a kopolymér vysuší. Zleka sa kopolymér v množatve 9,5 kg. Kopolymér má K hodnotu 57,1, obsah chlóru 52,9 % hmot. a tepelná stabilitu vyjádřená ako celková bieloba 59,3 %.A 50 da stainless steel autoclave and dosed with 25 kg of de-distilled water, 14 g of ethylhydroxypropylcellulose, 28.2 g of bie-4-tert-butylcyclohexylperoxycarbone205 496 tu (Perkadox 16) and 14.1 g of dilauroyl peroxide. The autoclave aa is inerted with dua and vinyl chloride. Then aa is charged into the autoclave 13 kg of vinyl chloride and 1.1 kg of propone. Thereafter, the autoclave wins to 48 ° C and maintains this temperature ea for 15 h. During this time aa unreacted monosers are degassed at 50 ° C. Suapenzia aa is pumped into a 100 dm reservoir, added with aa 10 cm @ 2 of a solution of 2,6-di-tert-butyl-4-methylphanol in dichloroethane with a conc. and while stirring, saturated water vapor is fed directly into the slurry at 60 kg for 40 min, reaching a temperature of 80 ° C. The suspension is then filtered without cooling and the copolymer is dried. A copolymer of 9.5 kg was added gently. The copolymer has a K value of 57.1, a chlorine content of 52.9% by weight. and a thermal stability expressed as total white of 59.3%.
Přiklad 6 oExample 6 o
Oo autoklávu o objeme 10 dm z nehrdzavejúcej ocele aa nadávkuje 5 kg destllovanej vody, 5 g metylhydroxypropylcelulózy, 15 g 2-etylhaxylperoxydikarbanátu vo forma 50 %-nóho roztoku v xyléne a 5 g dilauroylperoxidu. Autokláv aa potom Inertizuje dusikom a vinylchlorídom. Nato ea do autoklávu nadávkuje 2,5 kg vinylchloridu, 0,3 kg izobutánu a 0,1 kg 1-dodecánu. Autokláv ea vyhraje na teplotti 49 °C a táto teplota ea udržiava počaa 15 h. Po tejto doba aa nazreagovaná monomáry odplynia pri teplote 50 °C. Nato aa do autoklávu vpravi 10 cm dichlóretánovóho roztoku 2,6-di-terc-butyl-4-aetylfenolu o konc. 1 % hmot. a 10 cm dichlóretánovóho roztoku dilaurýltiodipropionátu o konc. 1 % hmot. Autokláv aa vyhrleva cez duplikótor na teplotu 90 °C pri aúčaanom privádzani priamej vodnej páry v množstva aai 10 kg. Potom aa suspenzia achladi, filtruje na laboratórnej nučke a vyauěi v listové J euSiarni. Zleka ea kopolymér o K hodnota 57,2, a obsahom chlóru 51,8 % hmot. a a tepelnou stabilitou vyjádřenou ako celková bieloba 60,4 %.A 10 dm stainless steel autoclave was charged with 5 kg of distilled water, 5 g of methylhydroxypropylcellulose, 15 g of 2-ethylhaxylperoxydicarbanate as a 50% solution in xylene and 5 g of dilauroyl peroxide. The autoclave is then inerted with nitrogen and vinyl chloride. Thereafter, 2.5 kg of vinyl chloride, 0.3 kg of isobutane and 0.1 kg of 1-dodecane are metered into the autoclave. The autoclave ea wins at 49 ° C and maintains this temperature ea for 15 hours. During this time aa unreacted monomers are degassed at 50 ° C. Thereafter, 10 cm @ 2 of a dichloroethane solution of 2,6-di-tert-butyl-4-ethylphenol of conc. 1 wt. and 10 cm < 3 > of a dichloroethane solution of dilauryl thiodipropionate with conc. 1 wt. The autoclave aa is heated through a duplicator to a temperature of 90 ° C with a direct supply of direct water vapor at a rate of aai 10 kg. Then, the suspension is cooled, filtered on a laboratory well and blown in a leafy flask. The pH of the copolymer was 57.2, with a chlorine content of 51.8% by weight. and a thermal stability expressed as total white of 60.4%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS655579A CS205496B1 (en) | 1979-09-28 | 1979-09-28 | Manufacturing process of copolimer vinylchloride/olefin and/or vinylchloride/olefins with increased thermal stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS655579A CS205496B1 (en) | 1979-09-28 | 1979-09-28 | Manufacturing process of copolimer vinylchloride/olefin and/or vinylchloride/olefins with increased thermal stability |
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| Publication Number | Publication Date |
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| CS205496B1 true CS205496B1 (en) | 1981-05-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS655579A CS205496B1 (en) | 1979-09-28 | 1979-09-28 | Manufacturing process of copolimer vinylchloride/olefin and/or vinylchloride/olefins with increased thermal stability |
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1979
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