JPH03212409A - Preparation of vinyl chloride polymer - Google Patents
Preparation of vinyl chloride polymerInfo
- Publication number
- JPH03212409A JPH03212409A JP905690A JP905690A JPH03212409A JP H03212409 A JPH03212409 A JP H03212409A JP 905690 A JP905690 A JP 905690A JP 905690 A JP905690 A JP 905690A JP H03212409 A JPH03212409 A JP H03212409A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl chloride
- polymer
- reflux condenser
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 63
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 239000012736 aqueous medium Substances 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- 238000007127 saponification reaction Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 abstract description 8
- 239000012778 molding material Substances 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 abstract description 2
- 230000011514 reflex Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000005484 gravity Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- FVAIEHAPKZFAGH-UHFFFAOYSA-N 6,6-dimethylheptanoyl 6,6-dimethylheptaneperoxoate Chemical compound CC(CCCCC(=O)OOC(CCCCC(C)(C)C)=O)(C)C FVAIEHAPKZFAGH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- IBRAHAYHUASIEH-UHFFFAOYSA-N carboxyoxy hexyl carbonate Chemical compound CCCCCCOC(=O)OOC(O)=O IBRAHAYHUASIEH-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000006185 dispersion Substances 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
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 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 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 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
- 239000003002 pH adjusting agent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 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 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、各種成形材料として有用な、高品質の塩化ビ
ニル系重合体の製造方法、とくには重合過程における抱
の発生を防止して得られる重合体の粒子形状を改善した
塩化ビニル系重合体の製造方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing high-quality vinyl chloride polymers useful as various molding materials, and in particular to a method for producing high-quality vinyl chloride polymers that are useful as various molding materials. The present invention relates to a method for producing a vinyl chloride polymer in which the particle shape of the polymer is improved.
（従来の技ｆｒ）
近年、塩化ビニル系重合体の製造では、効率を高めるた
め重合缶の大型化と重合時間の短縮が進められている。(Conventional Technique fr) In recent years, in the production of vinyl chloride polymers, polymerization cans have been made larger and polymerization times have been shortened in order to increase efficiency.
その方法の一つとして反応熱の除去を迅速に進めるため
に、重合缶に還流コンデンサーを併設し、これに塩化ビ
ニル単量体等を還流しながら重合を進めることがある。One of the methods is to install a reflux condenser in the polymerization vessel and proceed with the polymerization while refluxing the vinyl chloride monomer, etc. through the condenser in order to quickly remove the reaction heat.
（発明が解決しようとする課題）
しかし、この方法では還流コンデンサーによる除熱の際
に重合系に発泡現象が起こって重合生成粒子が嵩比重の
低い泡状のものとなり、この中には、ＪＩＳ Ｚ−８８
０１に準じて４８メツシユ（２９７ｐ）の篩を用いて粒
度を測定した場合に篩上に残るほどの、大きな粒径のも
のが混入したり、この泡状粒子のために重合缶の上部内
面に重合体スケールが付着するなどの問題があった。(Problem to be solved by the invention) However, in this method, a foaming phenomenon occurs in the polymerization system during heat removal using a reflux condenser, and the polymerization particles become foam-like with a low bulk specific gravity. Z-88
When particle size is measured using a 48-mesh (297p) sieve in accordance with 01, particles large enough to remain on the sieve may be mixed in, or these foam particles may form on the inner surface of the upper part of the polymerization can. There were problems such as polymer scale adhesion.
そのため、消泡羽根等を用いて機械的に破泡する方法も
提案されているが、この方法では破泡した残りが消泡羽
根や重合缶の内面に付着して重合体スケールとなること
があり、対策として必ずしも有効とはいえないものであ
った。Therefore, a method of mechanically breaking the bubbles using a defoaming blade has been proposed, but with this method, the remaining foam may adhere to the defoaming blade or the inner surface of the polymerization can and form polymer scale. However, it was not necessarily an effective countermeasure.
（課題を解決するための手段）
そこで、本発明者らはこの問題を解決すべく鋭意研究の
結果、塩化ビニル単量体、または塩化ビニルを主体とす
るビニル系単量体の混合物（以下、塩化ビニル単量体等
とする）を、還流コンデンサー付き重合缶内に仕込んで
水性媒体中で重合を始めた後、その１００重量部当り。(Means for Solving the Problem) Therefore, as a result of intensive research in order to solve this problem, the present inventors found that a vinyl chloride monomer or a mixture of vinyl monomers mainly composed of vinyl chloride (hereinafter referred to as per 100 parts by weight of vinyl chloride monomer (vinyl chloride monomer, etc.) is charged into a polymerization vessel equipped with a reflux condenser and polymerization is started in an aqueous medium.
イ）けん化度２０〜５０モル％、平均重合度２００〜４
００の部分けん化ポリビニルアルコール０．００２〜０
゜００７重量部と、
口）消泡剤０．００１〜ｏ、ｏｉ重量部とを、それまで
の重合による還流コンデンサーでの全除熱量が全重合発
熱量の１０％を超えない内に、重合系に添加すると１発
泡現象が抑えられて泡状の重合体粒子が生成したり、重
合缶に重合体スケールの付着することもなくなり、得ら
れたポリ塩化ビニル粒子が高品質のものとなることを見
出し、本発明に到達した。b) Saponification degree 20-50 mol%, average polymerization degree 200-4
00 partially saponified polyvinyl alcohol 0.002-0
0.007 parts by weight of the antifoaming agent and 0.001 to 0.00 parts by weight of the antifoaming agent were polymerized while the total amount of heat removed in the reflux condenser due to the previous polymerization did not exceed 10% of the total polymerization calorific value. When added to the system, the foaming phenomenon is suppressed, the formation of foamy polymer particles and the adhesion of polymer scale to the polymerization can are eliminated, and the resulting polyvinyl chloride particles are of high quality. They discovered this and arrived at the present invention.
これを説明すると、本発明の塩化ビニル系重合体の製造
方法において、塩化ビニル単量体等を還流コンデンサー
付き重合缶内に仕込んで水性媒体中で重合を始めた後１
重合系に添加される、イ）成分としての、けん化度２０
〜５０モル％、平均重合度２００〜４００の部分けん化
ポリビニルアルコールは、塩化ビニル単量体等１００重
量部当り、０．００２〜０゜００７重量部の割合で用い
られるのであるが、この添加量が０．００２重量部未満
では消泡効果が低下し、泡状重合体が多量にできるため
、嵩比重が小さくなる。また、添加量が０．００７重量
部を超えるときも重合粒子の形成に影響を与えて嵩比重
が小さくなるので好ましくない。To explain this, in the method for producing a vinyl chloride polymer of the present invention, vinyl chloride monomer etc. are charged into a polymerization vessel equipped with a reflux condenser and polymerization is started in an aqueous medium.
Saponification degree of 20 as a) component added to the polymerization system
Partially saponified polyvinyl alcohol with an average polymerization degree of 200 to 400 mol % is used at a ratio of 0.002 to 0.007 parts by weight per 100 parts by weight of vinyl chloride monomer, etc., and the amount added is If the amount is less than 0.002 parts by weight, the defoaming effect will be reduced and a large amount of foamy polymer will be produced, resulting in a decrease in bulk specific gravity. Further, when the amount added exceeds 0.007 parts by weight, it is also not preferable because it affects the formation of polymerized particles and the bulk specific gravity becomes small.
さらに、この部分けん化ポリビニルアルコールのけん化
度と平均重合度とがそれぞれ上記範囲外のときも、消泡
効果が低下し、泡状重合体が多量にできるため、嵩比重
が小さくなって好ましくない。Furthermore, when the degree of saponification and the average degree of polymerization of the partially saponified polyvinyl alcohol are outside the above ranges, the antifoaming effect decreases and a large amount of foamy polymer is formed, which is undesirable because the bulk specific gravity becomes small.
口）成分としての消泡剤には、ポリシロキサン、ジメチ
ルポリシロキサン、ジフェニルポリシロキサン等のシリ
コーンオイル類、炭素原子数が１０〜３０の脂肪族また
は芳香族のアルコール類のように、一般によく知られて
いるものがよく、これらを単独または２種以上の組合せ
て使用することができる。これらの内では重合への影響
の小さいシリコーンオイル系のものがよく、その中でも
シリコーンオイル１００重量部に対して微粒子の疎水性
シリカをＯ，ＯＳ〜０．４重量部の割合で添加してエマ
ルジョン化させたものが好ましい。Antifoaming agents as components include generally well-known silicone oils such as polysiloxane, dimethylpolysiloxane, and diphenylpolysiloxane, and aliphatic or aromatic alcohols having 10 to 30 carbon atoms. These can be used alone or in combination of two or more. Among these, silicone oil-based ones that have a small effect on polymerization are preferred, and among these, fine particles of hydrophobic silica are added at a ratio of O,OS ~ 0.4 parts by weight to 100 parts by weight of silicone oil to form an emulsion. It is preferable to use
この消泡剤は塩化ビニル単量体等１００重量部当り、ｏ
、ｏｏｉ〜０．０１重量部の割合で添加されるのである
が、この添加量がｏ、ｏｏｔ重量部未満では消泡効果が
なく、泡状重合体が多量にできて好ましくなく、また添
加量が０．０１重量部を超えると、それ以上の消泡効果
が期待されないので経済的でなく。This antifoaming agent is o per 100 parts by weight of vinyl chloride monomer etc.
, ooi to 0.01 parts by weight, but if the amount added is less than o, oot parts by weight, there will be no defoaming effect and a large amount of foamy polymer will be formed, which is undesirable. If it exceeds 0.01 part by weight, no further defoaming effect can be expected and it is not economical.
また得られる重合体粒子の形成に影響を与えるので好ま
しくない。It is also undesirable because it affects the formation of the resulting polymer particles.
この重合系へのイ）、口）両成分の添加は、前述したよ
うに、塩化ビニル単量体等を還流コンデンサー付き重合
缶内に仕込んで水性媒体中で重合を始めた後、それまで
の重合による還流コンデンサーでの全除熱量が全重合発
熱量の１０％を超えない内に行われるが、とくには０％
、すなわち還流コンデンサーでの除熱が開始される前に
行うのが好ましい。これは還流コンデンサーでの全除熱
量が１０％を超えるような時点になると、発泡現象が強
く、その後に消泡剤を添加してもあまり効果が期待され
ないためである。As mentioned above, the addition of both components (a) and (i) to this polymerization system is carried out after charging vinyl chloride monomer etc. into a polymerization vessel equipped with a reflux condenser and starting polymerization in an aqueous medium. The total amount of heat removed by the reflux condenser due to polymerization does not exceed 10% of the total polymerization calorific value, but in particular 0%.
In other words, it is preferable to carry out the process before heat removal in the reflux condenser is started. This is because when the total amount of heat removed in the reflux condenser exceeds 10%, the foaming phenomenon is strong and adding an antifoaming agent thereafter is not expected to be very effective.
なお、還流コンデンサーの運転開始は、重合初期段階に
おける粒子形成への影響を考慮してできるだけ重合が進
行した時点で行うのが望ましいが。Note that it is desirable to start the operation of the reflux condenser as soon as possible after the polymerization has progressed, taking into account the effect on particle formation in the initial stage of the polymerization.
通常は重合率が５〜２０％に達した時期に行われる。This is usually carried out when the polymerization rate reaches 5 to 20%.
また、上記において全重合発熱量および還流コンデンサ
ーでの全除熱量は、それぞれ下式によって得られた値を
意味する。Furthermore, in the above, the total polymerization heat amount and the total heat removal amount in the reflux condenser each mean a value obtained by the following formula.
全重合発熱量＝仕込んだ全塩化ビニル単量体量（実測値
）
×塩化ビニル単量体の単位重量当りの発熱量（文献値）
還流コンデンサーでの全除熱量＝コンデンサー冷却水量
（実測値）
Ｘコンデンサー冷却水の出入温度差
（実測値）
本発明の方法は塩化ビニル単量体等を水性媒体中で重合
する場合、例えば懸濁重合法、乳化重合法等に適用され
るが、とくに懸濁重合法によるときに大きな効果がもた
らされる。Total polymerization calorific value = Total amount of vinyl chloride monomer charged (actually measured value) × Calorific value per unit weight of vinyl chloride monomer (literature value) Total heat removal amount in reflux condenser = Condenser cooling water amount (actually measured value) The method of the present invention is applicable to suspension polymerization, emulsion polymerization, etc. when vinyl chloride monomer etc. are polymerized in an aqueous medium, but it is particularly important to Great effects are brought about when using the turbidity polymerization method.
この重合は、塩化ビニル単量体単独に限られず、塩化ビ
ニルを主体とするこれと共重合可能なビニル系単量体（
コモノマー）との混合物（塩化ビニルが５０重量％以上
）であってもよく、このコモノマーとしては、酢酸ビニ
ル、プロピオン酸ビニルなどのビニルエステル；アクリ
ル酸メチル、アクリル酸エチルなどのアクリル酸エステ
ルもしくはメタアクリル酸エステル；エチレン、プロピ
レンなどのオレフィン；ラウリルビニルエーテル、イソ
ブチルビニルエーテルなどのビニルエーテル；無水マレ
イン酸；アクリロニトリル；スチレン；塩化ビニリデン
；その低塩化ビニルと共重合可能な単量体などが挙げら
れる。This polymerization is not limited to vinyl chloride monomer alone, but also vinyl monomers that are copolymerizable with vinyl chloride (based on vinyl chloride) (
comonomer) (50% by weight or more of vinyl chloride); examples of the comonomer include vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters such as methyl acrylate and ethyl acrylate; Acrylic acid esters; olefins such as ethylene and propylene; vinyl ethers such as lauryl vinyl ether and isobutyl vinyl ether; maleic anhydride; acrylonitrile; styrene; vinylidene chloride; monomers that can be copolymerized with low vinyl chloride.
重合開始剤は従来塩化ビニル系の重合に使用されている
油溶性触媒あるいは水溶性触媒でよく、油溶性触媒とし
ては、ジイソプロピルパーオキシジカーボネート、ジー
２−エチルヘキシルパーオキシジカーボネート、ジェト
キシエチルパーオキシジカーボネートなどのバーカーボ
ネート化合物某ｔ−ブチルパーオキシネオデカネート、
ｔ−ブチルパーオキシピバレート、ｔ−ヘキシルパーオ
キシピバレート、α−クミルパーオキシネオデカネート
などのパーエステル化合物；アセチルシクロヘキシルス
ルホニルパーオキシド、２，４．４−トリメチルペンチ
ル−２−パーオキシフェノキシアセテート、３，５．５
− トリメチルヘキサノイルパーオキシド、ラウロイル
パーオキシドなどの過酸化物；アゾビス−２，４−ジメ
チルバレロニトリル、アゾビス（４−メトキシ−２，４
−ジメチルバレロニトリル）などのアゾ化合物が例示さ
れ、これらは単独または２種以上の組み合わせで使用す
ることができる。The polymerization initiator may be an oil-soluble catalyst or a water-soluble catalyst conventionally used for vinyl chloride polymerization. Examples of oil-soluble catalysts include diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and jetoxyethyl peroxydicarbonate. Bar carbonate compounds such as oxydicarbonate, certain t-butyl peroxyneodecanate,
Perester compounds such as t-butylperoxypivalate, t-hexylperoxypivalate, α-cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide, 2,4.4-trimethylpentyl-2-peroxyphenoxy Acetate, 3,5.5
- Peroxides such as trimethylhexanoyl peroxide and lauroyl peroxide; azobis-2,4-dimethylvaleronitrile, azobis(4-methoxy-2,4
-dimethylvaleronitrile), which can be used alone or in combination of two or more.
また水溶性触媒としては過硫酸カリウム、過硫酸アンモ
ニウム、過酸化水素、キュメンハイドロパーオキシド等
が例示され、これらは前記油溶性触媒と組合せて使用さ
れる。Examples of water-soluble catalysts include potassium persulfate, ammonium persulfate, hydrogen peroxide, and cumene hydroperoxide, which are used in combination with the oil-soluble catalyst.
単量体の水媒体への分散助剤は従来一般に知られている
ものでよく５例えばメチルセルロース、エチルセルロー
ス、ヒドロキシエチルセルロース、ヒドロキシプロピル
セルロース、ヒドロキシプロピルメチルセルロースなど
の水溶性セルロースエーテル；けん化度６０〜９９モル
％、平均重合度７００〜３０００の水溶性部分けん化ポ
リビニルアルコール；アクリル酸重合体；ゼラチンなど
の水溶性ポリマー；ソルビタンモノラウレート、トリオ
レート、ソルビタンモノステアレート、グリセリントリ
ステアレート、エチレンオキシドプロピレンオキシドブ
ロックコポリマーなどの油溶性乳化剤；ポリオキシエチ
レンソルビタンモノラウレート、ポリオキシエチレング
リセリンオレート、ラウリル硫酸ナトリウムなどの水溶
性乳化剤；炭酸カルシウム、りん酸カルシウム、ドデシ
ルベンゼンスルホン酸ナトリウムなどがあり、これらは
単独または２種以上の組み合わせで使用される。Dispersion aids for monomers in aqueous media may be conventionally known agents such as water-soluble cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose; saponification degree of 60 to 99 mol. %, water-soluble partially saponified polyvinyl alcohol with an average degree of polymerization of 700 to 3000; acrylic acid polymer; water-soluble polymers such as gelatin; sorbitan monolaurate, triolate, sorbitan monostearate, glycerin tristearate, ethylene oxide propylene oxide block Oil-soluble emulsifiers such as copolymers; water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerol oleate, and sodium lauryl sulfate; calcium carbonate, calcium phosphate, and sodium dodecylbenzenesulfonate, which can be used alone or Used in combination of two or more types.
この重合に際しての他の条件、重合器への水性媒体、塩
化ビニル単量体、場合によっては他のコモノマー、懸濁
剤などの仕込み方法は従来と同様にして行えばよく、こ
れらの仕込み割合、重合温度などの重合条件もまた同様
でよい。The other conditions for this polymerization, the method of charging the aqueous medium, vinyl chloride monomer, other comonomers, suspending agent, etc. Polymerization conditions such as polymerization temperature may also be the same.
さらに必要に応じて、塩化ビニル系の重合に適宜使用さ
れる重合調整剤、連鎖移動剤、ｐＨ調整剤、ゲル化改良
剤、帯電防止剤、架橋剤、安定剤。Furthermore, if necessary, a polymerization regulator, a chain transfer agent, a pH adjuster, a gelling improver, an antistatic agent, a crosslinking agent, and a stabilizer are used as appropriate for vinyl chloride polymerization.
充てん剤、酸化防止剤、緩衝剤、スケール防止剤などを
添加することも任意である。It is also optional to add fillers, antioxidants, buffers, scale inhibitors, and the like.
以上のように本発明は塩化ビニル系重合体の製造時に生
成する泡の消泡方法を確立したもので。As described above, the present invention establishes a method for defoaming foam generated during the production of vinyl chloride polymers.
その工業的価値は非常に大きいものである。Its industrial value is extremely large.
（実施例）
以下、本発明の具体的態様を実施例および比較例により
説明するが、本発明はこれに限定されるものではない。(Examples) Hereinafter, specific aspects of the present invention will be explained using Examples and Comparative Examples, but the present invention is not limited thereto.
実施例 １゜
内容積２０００ ｍの攪拌器およびジャケット付きのス
テンレス製重合器に、脱イオン水を９００ ｋｇ、けん
化度８０モル％、平均重合度２０００の部分けん化ポリ
ビニルアルコールを４２０ｇ、ジー２−エチルへキシル
パーオキシジカーボネートを２６０ｇ、それぞれ仕込み
、器内を脱気後、塩化ビニル単量体６００−を仕込み、
攪拌しながらジャケットに熱水を通して５７℃まで昇温
し、重合を開始した。Example 1 900 kg of deionized water, 420 g of partially saponified polyvinyl alcohol with a saponification degree of 80 mol% and an average degree of polymerization of 2000, and di-2-ethyl were placed in a stainless steel polymerization vessel with an internal volume of 2000 m and a stirrer and a jacket. After charging 260g of hexyl peroxydicarbonate and degassing the inside of the container, 600g of vinyl chloride monomer was charged.
While stirring, hot water was passed through the jacket and the temperature was raised to 57°C to initiate polymerization.
５７℃になった時点で、表−１に示した種類と量の添加
剤を加え、さらに１時間３０分後（重合率１０％のとき
）より２時間還流コンデンサーによる除熱を行いながら
重合を続けた。When the temperature reached 57°C, the types and amounts of additives shown in Table 1 were added, and after another 1 hour and 30 minutes (when the polymerization rate was 10%), polymerization was continued while removing heat using a reflux condenser for 2 hours. continued.
重合器の内圧が６．０ｋｇ／ａｊＧに低下したところで
未反応単量体を回収し、重合体スラリーを器外に取り出
し、脱水乾燥して塩化ビニル系重合体を得た。When the internal pressure of the polymerization vessel decreased to 6.0 kg/ajG, unreacted monomers were collected, and the polymer slurry was taken out of the vessel and dehydrated and dried to obtain a vinyl chloride polymer.
スラリーを器外に取り出した後の重合器内におけるスケ
ールの付着状態を観察し、次の判断基準で評価した。After the slurry was taken out of the vessel, the state of scale adhesion inside the polymerization vessel was observed and evaluated using the following criteria.
スケールの付着なし ・・・・・・・・・・・・０
〃 少々あり ・・・・・・・・・・・・Δ〃 多量に
あり・・・・・・・・・・・・Ｘまた、得られた塩化ビ
ニル系重合体の嵩比重をＪＩＳ Ｋ−６７２１にしたが
って測定すると共に、その重合体１０ｋｇ中の泡状重合
物の量を把握するため、ＪＩＳ Ｚ−８８０１に準じた
４８メツシユの篩を用いて、その篩上残量を測定し、こ
れらの結果を表−１に併記した。No scale adhesion ・・・・・・・・・・・・0
〃 A small amount ・・・・・・・・・・・・Δ〃 A large amount ・・・・・・・・・・・・X Also, the bulk specific gravity of the obtained vinyl chloride polymer is determined by JIS K- 6721, and in order to ascertain the amount of foamy polymer in 10 kg of the polymer, a 48 mesh sieve according to JIS Z-8801 was used to measure the amount remaining on the sieve. The results are also listed in Table-1.
なお、表中の添加剤の種類は下記の通りである。The types of additives in the table are as follows.
Ａ：けん化度４０モル％、平均重合度３００の部分けん
化ポリビニルアルコール３０重量％とメタノール３５重
量％とを含有する水溶液。A: An aqueous solution containing 30% by weight of partially saponified polyvinyl alcohol with a degree of saponification of 40 mol% and an average degree of polymerization of 300 and 35% by weight of methanol.
Ｂニジメチルポリシロキサン５０重量％、シリカ０．１
重量％を含有する水性エマルジョン。B Nidimethylpolysiloxane 50% by weight, silica 0.1
Aqueous emulsion containing % by weight.
表
（＊：４８メツシュ篩上％）
実施例 ２゜
前例の実験Ｎｏ、５において、添加剤Ａ、Ｂの添加時期
を表−２に示すようにを変えて加えたほかは、同様にし
て重合を行い、得られた重合体について同様の測定を行
い、その結果を表−２に併記した。Table (*: % on 48 mesh sieve) Example 2゜Polymerization was carried out in the same manner as in the previous experiment No. 5, except that additives A and B were added at different times as shown in Table-2. The obtained polymer was subjected to similar measurements, and the results are also listed in Table 2.
表
（拳＝４８メツシュ篩上％）
（発明の効果）
本発明によれば、重合器内のスケールの付着がなく、高
い嵩比重の均一な品質のポリ塩化ビニル製品を高い生産
性で得ることが可能となり、工業的効果が極めて大であ
る。Table (Fist = 48% on mesh sieve) (Effect of the invention) According to the present invention, there is no scale adhesion in the polymerization vessel, and a polyvinyl chloride product of high bulk specific gravity and uniform quality can be obtained with high productivity. This makes it possible to have an extremely large industrial effect.
Claims (1)
ビニル系単量体の混合物を、還流コンデンサー付き重合
缶内に仕込んで水性媒体中で重合を始めた後、その１０
０重量部当り、 イ）けん化度２０〜５０モル％、平均重合度２００〜４
００の部分けん化ポリビニルアルコール０．００２〜０
．００７重量部と、 ロ）消泡剤０．００１〜０．０１重量部とを、それまで
の重合による還流コンデンサーでの全除熱量が全重合発
熱量の１０％を超えない内に、重合系に添加することを
特徴とする塩化ビニル系重合体の製造方法。[Claims] 1. A vinyl chloride monomer or a mixture of vinyl monomers mainly composed of vinyl chloride is charged into a polymerization vessel equipped with a reflux condenser and polymerization is started in an aqueous medium. 10
0 parts by weight, a) degree of saponification 20-50 mol%, average degree of polymerization 200-4
00 partially saponified polyvinyl alcohol 0.002-0
．． 007 parts by weight and b) 0.001 to 0.01 parts by weight of antifoaming agent to the polymerization system while the total amount of heat removed in the reflux condenser due to the polymerization up to that point does not exceed 10% of the total polymerization calorific value. 1. A method for producing a vinyl chloride polymer, characterized in that the vinyl chloride polymer is added to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009056A JP2807526B2 (en) | 1990-01-18 | 1990-01-18 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009056A JP2807526B2 (en) | 1990-01-18 | 1990-01-18 | Method for producing vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03212409A true JPH03212409A (en) | 1991-09-18 |
| JP2807526B2 JP2807526B2 (en) | 1998-10-08 |
Family
ID=11709972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009056A Expired - Fee Related JP2807526B2 (en) | 1990-01-18 | 1990-01-18 | Method for producing vinyl chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2807526B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613853B1 (en) | 1999-10-28 | 2003-09-02 | The Nippon Synthetic Chemical Industry Co., Ltd. | Production method of vinyl resin |
| US7193012B2 (en) | 2003-01-30 | 2007-03-20 | The Nippon Synthetic Chemical Industry Co., Ltd. | Dispersing agent comprising vinyl alcohol polymer having conjugated double bonds in its molecule |
| CN102311516A (en) * | 2011-06-09 | 2012-01-11 | 天津辛德玛悬浮剂有限公司 | Method for preparing PVA (polyvinyl alcohol) assisted dispersant for manufacturing polyvinyl chloride by using suspension method |
| WO2021049883A1 (en) | 2019-09-10 | 2021-03-18 | 한화솔루션 주식회사 | Batch-type stirrer for suspension polymerization of polyvinyl chloride resin, and batch-type suspension polymerization reactor using same |
| KR20210030884A (en) | 2019-09-10 | 2021-03-18 | 한화솔루션 주식회사 | Agitator for Batch Suspension Polymerization for Production of Vinyl Chloride Resin and Batch Suspension Polymerization Reactor Using the Same |
-
1990
- 1990-01-18 JP JP2009056A patent/JP2807526B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613853B1 (en) | 1999-10-28 | 2003-09-02 | The Nippon Synthetic Chemical Industry Co., Ltd. | Production method of vinyl resin |
| US7193012B2 (en) | 2003-01-30 | 2007-03-20 | The Nippon Synthetic Chemical Industry Co., Ltd. | Dispersing agent comprising vinyl alcohol polymer having conjugated double bonds in its molecule |
| CN102311516A (en) * | 2011-06-09 | 2012-01-11 | 天津辛德玛悬浮剂有限公司 | Method for preparing PVA (polyvinyl alcohol) assisted dispersant for manufacturing polyvinyl chloride by using suspension method |
| WO2021049883A1 (en) | 2019-09-10 | 2021-03-18 | 한화솔루션 주식회사 | Batch-type stirrer for suspension polymerization of polyvinyl chloride resin, and batch-type suspension polymerization reactor using same |
| KR20210030884A (en) | 2019-09-10 | 2021-03-18 | 한화솔루션 주식회사 | Agitator for Batch Suspension Polymerization for Production of Vinyl Chloride Resin and Batch Suspension Polymerization Reactor Using the Same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2807526B2 (en) | 1998-10-08 |
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