JPH0350762B2 - - Google Patents
Info
- Publication number
- JPH0350762B2 JPH0350762B2 JP58193429A JP19342983A JPH0350762B2 JP H0350762 B2 JPH0350762 B2 JP H0350762B2 JP 58193429 A JP58193429 A JP 58193429A JP 19342983 A JP19342983 A JP 19342983A JP H0350762 B2 JPH0350762 B2 JP H0350762B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- polymerization initiator
- water
- vinyl chloride
- charged
- 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.)
- Expired - Lifetime
Links
- 238000006116 polymerization reaction Methods 0.000 claims description 57
- 239000003505 polymerization initiator Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 11
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- -1 amphoteric Chemical group 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000000375 suspending agent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 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 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- AMEVLYGGLRIBIO-UHFFFAOYSA-N octoxycarbonyloxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOC(=O)OCCCCCCCC AMEVLYGGLRIBIO-UHFFFAOYSA-N 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229950010765 pivalate Drugs 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
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 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
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 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
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical class CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- NEIOXSKRYNIBEI-UHFFFAOYSA-N 2-methoxypropoxycarbonyloxy 2-methoxypropyl carbonate Chemical compound COC(C)COC(=O)OOC(=O)OCC(C)OC NEIOXSKRYNIBEI-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- NOSKGILFKXJBMP-UHFFFAOYSA-N CC(C)(C)CCCCCC(=O)OOOC(C)(C)C1=CC=CC=C1 Chemical compound CC(C)(C)CCCCCC(=O)OOOC(C)(C)C1=CC=CC=C1 NOSKGILFKXJBMP-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical group CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- IAWYWVVBKGWUEP-UHFFFAOYSA-N benzyl phenylmethoxycarbonyloxy carbonate Chemical compound C=1C=CC=CC=1COC(=O)OOC(=O)OCC1=CC=CC=C1 IAWYWVVBKGWUEP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DDMBAIHCDCYZAG-UHFFFAOYSA-N butyl 7,7-dimethyloctaneperoxoate Chemical compound CCCCOOC(=O)CCCCCC(C)(C)C DDMBAIHCDCYZAG-UHFFFAOYSA-N 0.000 description 1
- LQKBKHFGCGFBAF-UHFFFAOYSA-N butyl carboxyoxy carbonate Chemical group CCCCOC(=O)OOC(O)=O LQKBKHFGCGFBAF-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- DHRQKFYLKJURNK-UHFFFAOYSA-N dodecoxycarbonyloxy dodecyl carbonate Chemical compound CCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCC DHRQKFYLKJURNK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 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
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 本発明は塩化ビニルの重合方法に関する。[Detailed description of the invention] The present invention relates to a process for polymerizing vinyl chloride.
塩化ビニル樹脂は安定剤、可塑剤の使用量によ
り硬質樹脂から軟質樹脂まで広い用途に用いうる
有用な樹脂である。この有用な塩化ビニル樹脂は
水性媒体中に懸濁重合により製造されるのが常で
ある。 Vinyl chloride resin is a useful resin that can be used in a wide variety of applications, from hard resins to soft resins, depending on the amount of stabilizers and plasticizers used. This useful vinyl chloride resin is commonly prepared by suspension polymerization in an aqueous medium.
ところで、この水性溶媒中で塩化ビニルを重合
すると重合機内面に重合物が付着し（通常この付
着物はスケールと呼ばれる。）、重合に際し発生す
る熱を除去する能力を低下させ、かつ、スケール
が付いた場合には可塑剤で可塑化できない重合体
粒子（通常、フイツシユ・アイと呼ばれる。）が
多くなり問題となる。 By the way, when vinyl chloride is polymerized in this aqueous solvent, the polymer adheres to the inner surface of the polymerization machine (this adherent is usually called scale), which reduces the ability to remove the heat generated during polymerization, and the scale increases. If this occurs, there will be a large number of polymer particles that cannot be plasticized by plasticizers (usually called plastic eyes), which will cause problems.
重合開始剤は通常塩化ビニルを装入する前に
水、懸濁剤と共に装入され、次いで脱空気される
のであるが、前記のスケール付着防止、フイツシ
ユ・アイの生成防止のためには、塩化ビニルを装
入と共に、あるいはその後、重合開始前に装入さ
れるのが望ましいことが知られている。 The polymerization initiator is usually charged together with water and a suspending agent before charging vinyl chloride, and then deaerated. It is known that it is desirable to charge the vinyl with the charge, or afterwards, before the start of the polymerization.
ところで、重合開始剤の装入方法としては、固
体の重合開始剤を直接重合期に装入する方法、有
機溶倍に溶かした重合開始剤の溶液をポンプ等で
装入する方法等があり、特に重合開始剤の溶液を
用いる方法ではスケールの付着が驚くほど減少す
るが、残念ながら重合開始剤を装入したラインが
短期間で詰まつてしまい、工業的な方法とは言え
ない。そのために、重合開始剤を装入したのち溶
媒で洗浄することが詰まり防止には有効である
が、完全ではなく、かつ、重合終了後に回収する
単量体に溶媒が含まれたり、塩化ビニル樹脂を乾
燥するときの廃ガスに含まれたり、あるいは廃水
のCODを増加させる問題がある。また、重合開
始剤を溶かすのに用いた溶媒や装入ラインの洗浄
に用いた溶媒が高沸点のものでは塩化ビニル樹脂
に多量に残存し、揮発分の増大、品質の低下、熱
安定性不足の原因となる。 By the way, methods for charging the polymerization initiator include a method in which a solid polymerization initiator is directly charged into the polymerization period, a method in which a solution of the polymerization initiator dissolved in an organic solvent is charged using a pump, etc. Particularly, a method using a solution of a polymerization initiator surprisingly reduces scale adhesion, but unfortunately the line into which the polymerization initiator is charged becomes clogged in a short period of time, so it cannot be called an industrial method. For this reason, cleaning with a solvent after charging the polymerization initiator is effective in preventing clogging, but it is not completely effective, and the monomer recovered after polymerization may contain solvent, or the vinyl chloride resin There is a problem that it is included in the waste gas when drying or increases the COD of wastewater. In addition, if the solvent used to dissolve the polymerization initiator or the solvent used to clean the charging line has a high boiling point, a large amount remains in the vinyl chloride resin, resulting in an increase in volatile content, a decrease in quality, and a lack of thermal stability. It causes
本発明者らは鋭意検討した結果、意外にも重合
開始剤装入ノズルの詰まりは重合反応中にノズル
の中に水を流すことにより防止できること、およ
び、得られる塩化ビニル樹脂の品質も良好である
ことを見出し、更に研究して遂に本発明を完成し
た。 As a result of intensive studies, the inventors of the present invention surprisingly found that clogging of the polymerization initiator charging nozzle can be prevented by flowing water into the nozzle during the polymerization reaction, and that the quality of the resulting vinyl chloride resin is also good. After discovering something, they conducted further research and finally completed the present invention.
本発明の目的は、重合開始剤装入ノズルが詰ま
らず、得られる塩化ビニル樹脂の品質の良好な塩
化ビニルの重合方法を提供することにある。 An object of the present invention is to provide a method for polymerizing vinyl chloride in which a polymerization initiator charging nozzle is not clogged and the resulting vinyl chloride resin is of good quality.
即ち、本発明の重合方法は、塩化ビニルのみま
たはこれと共重合しうる単量体との混合物を水性
媒体中で懸濁重合する際に、重合反応中に重合開
始剤装入ノズルから水を連続的もしくは間欠的に
装入することを特徴とする塩化ビニルの重合方法
である。 That is, in the polymerization method of the present invention, when vinyl chloride alone or a mixture of vinyl chloride and a monomer copolymerizable with vinyl chloride is subjected to suspension polymerization in an aqueous medium, water is introduced from a polymerization initiator charging nozzle during the polymerization reaction. This is a method for polymerizing vinyl chloride, which is characterized by continuous or intermittently charging.
本発明の重合方法は、一般に当業界で行なわれ
ている水性媒体中での懸濁重合方法に適用できる
ものである。 The polymerization method of the present invention can be applied to suspension polymerization methods in an aqueous medium that are generally practiced in the art.
重合に際し用いる水の量は、塩化ビニル等の単
量体100重量部に対し80〜300重量部が適当であ
り、これに懸濁剤必要に応じ乳化剤、重合開始剤
等が加えられ、撹拌下に30〜70℃で重合される。 The appropriate amount of water used during polymerization is 80 to 300 parts by weight per 100 parts by weight of a monomer such as vinyl chloride, and a suspending agent, an emulsifier, a polymerization initiator, etc. are added to this, and the mixture is stirred. It is polymerized at 30-70℃.
また、必要に応じ用いられる乳化剤としてはア
ニオン系、両性、カチオン系、ノニオン系のいず
れでもよい。 Further, the emulsifier used as necessary may be any of anionic, amphoteric, cationic, and nonionic emulsifiers.
使用される懸濁剤としては例えばポリビニルア
ルコール、セルローズ誘導体、無水マレイン酸−
スチレン共重合体、無水マレイン酸−メチルビニ
ルエーテル共重合体、ポリビニルピロリドン、ゼ
ラチン等があげられこれらは単独又は必要に応じ
二種類以上組み合わせて使用される。 Suspending agents used include, for example, polyvinyl alcohol, cellulose derivatives, maleic anhydride.
Examples include styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, polyvinylpyrrolidone, gelatin, etc., and these may be used alone or in combination of two or more as necessary.
本発明における塩化ビニルと共重合しうる単量
体としては、たとえばエチレン、プロピレン、１
−ブテン、１−ペンテン、１−ヘキセン、１−ヘ
プテン、１−オクテン、１−ノネン、１−デセ
ン、１−ウンデセン、１−ドデセン、１−トリデ
セン、１−テトラデセン等の炭素数が２〜30のα
−オレフイン、アクリル酸もしくはそのエステル
類、メタクリル酸もしくはそのエステル類、マレ
イン酸もしくはそのエステル類、酢酸ビニル、プ
ロピオン酸ビニル、アルキルビニルエーテル等の
ビニル化合物等が挙げられ、これらは１種以上が
用いられる。 Monomers copolymerizable with vinyl chloride in the present invention include, for example, ethylene, propylene,
-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, etc. with 2 to 30 carbon atoms α of
- Vinyl compounds such as olefin, acrylic acid or its esters, methacrylic acid or its esters, maleic acid or its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether, etc., and one or more of these may be used. .
使用される重合開始剤としては、ジイソプロピ
ルパーオキシジカーボネート、ジオクチルパーオ
キシジカーボネート、ジラウリルパーオキシジカ
ーボネート、ジセチルパーオキシジカーボネー
ト、ジターシヤリーブチルパーオキシジカーボネ
ート、ジ（２−エトキシエチル）パーオキシジカ
ーボネート、ジ（２−メトキシプロピル）パーオ
キシジカーボネート、ジベンジルパーオキシジカ
ーボネート、ジシクロヘキシルパーオキシジカー
ボネート、ジターシヤリーブチルシクロヘキシル
パーオキシジカーボネート等のパーオキシジカー
ボネート類、２・2′−アゾビス−２，４−ジメチ
ルバレロニトリル、２・2′−アゾビス−４−メト
キシ−２，４−ジメチルバレロニトリル等のアゾ
化合物、ターシヤリーブチルパーオキシネオデカ
ネート、α−クミルパーオキシネオデカネート、
ターシヤリーオクチルパーオキシネオデカネー
ト、アミルパーオキシネオデカネート、ターシヤ
リーブチルパーオキシピバレート、α−クミルパ
ーオキシピバレート、アミルパーオキシピバレー
ト、ジターシヤリーブチルオギザレート、イソブ
チリルパーオキサイド等のパーオキサイド、パー
オキシエステル類があげられ、これらはそのま
ま、溶剤に溶かした溶液あるいは乳化剤、懸濁剤
を用い水に分散されたものとして用いられる。ま
た、これらは重合反応速度を均一化する為に２種
以上が組み合わせて使用するのが好ましい。 Polymerization initiators used include diisopropyl peroxydicarbonate, dioctyl peroxydicarbonate, dilauryl peroxydicarbonate, dicetyl peroxydicarbonate, ditertiary butyl peroxydicarbonate, di(2-ethoxyethyl ) Peroxydicarbonates such as peroxydicarbonate, di(2-methoxypropyl)peroxydicarbonate, dibenzyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, ditertiarybutylcyclohexyl peroxydicarbonate, 2. Azo compounds such as 2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, tert-butylperoxyneodecanate, α-cumylperoxy neodecanate,
Tertiary octyl peroxy neodecanate, amyl peroxy neodecanate, tertiary butyl peroxy pivalate, α-cumyl peroxy pivalate, amyl peroxy pivalate, ditertiary butyl oxalate, isobutyryl peroxide These peroxides and peroxy esters are used as they are, either as a solution in a solvent or as a dispersion in water using an emulsifier or suspending agent. Moreover, in order to equalize the polymerization reaction rate, it is preferable to use two or more of these in combination.
水に分散した重合開始剤は、重合開始剤、乳化
剤、または乳化剤・懸濁剤、水より成り、凍結を
防止する為にメタノール、エタノール等のアルコ
ール、エチレングリコール等のグリコール類を添
加することもある。 The polymerization initiator dispersed in water consists of a polymerization initiator, an emulsifier, or an emulsifying/suspending agent, and water. Alcohols such as methanol and ethanol, and glycols such as ethylene glycol may also be added to prevent freezing. be.
ここに用いる乳化剤としてはアニオン系、両
性、カチオン系並びに非イオン系のものがある
が、中でも塩化ビニルの懸濁重合では塩化ビニル
樹脂の体積固有抵抗が重要視される為グリセリン
−モノステアレート、ソルビツト−モノラウレー
トおよび−オレートの如き多価アルコールの脂肪
酸部分エステル、脂肪酸または芳香族ヒドロキシ
化合物のポリオキシエチルエステル並びにポリプ
ロピレンオキサイド−ポリエチレンオキサイド−
縮合生成物等の非イオン系乳化剤が好ましい。こ
れらの乳化剤は単独又は必要に応じ二種類以上組
み合わせて使用される。 The emulsifiers used here include anionic, amphoteric, cationic, and nonionic emulsifiers, but among them, glycerin monostearate, glycerin monostearate, and Fatty acid partial esters of polyhydric alcohols such as sorbitol monolaurates and oleates, polyoxyethyl esters of fatty acids or aromatic hydroxy compounds and polypropylene oxides - polyethylene oxides.
Nonionic emulsifiers such as condensation products are preferred. These emulsifiers may be used alone or in combination of two or more, if necessary.
また、乳化剤と共に用いる懸濁剤としてはポリ
ビニルアルコール、セルローズ誘導体、無水マレ
イン酸−スチレン共重合体、無水マレイン酸−メ
チルビニルエーテル共重合体、ゼラチン、ポリビ
ニルピロリドン等が挙げられる。 Suspending agents used together with emulsifiers include polyvinyl alcohol, cellulose derivatives, maleic anhydride-styrene copolymers, maleic anhydride-methyl vinyl ether copolymers, gelatin, polyvinylpyrrolidone, and the like.
重合開始剤を溶かす溶剤としては、例えばメタ
ノール、エタノール等のアルコール、ヘキサン、
シエルゾール（商標）等のハイドロカーボン、ベ
ンゼン、トルエン、キシレン等の芳香族炭化水素
が挙げられる。 Examples of solvents for dissolving the polymerization initiator include alcohols such as methanol and ethanol, hexane,
Examples include hydrocarbons such as Cielzol (trademark), and aromatic hydrocarbons such as benzene, toluene, and xylene.
これら重合開始剤のうち、取扱いの容易さ、共
存する媒体等に問題が少ないことから、水に分散
した重合開始剤を用いるのが好ましい。 Among these polymerization initiators, it is preferable to use a polymerization initiator dispersed in water because it is easy to handle and there are few problems with coexisting media.
本発明で重要な点は、重合反応中に重合開始剤
を装入したノズルから水を連続的あるいは間欠的
に装入することである。 An important point in the present invention is that during the polymerization reaction, water is continuously or intermittently introduced through a nozzle containing a polymerization initiator.
この重合反応中に装入する水は、重合反応によ
り反応混合液の体積が低下するのに見合つた量を
圧入する水の一部あるいは全部とすることもでき
る。 The water charged during this polymerization reaction may be part or all of the water that is injected in an amount commensurate with the volume reduction of the reaction mixture due to the polymerization reaction.
重合開始剤装入ノズルに水を流さないと重合開
始剤装入ノズルが詰まると共に、詰まらない場合
でもスケールの付着あるいはフイツシユ・アイが
多くなる。 If water is not allowed to flow through the polymerization initiator charging nozzle, the polymerization initiator charging nozzle will become clogged, and even if it is not clogged, scale adhesion or fish eyes will increase.
本発明では重合開始剤の装入ノズルとしては特
別の構造のものは必要でなく、いずれのものでも
用いうるが、好ましい構造のものを例示すると、
第１図、第２図に示すものがあげられる。 In the present invention, no special structure is required for the polymerization initiator charging nozzle, and any type can be used, but examples of preferable structures include:
Examples include those shown in FIGS. 1 and 2.
第１図において、１は重合機壁を示す。重合開
始剤ノズル２は管３と重合開始剤装入口４より成
り、通常フランジ５により重合機ノズル６に接し
ている。しかし、フランジ５なしに管３が重合機
壁１に直接溶接されていても良い。管３の先端は
重合機内壁を結ぶ線７より重合機内側に突き出し
ていた方が重合開始剤の飛沫が内壁に付着しない
ので好ましい。 In FIG. 1, 1 indicates the wall of the polymerization machine. The polymerization initiator nozzle 2 consists of a tube 3 and a polymerization initiator inlet 4, and is usually in contact with a polymerizer nozzle 6 by a flange 5. However, the tube 3 can also be welded directly to the polymerizer wall 1 without the flange 5. It is preferable for the tip of the tube 3 to protrude inside the polymerizer from the line 7 connecting the inner walls of the polymerizer to prevent droplets of polymerization initiator from adhering to the inner walls.
重合開始剤は例えばポンプ又は水エゼクターに
より重合開始剤装入口４を経て管３を通り重合機
へ装入される。次いで水がポンプによりこの経路
により重合機へ装入され、ポンプ、配管、重合機
装入ノズルの内面に付着した重合開始剤を洗い流
す。 The polymerization initiator is charged into the polymerization machine via the polymerization initiator inlet 4 and through the pipe 3, for example by means of a pump or a water ejector. Water is then pumped into the polymerizer through this route to wash away the polymerization initiator adhering to the pump, piping, and inner surfaces of the polymerizer charging nozzle.
又、重合反応中水が重合開始剤装入口４を経て
管３を通り重合機へ連続的あるいは間欠的に注入
される。これらの操作はシークエンスにより自動
的に行なつても良い。 During the polymerization reaction, water is continuously or intermittently injected into the polymerization machine through the polymerization initiator inlet 4 and the pipe 3. These operations may be performed automatically by a sequence.
第２図は重合開始剤装入ノズル２にノズルの外
側を洗浄するための水を流す外管８が設けられた
ものをである。 FIG. 2 shows a polymerization initiator charging nozzle 2 provided with an outer pipe 8 through which water flows for washing the outside of the nozzle.
第２図において１は重合機壁を示す。重合開始
剤ノズル２は内管３、外管８、水装入口９、重合
開始剤装入口４より成り、通常フランジ５により
重合機ノズル６に接しているがフランジ５なしに
外管８が重合機壁に直接溶接されていても良い。
内管３の先端は重合機内壁を結ぶ線７より重合機
内側に突き出していた方が好ましい。 In FIG. 2, 1 indicates the wall of the polymerization machine. The polymerization initiator nozzle 2 consists of an inner tube 3, an outer tube 8, a water inlet 9, and a polymerization initiator inlet 4, and is normally in contact with a polymerization machine nozzle 6 through a flange 5, but if the outer tube 8 is used for polymerization without the flange 5. It may be directly welded to the machine wall.
It is preferable that the tip of the inner tube 3 protrudes into the polymerizer from the line 7 connecting the inner walls of the polymerizer.
重合開始剤は例えばポンプ又は水エゼクターに
より重合開始剤装入口４を経て内管３を通り重合
機へ装入される。次いで、水がポンプによりこの
経路により重合機に装入され、ポンプ、配管、重
合機装入ノズルの内面に付着した重合開始剤を洗
い流す。又、重合反応中は重合開始剤装入口４を
経て内管３を通り、又水装入口９を経て外管８と
内管２の間を通り重合機へ水が連続的に注入され
る。これらの操作はシークエンスにより自動的に
行なつても良い。 The polymerization initiator is charged into the polymerization machine via the polymerization initiator inlet 4 and through the inner pipe 3 by means of a pump or a water ejector, for example. Water is then pumped into the polymerizer through this route to wash away the polymerization initiator adhering to the pump, piping, and inner surfaces of the polymerizer charging nozzle. During the polymerization reaction, water is continuously injected into the polymerization machine through the polymerization initiator inlet 4, through the inner tube 3, and through the water supply inlet 9, between the outer tube 8 and the inner tube 2. These operations may be performed automatically by a sequence.
水に分散したり、有機溶媒に溶解した重合開始
剤を装入するポンプとしては金属による激しい摩
擦がないものが好ましく、このようなポンプの例
としてダイヤフラムポンプ、べローズポンプ、ホ
ースポンプ、モーノポンプ等が挙げられる。中で
も吐出圧力が高く金属による摩擦のない単連又は
多連のダイヤフラムポンプが好適に用いうる。 As a pump for charging a polymerization initiator dispersed in water or dissolved in an organic solvent, it is preferable to use a pump that does not have severe friction due to metal. Examples of such pumps include diaphragm pumps, bellows pumps, hose pumps, mono pumps, etc. can be mentioned. Among these, single or multiple diaphragm pumps with high discharge pressure and no friction due to metal can be preferably used.
本発明の方法では、重合開始剤装入ノズルにつ
まりが生じないので、スケールの付着やフイツシ
ユ・アイの少ない良好な塩化ビニル樹脂が得られ
る。 In the method of the present invention, since no clogging occurs in the polymerization initiator charging nozzle, a good vinyl chloride resin with less scale adhesion and fish eyes can be obtained.
以下実施例、比較令を挙げて本発明を更に具体
的に説明する。 The present invention will be explained in more detail below with reference to Examples and Comparative Examples.
実施例 １
内容積７m3の重合機に、水2250Kg、ケン化度80
モル％で平均重合度2000の部分ケン化ポリビニル
アルコール1.8Kgを装入し、内部の空気を真空ポ
ンプで排除した後、塩化ビニル2250Kgを装入し
た。次いで、40Wt％のジオクチルパーオキシジ
カーボネート水分散液1.1Kg、40Wt％のα−クミ
ルパーオキシネオデカネート水分散液2.1Kgを２
連のダイヤフラムポンプを用い、第２図に示す重
合開始剤装入ノズルを用い１重合機に装入し、次
いで水50Kgを２連のダイヤフラムポンプを用いて
装入した。重合温度を50.5℃に設定し反応を進行
せしめ、管３と管８に水を20／hrで流し内部の
圧力が５Kg／cm2Ｇに達するまで反応を続けた。反
応終了後未反応単量体を回収、重合体のスラリー
を排出し、デカンターにて脱水後乾燥し、製品と
して塩化ビニル樹脂を取得した。デカンター排水
のCODは30mg／であつた。Example 1 A polymerization machine with an internal volume of 7 m 3 contains 2250 kg of water and a degree of saponification of 80.
1.8 kg of partially saponified polyvinyl alcohol with an average degree of polymerization of 2000 in mole % was charged, and after the internal air was removed with a vacuum pump, 2250 kg of vinyl chloride was charged. Next, 1.1 kg of a 40 Wt% dioctyl peroxydicarbonate aqueous dispersion and 2.1 kg of a 40 Wt% α-cumyl peroxyneodecanate aqueous dispersion were
Using a series of diaphragm pumps, the polymerization initiator was charged into one polymerization machine using the polymerization initiator charging nozzle shown in FIG. 2, and then 50 kg of water was charged using a double series of diaphragm pumps. The polymerization temperature was set at 50.5°C to allow the reaction to proceed, water was flowed through tubes 3 and 8 at a rate of 20/hr, and the reaction was continued until the internal pressure reached 5 kg/cm 2 G. After the reaction was completed, unreacted monomers were collected, and the polymer slurry was discharged, dehydrated and dried in a decanter, and a vinyl chloride resin was obtained as a product. The COD of the decanter wastewater was 30mg/.
重合機内部を300Kg／cm2Ｇ圧の高圧水で洗浄し
剥がれたスケールを取得し乾燥したところ50ｇで
あつた。同様の操作を、１日１回、３ケ月間行な
つたが、重合開始剤装入ノズルに詰りはみられな
かつた。 The interior of the polymerization machine was washed with high-pressure water at a pressure of 300 kg/cm 2 G, and the peeled off scale was collected and dried, weighing 50 g. Similar operations were carried out once a day for three months, but no clogging was observed in the polymerization initiator charging nozzle.
比較例 １
実施例１において、重合反応中管３と管８に水
を流さず、通常の水装入ラインから水を圧入する
以外は全て実施例１と同様に重合を行なつた。同
様の操作を１日１回行なつたところ、15日目に重
合開始剤装入ノズルが詰り、重合開始剤の装入が
行なえなくなつた。Comparative Example 1 Polymerization was carried out in the same manner as in Example 1, except that water was not allowed to flow through tubes 3 and 8 during the polymerization reaction, and water was pressurized from the normal water charging line. When similar operations were carried out once a day, on the 15th day, the polymerization initiator charging nozzle became clogged, making it impossible to charge the polymerization initiator.
比較例 ２
内容積７m3の重合機に、水2250Kg、ケン化度80
モル％で平均重合度2000の部分ケン化ポリビニル
アルコール1.8Kgを装入し、内部の空気を真空ポ
ンプで排除した後、塩化ビニル2250Kgを装入し
た。塩化ビニルを装入している間にポツトにより
40Wt％のジオクチルパーオキシジカーボネート
水分散液1.1Kg、40Wt％のα−クミルパーオキシ
ネオデカネード水分散液2.1Kgを装入し、重合温
度を50.5℃に設定し、反応を進行せしめ内部の圧
力が５Kg／cm2Ｇに達するまで反応を続けた。反応
終了後未反応単量体を回収、重合体のスラリーを
排出しデカンターにて脱水後乾燥し製品として塩
化ビニル樹脂を取得した。同様の操作を１日１回
行なつたところ５日目に、ポツトを取付けた重合
機のノズルが詰まり、重合開発剤の装入が行なえ
なくなつた。Comparative Example 2 A polymerization machine with an internal volume of 7 m3 , 2250 kg of water, and a degree of saponification of 80
1.8 kg of partially saponified polyvinyl alcohol with an average degree of polymerization of 2000 in mole % was charged, and after the internal air was removed with a vacuum pump, 2250 kg of vinyl chloride was charged. While charging vinyl chloride, the pot
1.1 kg of a 40 Wt% dioctyl peroxydicarbonate aqueous dispersion and 2.1 kg of a 40 Wt% α-cumyl peroxyneodecanate aqueous dispersion were charged, and the polymerization temperature was set at 50.5°C to allow the reaction to proceed. The reaction was continued until the pressure reached 5 kg/cm 2 G. After the reaction was completed, unreacted monomers were collected, and the polymer slurry was discharged, dehydrated in a decanter, and then dried to obtain a vinyl chloride resin as a product. When similar operations were carried out once a day, on the fifth day, the nozzle of the polymerization machine to which the pot was attached became clogged, making it impossible to charge the polymerization developer.
実施例 ２
内容積７m3の重合機に水2250Kg、ケン化度80モ
ル％で平均重合度2000の部分のケン化ポリビニル
アルコール0.9Kg、ヒドロキシプロピルメチルセ
ルローズ0.9Kgを装入し、内部の空気を真空ポン
プで排除した後、塩化ビニル2025Kg、炭素数６、
８、10個のα−オレフイン混合物225Kgを装入し
た。塩化ビニルを装入している間にイソパラフイ
ンに溶解した70Wt％α−クミルパーオキシネオ
デカネート溶液29Kgを２連のダイヤフラムポンプ
を用い第１図に示す重合開始剤装入ノズルを用い
て重合機に装入し、次いで水75Kgを２連のダイヤ
フラムポンプを用いて装入した。重合温度を45℃
に設定し反応を進行せしめ、管３に水30／hrを
流し、内部の圧力が３Kg／cm2Ｇに達するまで反応
を続けた。反応終了後未反応単量体を回収し、重
合体のスラリーを排出しデカンターにて脱水後乾
燥し、製品として塩化ビニル樹脂を取得した。重
合機内部を300Kg／cm2Ｇの高圧水で洗浄し剥がれ
たスケールを取得し乾燥したところ140ｇであつ
た。同様の操作を、１日１回、３ケ月間行なつた
が重合開始剤装入ノズルに詰りはみられなかつ
た。Example 2 A polymerization machine with an internal volume of 7 m 3 was charged with 2250 kg of water, 0.9 kg of saponified polyvinyl alcohol with a degree of saponification of 80 mol% and an average degree of polymerization of 2000, and 0.9 kg of hydroxypropyl methyl cellulose, and the air inside was charged. After removing it with a vacuum pump, 2025 kg of vinyl chloride, 6 carbons,
225 kg of a mixture of 8 and 10 α-olefins was charged. While charging vinyl chloride, 29 kg of a 70 Wt% α-cumyl peroxyneodecanate solution dissolved in isoparaffin was polymerized using a polymerization initiator charging nozzle shown in Figure 1 using a double diaphragm pump. The machine was then charged with 75 kg of water using two diaphragm pumps. Polymerization temperature 45℃
was set to allow the reaction to proceed, water was flowed through tube 3 at 30/hr, and the reaction was continued until the internal pressure reached 3 kg/cm 2 G. After the reaction was completed, unreacted monomers were collected, and the polymer slurry was discharged, dehydrated in a decanter, and then dried to obtain a vinyl chloride resin as a product. The inside of the polymerization machine was washed with high-pressure water of 300 kg/cm 2 G, and the peeled scale was collected and dried, and it weighed 140 g. Similar operations were carried out once a day for three months, but no clogging of the polymerization initiator charging nozzle was observed.
比較例 ３
実施例２において、重合反応中水30／hrを流
す代りにメタノール20／hrを流した以外は全て
実施例２と同様に重合を行なつた。同様の操作を
１日１回行ない、３ケ月間重合開始剤装入ノズル
に詰まりは無かつたが、デカンター排水のCOD
は約45000mg／と高く、問題であつた。Comparative Example 3 Polymerization was carried out in the same manner as in Example 2, except that 20/hr of methanol was flowed instead of 30/hr of water during the polymerization reaction. The same operation was performed once a day, and the polymerization initiator charging nozzle was not clogged for 3 months, but the COD in the decanter drainage
The amount was high at approximately 45,000 mg/day, which was a problem.
実施例 ３
内容積７m3の重合機に、水2250Kgケン化度80モ
ル％で平均重合度2000の部分ケン化ポリビニルア
ルコール1.8Kgを装入した。先ず40W％のジオク
チルパーオキシジカーボネート水分散液0.6Kg、
40Wt％の２，２−アゾビス−２，４−ジメチル
バレロニトリル水分散液1.7Kgを２連のダイヤフ
ラムポンプを用い第１図に示す重合開始剤装入ノ
ズルを用いて重合機に装入し、次いで水50Kgを２
連のダイヤフラムポンプを用いて装入した。内部
の空気を真空ポンプで排除した後、塩化ビニル
2250Kgを装入し、重合温度を57℃に設定し反応を
進行せしめ管３に水を20／hrで流し、内部の圧
力が６Kg／cm2Ｇに達するまで反応を続けた。Example 3 A polymerization machine having an internal volume of 7 m 3 was charged with 2250 kg of water and 1.8 kg of partially saponified polyvinyl alcohol having an average degree of polymerization of 2000 and a saponification degree of 80 mol%. First, 0.6 kg of 40W% dioctyl peroxydicarbonate aqueous dispersion,
1.7 kg of 40 Wt% 2,2-azobis-2,4-dimethylvaleronitrile aqueous dispersion was charged into a polymerization machine using a dual diaphragm pump and a polymerization initiator charging nozzle shown in Figure 1. Next, add 2 50 kg of water.
It was charged using a series of diaphragm pumps. After removing the air inside with a vacuum pump, the vinyl chloride
2250 kg was charged, the polymerization temperature was set at 57°C, the reaction was allowed to proceed, and water was flowed through the tube 3 at a rate of 20/hr, and the reaction was continued until the internal pressure reached 6 kg/cm 2 G.
反応終了後未反応単量体を回収し、重合体のス
ラリーを排出しデカンターにて脱水後乾燥し、製
品として塩化ビニル樹脂を取得した。デカンター
排水のCODは25mg／であつた。 After the reaction was completed, unreacted monomers were collected, and the polymer slurry was discharged, dehydrated in a decanter, and then dried to obtain a vinyl chloride resin as a product. The COD of the decanter wastewater was 25mg/.
重合機内部を300Kg／cm2Ｇ圧の高圧水で洗浄し、
剥がれたスケールを取得し乾燥したところ250ｇ
であつた。同様の操作を１日１回、３ケ月間行な
つたが、重合開始剤装入ノズルに詰りはみられな
かつた。 Wash the inside of the polymerization machine with high pressure water of 300Kg/cm 2 G pressure,
250g of peeled scale obtained and dried
It was hot. Similar operations were carried out once a day for three months, but no clogging was observed in the polymerization initiator charging nozzle.
実施例 ４
内容積７m3の重合機に水2250Kg、ケン化度80モ
ル％で平均重合度2000の部分ケン化ポリビニルア
ルコール0.9Kg、ヒドロキシプロピルメチルセル
ローズ0.9Kgを装入し、内部の空気を真空ポンプ
で排除した後、塩化ビニル2250Kgを装入した。塩
化ビニルを装入した後、先ずイソパラフインに溶
解した70Wt％α−クミルパーオキシネオデカネ
ート溶液0.3Kg、イソパラフインに溶解した70Wt
％ターンシヤリーブチルパーオキシネオデカネー
ト溶液0.5Kgを２連のダイヤフラムポンプを用い
第２図に示す重合開始剤装入ノズルを用いて重合
機に装入し、次いで水50Kgを２連のダイヤフラム
ポンプを用いて装入した。重合温度を57℃に設定
し、反応を進行せしめ管３と管８に水を25／hr
で流し内部の圧力が６Kg／cm2Ｇに達するまで反応
を続けた。Example 4 2250 kg of water, 0.9 kg of partially saponified polyvinyl alcohol with a degree of saponification of 80 mol% and an average degree of polymerization of 2000, and 0.9 kg of hydroxypropyl methyl cellulose were charged into a polymerization machine with an internal volume of 7 m3, and the air inside was evacuated. After pumping out, 2250 kg of vinyl chloride was charged. After charging vinyl chloride, first 0.3Kg of 70Wt% α-cumyl peroxyneodecanate solution dissolved in isoparaffin, 70Wt dissolved in isoparaffin
0.5Kg of %Turn shearly butyl peroxyneodecanate solution was charged into the polymerization machine using the polymerization initiator charging nozzle shown in Figure 2 using two diaphragm pumps, and then 50Kg of water was pumped into the polymerization machine using two diaphragm pumps. Charged using a pump. Set the polymerization temperature to 57℃, let the reaction proceed, and add water to tubes 3 and 8 at 25/hr.
The reaction was continued until the internal pressure reached 6 kg/cm 2 G.
反応終了後未反応単量体を回収し、重合体のス
ラリーを排出しデカンターにて脱水後乾燥し製品
として塩化ビニル樹脂を取得した。デカンター排
水のCODは32mg／であつた。重合機内部を300
Kg／cm2Ｇ圧の高圧水で洗浄し剥がれたスケールを
取得し乾燥したところ50ｇであつた。同様の操作
を１日１回、３ケ月間行なつたが、重合開始剤装
入ノズルに詰りはみられなかつた。 After the reaction was completed, unreacted monomers were collected, and the polymer slurry was discharged, dehydrated in a decanter, and then dried to obtain a vinyl chloride resin as a product. The COD of the decanter wastewater was 32mg/. Inside the polymerization machine 300
The peeled off scale was washed with high-pressure water at Kg/cm 2 G pressure, and when dried, it weighed 50 g. Similar operations were carried out once a day for three months, but no clogging was observed in the polymerization initiator charging nozzle.
第１図、第２図は重合開始剤装入ノズルの例を
示す断面図である。
図において、１は重合機壁、２は重合開始剤装
入ノズル、３はノズルの管（内管）、４は重合開
始剤装入口、５はノズルのフランジ、６は重合機
の重合開始剤装入ノズル取付けノズル、７は重合
機内壁面を結ぶ線、８はノズルの内管をおおう外
管、９は外管に水を入れる口である。
FIGS. 1 and 2 are cross-sectional views showing examples of polymerization initiator charging nozzles. In the figure, 1 is the wall of the polymerization machine, 2 is the polymerization initiator charging nozzle, 3 is the nozzle pipe (inner pipe), 4 is the polymerization initiator charging port, 5 is the flange of the nozzle, and 6 is the polymerization initiator of the polymerization machine. A charging nozzle attachment nozzle, 7 is a line connecting the inner wall surface of the polymerization machine, 8 is an outer tube that covers the inner tube of the nozzle, and 9 is an opening for introducing water into the outer tube.
Claims (1)
量体との混合物を水性媒体中で懸濁重合する際
に、重合反応中に重合開始剤装入ノズルから水を
連結的もしくは間欠的に装入することを特徴とす
る塩化ビニルの重合方法。1. When vinyl chloride alone or a mixture of vinyl chloride and a monomer copolymerizable with vinyl chloride is subjected to suspension polymerization in an aqueous medium, water is continuously or intermittently charged from a polymerization initiator charging nozzle during the polymerization reaction. A method for polymerizing vinyl chloride, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19342983A JPS6086104A (en) | 1983-10-18 | 1983-10-18 | Polymerization of vinyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19342983A JPS6086104A (en) | 1983-10-18 | 1983-10-18 | Polymerization of vinyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6086104A JPS6086104A (en) | 1985-05-15 |
| JPH0350762B2 true JPH0350762B2 (en) | 1991-08-02 |
Family
ID=16307823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19342983A Granted JPS6086104A (en) | 1983-10-18 | 1983-10-18 | Polymerization of vinyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6086104A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11106407A (en) * | 1997-10-07 | 1999-04-20 | Nippon Shokubai Co Ltd | Production of resin particle and its product |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0674293B2 (en) * | 1988-05-19 | 1994-09-21 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JPH0625224B2 (en) * | 1987-09-08 | 1994-04-06 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JP2627303B2 (en) * | 1988-04-27 | 1997-07-02 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JPH0613571B2 (en) * | 1988-01-08 | 1994-02-23 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JPH0613575B2 (en) * | 1988-01-08 | 1994-02-23 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JPH0613573B2 (en) * | 1988-05-19 | 1994-02-23 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JPH0613576B2 (en) * | 1988-10-14 | 1994-02-23 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| JPH0613577B2 (en) * | 1988-12-23 | 1994-02-23 | 信越化学工業株式会社 | Method for producing vinyl chloride polymer |
| US5187245A (en) * | 1989-11-13 | 1993-02-16 | Tosoh Corporation | Method of addition of polymerization initiator |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55157608A (en) * | 1979-05-28 | 1980-12-08 | Nippon Zeon Co Ltd | Polymerization of vinyl chloride |
-
1983
- 1983-10-18 JP JP19342983A patent/JPS6086104A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55157608A (en) * | 1979-05-28 | 1980-12-08 | Nippon Zeon Co Ltd | Polymerization of vinyl chloride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11106407A (en) * | 1997-10-07 | 1999-04-20 | Nippon Shokubai Co Ltd | Production of resin particle and its product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6086104A (en) | 1985-05-15 |
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