JPH0212963B2 - - Google Patents
Info
- Publication number
- JPH0212963B2 JPH0212963B2 JP9727481A JP9727481A JPH0212963B2 JP H0212963 B2 JPH0212963 B2 JP H0212963B2 JP 9727481 A JP9727481 A JP 9727481A JP 9727481 A JP9727481 A JP 9727481A JP H0212963 B2 JPH0212963 B2 JP H0212963B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- condenser
- conversion rate
- amount
- temperature
- 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
Links
- 238000006116 polymerization reaction Methods 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 19
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 10
- 238000005187 foaming Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims 1
- 239000000498 cooling water Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-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
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- DTGWMJJKPLJKQD-UHFFFAOYSA-N butyl 2,2-dimethylpropaneperoxoate Chemical compound CCCCOOC(=O)C(C)(C)C DTGWMJJKPLJKQD-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 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
- 150000002148 esters Chemical class 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 231100000234 hepatic damage Toxicity 0.000 description 1
- 230000008818 liver damage Effects 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
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- -1 nitrile compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 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
- 230000009291 secondary effect Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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、コンデンサを付設した重合器を用い
て塩化ビニル系樹脂を懸濁重合する方法の改善に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a method for suspension polymerizing vinyl chloride resin using a polymerization vessel equipped with a condenser.
塩化ビニル系樹脂の製造において、生産性向上
並びに省エネルギーを図る目的でコンデンサがし
ばしば用いられるが、コンデンサによる冷却を伴
なう懸濁重合では重合系に著しい発泡現象を生じ
ることが知られており、例えば弁の開閉により重
合転化率が５％以降にコンデンサを作動する方法
（特公昭53−38311）、予備攪拌した後、開始剤を
装入して重合を開始する方法（特公昭48−29795）
などが提案されているが、実用上は重合の中間以
降において重合懸濁液の粘度の上昇に伴ない攪拌
効果が低下するため、発生した気泡が浮上すると
共に懸濁液のホールドアツプが増加し、極端な場
合には重合体が導管あるいはコンデンサ内部へ侵
入し、再び懸濁液系へ巻き込まれることなく、そ
こで重合しスケールの塊となることがあり、コン
デンサを正常に稼働させることが困難となる他、
品質上も好ましくない等の問題があつた。 In the production of vinyl chloride resins, condensers are often used to improve productivity and save energy, but suspension polymerization that involves cooling with condensers is known to cause significant foaming in the polymerization system. For example, a method in which a condenser is activated when the polymerization conversion rate reaches 5% or more by opening and closing a valve (Japanese Patent Publication No. 53-38311), a method in which after preliminary stirring, an initiator is charged to start polymerization (Japanese Patent Publication No. 48-29795)
However, in practice, as the viscosity of the polymerization suspension increases after the middle of polymerization, the stirring effect decreases, so the generated air bubbles float to the surface and the hold-up of the suspension increases. In extreme cases, the polymer may enter the conduit or the condenser and polymerize there, forming a lump of scale without being drawn into the suspension system again, making it difficult to operate the condenser normally. Naru et al.
There were problems such as unfavorable quality.
本発明者はかかる問題を解決すべく鋭意研究を
重ねた結果、重合の中期（重合転化率50％）以降
に重合温度を徐々に上昇させながら、コンデンサ
での除熱量を調節することにより発泡を制御しつ
つ重合を行なう方法が極めて有効であることを見
出し、本発明を完成した。以下に本発明の方法を
詳細に説明する。 As a result of extensive research in order to solve this problem, the inventor of the present invention found that foaming can be prevented by adjusting the amount of heat removed by the condenser while gradually increasing the polymerization temperature after the middle stage of polymerization (polymerization conversion rate of 50%). The present invention was completed based on the discovery that a controlled polymerization method is extremely effective. The method of the present invention will be explained in detail below.
近年、塩化ビニル単量体が肝臓障害を生ぜしめ
る危険性があることが明らかにされて以来、重合
体粒子に残存せる未反応単量体を減少させるため
重合終了後の懸濁液を減圧下に攪拌しながら加熱
する方法が一般的に採用されており、この加熱に
要する蒸気コストの製品に占める割合はかなり大
きなものとなつている。 In recent years, it has been revealed that vinyl chloride monomers pose a risk of causing liver damage, and in order to reduce unreacted monomers remaining in the polymer particles, the suspension after polymerization has been processed under reduced pressure. A method of heating the product while stirring is generally employed, and the steam cost required for this heating accounts for a fairly large proportion of the product.
一方、重合の中間以降において重合懸濁液の粘
度が上昇し、発生した気泡が懸濁液から抜けにく
くなり、同時に攪拌効果が低下するので懸濁液の
ホールドアツプが急激に増加し、極端な場合には
懸濁液が導管あるいはコンデンサ内まで達し、そ
こで塊状の重合体となることがあり、コンデンサ
を正常に稼働させることが困難となる他、フイツ
シユアイなど品質上も好ましくない結果を生じる
ことが多い。 On the other hand, after the middle of polymerization, the viscosity of the polymerization suspension increases, making it difficult for the generated air bubbles to come out of the suspension, and at the same time, the stirring effect decreases, resulting in a rapid increase in suspension hold-up and extreme In some cases, the suspension may reach the inside of the conduit or condenser, where it may form a lump of polymer, making it difficult to operate the condenser properly and causing unfavorable quality results such as sticking. many.
重合器のスケールアツプに伴ない、この発泡現
象は益々著しくなるとともに除熱が困難となる
が、本発明によれば重合温度を徐々に上昇させな
がらコンデンサの除熱量を調節することにより重
合中期以降の発泡を制御しつつ重合を行なうこと
により、重合仕込量を増加できる外、重合転化率
を上昇できるため生産性の向上が図れると共に重
合の反応熱を懸濁液の加熱に利用できるので加熱
用蒸気の節減が図れるという副次的効果が得られ
る。尚、コンデンサの除熱量の調節は、コンデン
サへの冷却水の供給量を調節する方法、冷却水の
温度を調節する方法などが一般的であるが特に限
定されない。また、仕込み水に対する単量体の比
率は大きい程生産性の点で好ましいが、重合転化
率25〜30％から重合懸濁液の粘度が急激に上昇し
攪拌が困難となるため、重合による体積収縮分に
相当する量以下の水を重合中に注水することによ
り懸濁液の粘度を下げる方法が好ましい。 As the scale of the polymerization reactor increases, this foaming phenomenon becomes more and more noticeable and heat removal becomes difficult. However, according to the present invention, by adjusting the amount of heat removal from the condenser while gradually increasing the polymerization temperature, the foaming phenomenon can be improved after the middle stage of polymerization. By performing polymerization while controlling foaming, it is possible to increase the amount of polymerization charged, increase the polymerization conversion rate, improve productivity, and use the reaction heat of polymerization to heat the suspension, making it suitable for heating. A secondary effect is that steam can be saved. Note that the amount of heat removed from the condenser is generally adjusted by a method of adjusting the amount of cooling water supplied to the condenser, a method of adjusting the temperature of the cooling water, etc., but is not particularly limited. In addition, the larger the ratio of monomer to charging water is, the better from the viewpoint of productivity, but the viscosity of the polymerization suspension increases rapidly from a polymerization conversion rate of 25 to 30%, making stirring difficult. A preferred method is to lower the viscosity of the suspension by pouring water during polymerization in an amount equal to or less than the amount of shrinkage.
本発明において使用される塩化ビニル、又はこ
れを主体とするビニル系単量体混合物としては、
例えばエチレン，プロピレンなどのオレフイン
類；酢酸ビニル，ステアリン酸ビニルなどのビニ
ルエステル類；アクリル酸メチル，メタクリル酸
メチルなどのアクリル酸エステル類；マレイン酸
又はフマル酸などの酸のエステル類及び無水物；
アクリロニトリルなどのニトリル化合物あるいは
塩化ビニリデンの如きビニリデン化合物等が挙げ
られる。 Vinyl chloride or a vinyl monomer mixture mainly composed of vinyl chloride used in the present invention includes:
For example, olefins such as ethylene and propylene; vinyl esters such as vinyl acetate and vinyl stearate; acrylic acid esters such as methyl acrylate and methyl methacrylate; esters and anhydrides of acids such as maleic acid or fumaric acid;
Examples include nitrile compounds such as acrylonitrile and vinylidene compounds such as vinylidene chloride.
本発明において使用される重合開始剤として
は、塩化ビニル懸濁重合で通常用いられる開始
剤、例えばラウロイルパーオキサイド，３，５，
５―トリメチルヘキサノイルパーオキサイド，ｔ
―ブチルパーオキシピバレート，ジイソプロピル
パーオキシジカーボネート，ジ―２―エチルヘキ
シルパーオキシジカーボネート及びアセチルシク
ロヘキシルスルフオニルパーオキサイドなどのよ
うな有機過酸化物並びにα，α′―アゾビスイソブ
チロニトリル及びα，α′―アゾビス２，４―ジメ
チルバレロニトリルなどの化合物の一種又は二種
以上の混合物が挙げられる。 The polymerization initiator used in the present invention includes initiators commonly used in vinyl chloride suspension polymerization, such as lauroyl peroxide, 3,5,
5-trimethylhexanoyl peroxide, t
- organic peroxides such as butyl peroxypivalate, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and acetylcyclohexylsulfonyl peroxide, and α,α′-azobisisobutyronitrile. and α,α′-azobis2,4-dimethylvaleronitrile, or a mixture of two or more thereof.
本発明において使用される分散剤としては公知
の分散剤でよく、例えば部分ケン化ポリビニルア
ルコール，ポリビニルピロリドン，酢酸ビニル―
無水マレイン酸共重合体，無水マレイン酸―スチ
レン共重合体，メチルセルローズなどが挙げられ
る。 The dispersant used in the present invention may be any known dispersant, such as partially saponified polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate, etc.
Examples include maleic anhydride copolymer, maleic anhydride-styrene copolymer, and methyl cellulose.
本発明における重合温度範囲は通常40〜75℃で
あり、重合中間の重合温度の上昇範囲は通常５〜
20℃であるが特に限定はされない。 The polymerization temperature range in the present invention is usually 40 to 75°C, and the range of increase in polymerization temperature during polymerization is usually 5 to 75°C.
Although the temperature is 20°C, there is no particular limitation.
本発明によれば、コンデンサを付設した重合器
を用いて塩化ビニル系樹脂を懸濁重合する際、導
管及びコンデンサ内部へ懸濁液を侵入させること
なく、重合仕込量を増量することが可能となり、
スケールの生成を防止しフイツシユアイなどの品
質上の問題を生じることなく、重合時間の短縮と
併わせて大巾な生産性向上が可能となり、加熱用
蒸気の節減が可能となるので、本発明は工業的価
値の大きいものである。 According to the present invention, when carrying out suspension polymerization of vinyl chloride resin using a polymerization vessel equipped with a condenser, it is possible to increase the amount of polymerization without allowing the suspension to enter the conduit or the inside of the condenser. ,
The present invention prevents the formation of scale and does not cause quality problems such as stickiness, shortens polymerization time, greatly improves productivity, and saves heating steam. It has great industrial value.
以下、本発明の実施例により具体的に説明す
る。 Hereinafter, the present invention will be specifically explained using examples.
実施例 １
伝熱面積が５m2のコンデンサを付設した内容積
が1.5m3の重合器に純水705Kg，ジ―２―エチルヘ
キシルパーオキシジカーボネート360ｇ，３％部
分ケン化ポリピニルアルコール水溶液13.5を装
入し、攪拌しつつ重合器内を15分間脱気し、600
Kgの塩化ビニルを仕込み58℃まで昇温して重合を
開始させ、重合転化率が５％になつた時点でコン
デンサへ冷却水を通水開始し、徐々に冷却水量を
増加させ30分目以降のコンデンサの除熱量を約
50000kcal／Hrとなるよう調節しつつ重合を継続
し、重合開始後３時間目（重合転化率50％）から
コンデンサへの冷却水供給を停止し、重合温度を
徐々に上昇させて重合を行なつた。Example 1 705 kg of pure water, 360 g of di-2-ethylhexyl peroxydicarbonate, and 13.5 g of a 3% partially saponified polypinyl alcohol aqueous solution were placed in a polymerization vessel with an internal volume of 1.5 m 3 equipped with a condenser with a heat transfer area of 5 m 2 . was charged, the inside of the polymerization vessel was degassed for 15 minutes while stirring, and 600
Kg of vinyl chloride is charged and the temperature is raised to 58℃ to start polymerization. When the polymerization conversion rate reaches 5%, cooling water is started flowing through the condenser, and the amount of cooling water is gradually increased from 30 minutes onwards. The amount of heat removed from the capacitor is approximately
Polymerization was continued while adjusting the temperature to 50,000 kcal/Hr, and from 3 hours after the start of polymerization (polymerization conversion rate 50%), the cooling water supply to the condenser was stopped, and the polymerization temperature was gradually raised to carry out polymerization. Ta.
４時間目に重合温度が75℃に達したので未反応
単量体を回収し、重合を停止させた。尚、攪拌中
は300c.c.／分の水を連続的に追加した。重合終了
後、点検した所、コンデンサ及び導管でのスケー
ルの生成はみられなかつた。又、この時の重合転
化率は83％であつた。 After 4 hours, the polymerization temperature reached 75°C, so unreacted monomers were collected and the polymerization was stopped. During stirring, water was continuously added at a rate of 300 c.c./min. After completion of polymerization, no scale formation was observed in the condenser or conduit when inspected. Moreover, the polymerization conversion rate at this time was 83%.
実施例 ２
伝熱面積50m2のコンデンサを付設した内容積10
m3の重合器に純水4300Kg，ジ―２―エチルヘキシ
ルパーオキシジカーボネート2.2Kg，３％部分ケ
ン化ポリビニルアルコール水溶液80を装入し、
攪拌しつつ重合器内を15分間脱気し、3600Kgの塩
化ビニルを仕込み58℃まで昇温して重合を開始さ
せ、重合転化率が３％になつた時点でコンデンサ
へ通水開始し、徐々に冷却水量を増加させ30分目
以降のコンデンサの除熱量を約200000kcal／Hr
となるよう調節しつつ重合を継続させ、重合開始
後３時間目（重合転化率50％）からコンデンサへ
の冷却水量を徐々に減少させつつ重合温度を徐々
に上昇させて重合を行つた。Example 2 Internal volume 10 with a condenser with a heat transfer area of 50 m 2
A 3 m3 polymerization vessel was charged with 4300 kg of pure water, 2.2 kg of di-2-ethylhexyl peroxydicarbonate, and 80 kg of a 3% partially saponified polyvinyl alcohol aqueous solution.
The inside of the polymerization vessel was degassed for 15 minutes while stirring, and 3,600 kg of vinyl chloride was charged and the temperature was raised to 58°C to start polymerization. When the polymerization conversion rate reached 3%, water flow to the condenser was started and gradually The amount of heat removed from the condenser after 30 minutes was increased to approximately 200,000kcal/Hr by increasing the amount of cooling water.
The polymerization was continued while adjusting the temperature to be as follows, and from 3 hours after the start of the polymerization (polymerization conversion rate 50%), the amount of cooling water to the condenser was gradually decreased and the polymerization temperature was gradually raised.
４時間目に重合温度が73℃まで達したので未反
応単量体を回収し重合を停止させた。尚、攪拌中
は２／分の水を連続的に追加した。この方法で
10バツチの重合を繰返した後、点検した所コンデ
ンサ及び導管でのスケールの生成はみられなかつ
た。又、この時の重合転化率は83％であつた。 After 4 hours, the polymerization temperature reached 73°C, so the unreacted monomers were collected and the polymerization was stopped. During stirring, water was continuously added at a rate of 2/min. using this method
After repeating 10 batches of polymerization, no scale formation was observed in the capacitor or conduit when inspected. Moreover, the polymerization conversion rate at this time was 83%.
実施例 ３
実施例１と同じコンデンサを付設した重合器に
純水705Kg，ジ―２―エチルヘキシルパーオキシ
ジカーボネート220ｇ，３％部分ケン化ポリビニ
ルアルコール水溶液13.5を装入し、攪拌しつつ
重合器内を15分間脱気し、600Kgの塩化ビニルを
仕込み52℃まで昇温し重合を開始させ、重合転化
率８％になつた時点でコンデンサへ冷却水を通水
開始し、除熱量を約30000kcal／Hrとなるよう調
節し、重合開始６時間目（重合転化率50％）から
コンデンサへの冷却水供給を停止し、重合温度を
徐々に上昇させて8.5時間目に重合温度が68℃に
達したので未反応単量体を回収し重合を停止させ
た。尚、攪拌中は150c.c.／分の水を連続的に追加
した。重合終了後、点検した所コンデンサ及び導
管へのスケールの生成はみられず重合転化率は85
％であつた。Example 3 A polymerization vessel equipped with the same condenser as in Example 1 was charged with 705 kg of pure water, 220 g of di-2-ethylhexyl peroxydicarbonate, and 13.5 kg of a 3% partially saponified polyvinyl alcohol aqueous solution, and the mixture was poured into the polymerization vessel while stirring. was degassed for 15 minutes, then 600Kg of vinyl chloride was charged and the temperature was raised to 52℃ to start polymerization. When the polymerization conversion rate reached 8%, cooling water was started to flow through the condenser, and the amount of heat removed was approximately 30,000kcal/ The cooling water supply to the condenser was stopped 6 hours after the start of polymerization (polymerization conversion rate 50%), and the polymerization temperature was gradually increased until it reached 68°C at 8.5 hours. Therefore, unreacted monomers were collected and polymerization was stopped. During stirring, 150 c.c./min of water was continuously added. After polymerization was completed, no scale was observed on the condenser or conduit, and the polymerization conversion rate was 85.
It was %.
比較例 １
実施例１と同様の方法で重合を開始し、重合転
化率が５％になつた時点でコンデンサへ冷却水を
通水開始し徐々に冷却水量を増加させ、30分目以
降のコンデンサの除熱量を約50000kcal／Hrとな
るよう調節しつつ58℃で重合を継続し、４時間目
に未反応単量体を回収し重合を停止させた。重合
終了後、点検した所コンデンサ及び導管に溢流し
た樹脂が詰つていた。この時の重合転化率は77％
であつた。Comparative Example 1 Polymerization was started in the same manner as in Example 1, and when the polymerization conversion rate reached 5%, cooling water was started flowing through the condenser, and the amount of cooling water was gradually increased. Polymerization was continued at 58° C. while adjusting the amount of heat removed to be about 50,000 kcal/Hr, and at 4 hours, unreacted monomers were collected and polymerization was stopped. After polymerization was completed, an inspection revealed that the condenser and conduit were clogged with overflowing resin. The polymerization conversion rate at this time was 77%
It was hot.
比較例 ２
実施例３と同様の方法で重合を開始し、重合転
化率が８％になつた時点からコンデンサへの冷却
水の通水を開始し、徐々に冷却水量を増加させ、
除熱量を約30000kcal／Hrとなるよう調節しつつ
52℃で重合を行ない、重合開始後8.5時間目に未
反応単量体を回収し重合を停止させた。尚、攪拌
中は150c.c.／分の水を連続的に追加した。重合終
了後、点検した所コンデンサ及び導管に溢流した
樹脂が詰つていた。又、この時の重合転化率は78
％であつた。Comparative Example 2 Polymerization was started in the same manner as in Example 3, and when the polymerization conversion rate reached 8%, the flow of cooling water to the condenser was started, and the amount of cooling water was gradually increased.
While adjusting the heat removal amount to approximately 30000kcal/Hr.
Polymerization was carried out at 52°C, and unreacted monomers were collected 8.5 hours after the start of polymerization to stop the polymerization. During stirring, 150 c.c./min of water was continuously added. After polymerization was completed, an inspection revealed that the condenser and conduit were clogged with overflowing resin. Also, the polymerization conversion rate at this time was 78
It was %.
Claims (1)
設した重合機を用いて塩化ビニル又はこれを主体
とするビニル系単量体混合物を懸濁重合するに際
し、重合転化率50％以降において重合温度を徐々
に上昇させながらコンデンサでの除熱量を調節す
ることにより発泡を抑制することを特徴とする塩
化ビニル系樹脂の製造方法。1. When performing suspension polymerization of vinyl chloride or a vinyl monomer mixture mainly composed of vinyl chloride using a polymerization machine equipped with a reflux condenser (hereinafter referred to as a condenser), the polymerization temperature is gradually increased after the polymerization conversion rate is 50%. A method for producing a vinyl chloride resin, characterized in that foaming is suppressed by adjusting the amount of heat removed in a condenser while increasing the temperature.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9727481A JPS57212213A (en) | 1981-06-22 | 1981-06-22 | Preparation of vinyl chloride resin |
| GB08217773A GB2101614A (en) | 1981-06-22 | 1982-06-18 | Production of vinyl chloride resin |
| KR8202721A KR860001114B1 (en) | 1981-06-22 | 1982-06-18 | A method for production of vinyl chloride resin |
| US06/390,845 US4455413A (en) | 1981-06-22 | 1982-06-22 | Method for suppressing bubbling in polymerization of vinyl chloride resin |
| DE19823223262 DE3223262A1 (en) | 1981-06-22 | 1982-06-22 | METHOD FOR PRODUCING VINYL CHORIDE RESIN |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9727481A JPS57212213A (en) | 1981-06-22 | 1981-06-22 | Preparation of vinyl chloride resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57212213A JPS57212213A (en) | 1982-12-27 |
| JPH0212963B2 true JPH0212963B2 (en) | 1990-04-03 |
Family
ID=14187939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9727481A Granted JPS57212213A (en) | 1981-06-22 | 1981-06-22 | Preparation of vinyl chloride resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57212213A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0696618B2 (en) * | 1987-08-03 | 1994-11-30 | チッソ株式会社 | Method for producing vinyl chloride polymer |
-
1981
- 1981-06-22 JP JP9727481A patent/JPS57212213A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57212213A (en) | 1982-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH08259609A (en) | Dispersion stabilizer for suspension polymerization of vinylic compound | |
| KR0160332B1 (en) | Processing method of high porous vinyl chloride resin | |
| JPH02180908A (en) | Production of vinyl chloride polymer | |
| JPH0118082B2 (en) | ||
| US4455413A (en) | Method for suppressing bubbling in polymerization of vinyl chloride resin | |
| JPH0212963B2 (en) | ||
| JP2807526B2 (en) | Method for producing vinyl chloride polymer | |
| JPH02305804A (en) | Production of vinyl chloride polymer | |
| JP4993268B2 (en) | Method for producing vinyl chloride polymer | |
| JP7408405B2 (en) | Method for producing vinyl chloride polymer | |
| JP3440646B2 (en) | Method for producing vinyl chloride polymer | |
| JPS6043846B2 (en) | Method for producing vinyl chloride resin using a reflux condenser | |
| JP2878874B2 (en) | Method for producing vinyl chloride polymer | |
| JP3369339B2 (en) | Method for producing vinyl chloride polymer | |
| JPH0150243B2 (en) | ||
| JPS62246908A (en) | Production of vinyl chloride polymer | |
| JPS6047007A (en) | Suspension polymerization of venyl chloride monomer | |
| JPS61195101A (en) | Polymerization of vinyl chloride monomer | |
| JPH0987303A (en) | Method for polymerizing vinyl chloride | |
| JPH04110301A (en) | Production of vinyl chloride polymer | |
| JP3197151B2 (en) | Method for producing vinyl chloride polymer | |
| JPH066607B2 (en) | Method for producing vinyl chloride resin | |
| JPH0649106A (en) | Production of vinyl chloride polymer | |
| JPS61115908A (en) | Production of vinyl chloride resin | |
| JPH055008A (en) | Method for polymerizing vinyl chloride-based monomer |