JPH0696618B2 - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymerInfo
- Publication number
- JPH0696618B2 JPH0696618B2 JP62194092A JP19409287A JPH0696618B2 JP H0696618 B2 JPH0696618 B2 JP H0696618B2 JP 62194092 A JP62194092 A JP 62194092A JP 19409287 A JP19409287 A JP 19409287A JP H0696618 B2 JPH0696618 B2 JP H0696618B2
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- Prior art keywords
- vinyl chloride
- temperature
- polymerization
- chloride monomer
- monomer
- Prior art date
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は塩化ビニル重合体の製造方法に関し物性を損う
ことなく収率よく該重合体を製造する方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a vinyl chloride polymer, and to a method for producing the polymer in good yield without impairing the physical properties.
従来塩化ビニルの重合は重合率が85%程度になると反応
容器空間部のモノマーガスが少なくなり圧力が下り、こ
れ以上は反応はほとんど進まないため圧力が1〜3kg/cm
2程度下がつた時点で反応終了とみなし次の工程へ進ん
でいた。次の工程とは、未反応の塩化ビニルモノマーを
重合器から減圧除去し、次いでスラリー(重合体水分散
液)を脱モノマー装置等で処理し回収することである。
この回収された塩化ビニルモノマーガスは水と分離され
液化精製され再利用されている。In the conventional polymerization of vinyl chloride, when the polymerization rate reaches about 85%, the monomer gas in the reaction vessel space decreases and the pressure falls, and the reaction hardly progresses beyond this, so the pressure is 1 to 3 kg / cm
The reaction was considered to be complete when the temperature dropped by about 2 and proceeded to the next step. The next step is to remove unreacted vinyl chloride monomer from the polymerization vessel under reduced pressure, and then treat the slurry (polymer aqueous dispersion) with a demonomerization device or the like to collect.
The recovered vinyl chloride monomer gas is separated from water, liquefied and purified, and reused.
即ち、T/m3Month(T:塩化ビニル重合体でき高トン数、m
3:重合器容量、Month:1か月)を大きくするために、重
合器内圧が1〜3kg/cm2下がつた後長時間だらだら運転
して若干の収率を上げる方法よりも短時間で切り上げ1
サイクルの時間を短かくする方法が採用されていた。That is, T / m 3 Month (T: vinyl chloride polymer can be produced with high tonnage, m
3 : To increase the capacity of the polymerization vessel, Month: 1 month), it takes less time than the method in which the internal pressure of the polymerization vessel is lowered by 1 to 3 kg / cm 2 and then the operation is carried out for a long time to slightly increase the yield. Round up 1
The method of shortening the cycle time was adopted.
本発明は得られる重合体の品質を損わずかつ短時間で収
率を上げる塩化ビニル重合体の製造方法を提供すること
を目的とする。An object of the present invention is to provide a method for producing a vinyl chloride polymer, which impairs the quality of the obtained polymer and increases the yield in a short time.
本発明は、塩化ビニル単量体又は塩化ビニル単量体を含
む混合物を水性媒体中で懸濁重合させるにあたり、懸濁
剤としてけん化度70〜78%の部分けん化ポリビニルアル
コールを用い、該塩化ビニル単量体又は塩化ビニル単量
体を含むビニル系単量体混合物の重合が進み、重合器内
圧が下がり始めた時から40分以内にスラリーの温度を重
合器内圧が下がり始める直前のスラリーの温度より5〜
10℃上げる操作を行ない、所定の温度に上つた時点より
モノマーを回収する塩化ビニル重合体の製造方法であ
る。The present invention uses a partially saponified polyvinyl alcohol having a saponification degree of 70 to 78% as a suspending agent in suspension polymerization of a vinyl chloride monomer or a mixture containing a vinyl chloride monomer in an aqueous medium. Polymerization of vinyl-based monomer mixture containing monomer or vinyl chloride monomer proceeds, and the temperature of the slurry is changed within 40 minutes from the time when the internal pressure of the polymerization reactor begins to decrease. More than 5
This is a method for producing a vinyl chloride polymer in which the monomer is recovered when the temperature rises to a predetermined temperature by raising the temperature by 10 ° C.
本発明に使用される懸濁剤はけん化度70〜78%が適当で
ある。けん化度がこれより高いと可塑剤吸収性を悪くす
るからである。これはけん化度が高い懸濁剤を使用した
場合生成する塩化ビニル重合体のスキン層が厚くなるた
め、重合が進むにつれ内部空隙率が小さくなるためと考
えられる。一方けん化度が70%より低い懸濁剤は、通常
重合が不安定になるため単独で使用される事はないから
である。The suspending agent used in the present invention preferably has a saponification degree of 70 to 78%. This is because if the saponification degree is higher than this, the plasticizer absorbability is deteriorated. It is considered that this is because the skin layer of the vinyl chloride polymer produced when a suspending agent having a high degree of saponification is used becomes thicker and the internal porosity becomes smaller as the polymerization proceeds. On the other hand, a suspending agent having a saponification degree of less than 70% is not used alone because the polymerization is usually unstable.
昇温時期は落圧開始時から40分以内とするのが適当であ
る。落圧開始前に昇温を開始するとまだ反応がさかんな
段階なので重合器内圧が上がつてしまい安全上好ましく
ない。又、当然重合度にも影響が与えるため、安定した
重合度調整が困難になる。一方落圧開始後40分より後に
昇温を開始した場合、所定の温度に上げるための時間が
加わるのみならず末期発熱を利用して効率的にスラリー
の温度を上げる操作ができず、温度上昇に時間を要する
ため不利となる。It is appropriate to raise the temperature within 40 minutes from the start of depressurization. If the temperature rise is started before the pressure drop, the reaction is still at a stage where the pressure inside the polymerization vessel rises, which is not preferable for safety. Further, since the degree of polymerization is also affected, it becomes difficult to adjust the degree of polymerization stably. On the other hand, if the temperature rise is started more than 40 minutes after the pressure drop starts, not only the time for raising the temperature to the predetermined temperature will be added but also the temperature of the slurry cannot be increased efficiently by utilizing the end-stage heat generation and the temperature rise. It is disadvantageous because it takes time.
本発明では昇温の間に塩化ビニルモノマーは系外へ出さ
ない。この間系外へ出すと液体の状態にある塩化ビニル
モノマーが気体の状態に変化するため重合反応が事実上
起こらなくなり、収率の向上が図れないためである。In the present invention, the vinyl chloride monomer does not come out of the system during the temperature rise. This is because the vinyl chloride monomer in a liquid state is changed to a gas state when it is taken out of the system during this period, so that the polymerization reaction practically does not occur and the yield cannot be improved.
昇温温度は落圧開始直前のスラリーの温度より5〜10℃
高めとする。5℃より低いと重合速度が遅く短時間での
収率上昇につながらないからである。一方温度が上れば
上る程収率は良くなるが10℃を越えると生成する塩化ビ
ニル重合体の熱安定性を損ない品質が低下して好ましく
ない。又、所定の温度に昇温できればそれより温度が高
くならないよう直ちに冷却操作をするのが望ましい。も
しこの操作をしないとスラリーの温度が高くなり過ぎて
上記と同じ理由で生成する塩化ビニル重合体の熱安定性
を損うおそれがあるからである。The temperature rise is 5 to 10 ° C above the temperature of the slurry just before the start of pressure reduction.
Higher. This is because if it is lower than 5 ° C, the polymerization rate is slow and the yield is not increased in a short time. On the other hand, the higher the temperature, the better the yield, but if the temperature exceeds 10 ° C., the vinyl chloride polymer produced is unfavorably deteriorated in thermal stability and its quality is deteriorated. Further, if it is possible to raise the temperature to a predetermined temperature, it is desirable to immediately perform a cooling operation so that the temperature does not become higher than that. If this operation is not carried out, the temperature of the slurry becomes too high and the thermal stability of the vinyl chloride polymer produced for the same reason as above may be impaired.
本発明における昇温の際の温度コントロールは通常重合
器ジヤケツトの流体(通常は水)の温度の上下で行な
う。In the present invention, the temperature control at the time of raising the temperature is usually performed above and below the temperature of the fluid (usually water) in the polymerization vessel jacket.
重合器よりスラリーを抜き出す場合、塩化ビニル重合体
中の塩化ビニルモノマーの残存量を少なくするため、通
常5kg/cm2G程度以下になつてから前記抜き出しが行なわ
れる。ところで驚くべき事に落圧開始時から40分以内に
昇温させその間塩化ビニルモノマーを系外に回収しない
場合、所定の温度に昇温させる迄に時間がそれだけかか
るにもかかわらず、昇温させずに塩化ビニルモノマーを
回収させた場合と比較して5kg/cm2G以下の圧に重合器内
圧が下がるのに要する時間はほとんど同じである。When the slurry is withdrawn from the polymerization vessel, in order to reduce the amount of vinyl chloride monomer remaining in the vinyl chloride polymer, the withdrawal is usually performed after the amount becomes about 5 kg / cm 2 G or less. By the way, surprisingly, if the temperature is raised within 40 minutes from the start of depressurization and the vinyl chloride monomer is not recovered outside the system during that time, the temperature is raised even though it takes time to reach the prescribed temperature. The time required for the internal pressure of the polymerization vessel to fall to a pressure of 5 kg / cm 2 G or less is almost the same as that when the vinyl chloride monomer is recovered without it.
本発明において、重合時、他の分散剤を併用することが
できる。併用できる分散剤としては例えばけん化度が70
〜78%の範囲以外のPVA、メチルセルローズ、ヒドロキ
シプロピルセルローズのごときセルローズ誘導体、ポリ
ビニルピロリドン、無水マレイン酸−酢酸ビニル共重合
体のごとき合成高分子物質、ソルビタンモノラウレート
のごときノニオン系界面活性剤等が挙げられ、通常懸濁
重合に用いられるものならばいずれでもよい。In the present invention, another dispersant may be used together during the polymerization. Examples of the dispersant that can be used in combination include a saponification degree of 70.
PVA out of the range of up to 78%, cellulose derivatives such as methylcellulose and hydroxypropylcellulose, synthetic polymer substances such as polyvinylpyrrolidone, maleic anhydride-vinyl acetate copolymer, and nonionic surfactants such as sorbitan monolaurate And the like, and any of those usually used for suspension polymerization may be used.
本発明の方法は前記特定の分散剤を使用することと前記
特定条件で重合させること以外は通常の懸濁重合方法と
何ら変るところはない。The method of the present invention is no different from the usual suspension polymerization method except that the specific dispersant is used and the polymerization is performed under the specific conditions.
従つて開始剤としては過酸化ラウロイル、過酸化ベンゾ
イル、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、ジシクロヘキシルパーオ
キシジカーボネート、ジ(3−メトキシブチル)パーオ
キシジカーボネート、アセチルシクロヘキシルスルホニ
ルパーオキサイド等のごとき有機過酸化物あるいはα,
α′−アゾビスイソブチロニトリル、α,α′−アゾビ
ス−2,4−ジメチルバレロニトリル、α,α′−アゾビ
ス−4−メトキシ−2,4−ジメチルバレロニトリルのご
ときアゾ化合物の一種類又は二種類以上の混合物を用い
ることができる。Therefore, as the initiator, lauroyl peroxide, benzoyl peroxide, t-butyl peroxypivalate, diisopropyl peroxy dicarbonate, dicyclohexyl peroxy dicarbonate, di (3-methoxybutyl) peroxy dicarbonate, acetylcyclohexyl sulfonyl peroxide are used. Organic peroxides such as oxides or α,
One type of azo compound such as α'-azobisisobutyronitrile, α, α'-azobis-2,4-dimethylvaleronitrile, α, α'-azobis-4-methoxy-2,4-dimethylvaleronitrile Alternatively, a mixture of two or more kinds can be used.
又分散剤、開始剤以外の公知の添加剤を重合系に添加す
ることは本発明の範囲を逸脱するものではない。Further, addition of known additives other than the dispersant and the initiator to the polymerization system does not depart from the scope of the present invention.
本発明の方法は主として塩化ビニル単量体の重合法に適
用されるが、これはまた塩化ビニル単量体を50%以上含
む塩化ビニル単量体と共重合しうるビニル系単量体との
共重合にも適用できる。そのようなビニル系単量体とし
ては例えば酢酸ビニルのごときアルキルビニルエステ
ル、セチルビニルエーテルのごときアルキルビニルエー
テル、エチレン又はプロピレンのごときα−モノオレフ
イン系単量体、アクリル酸エチルのごときアクリル酸ア
ルキルエステル又はメタアクリル酸メチルのごときメタ
アクリル酸アルキルエステルなどが挙げられる。更に本
発明方法はエチレン−酢酸ビニル共重合体又はエチレン
・プロピレン共重合体等のオレフイン系重合体への塩化
ビニル単量体のグラフト重合にも適用することができ
る。The method of the present invention is mainly applied to a method for polymerizing vinyl chloride monomer, which is also applicable to vinyl chloride monomer containing 50% or more of vinyl chloride monomer and copolymerizable vinyl monomer. It can also be applied to copolymerization. Examples of such vinyl monomers include alkyl vinyl esters such as vinyl acetate, alkyl vinyl ethers such as cetyl vinyl ether, α-monoolefin monomers such as ethylene or propylene, acrylic acid alkyl esters such as ethyl acrylate, or Examples thereof include methacrylic acid alkyl esters such as methyl methacrylic acid. Furthermore, the method of the present invention can also be applied to the graft polymerization of vinyl chloride monomer onto an olefin polymer such as an ethylene-vinyl acetate copolymer or an ethylene / propylene copolymer.
本発明の塩化ビニル単量体等の重合反応は通常35〜70℃
の温度で撹拌下に行う。The polymerization reaction of the vinyl chloride monomer of the present invention is usually 35 to 70 ° C.
With stirring at the temperature of.
本発明方法によれば、得られる重合体の品質を損なわ
ず、短時間で収率を向上させることができる。According to the method of the present invention, the yield can be improved in a short time without impairing the quality of the obtained polymer.
以下に実施例を示すが、本発明はこれに限定されるもの
ではない。以下の記載において「部」とあるのは特にこ
とわらない限り重量部を表わす。Examples will be shown below, but the present invention is not limited thereto. In the following description, “part” means part by weight unless otherwise specified.
尚、実施例及び比較例中で説明している塩化ビニル重合
体の品質は夫々次の測定法によつて行つたものである。The qualities of the vinyl chloride polymers described in the examples and comparative examples were measured by the following measuring methods.
(イ)可塑剤の吸収性 プラストグラフに接続させたプラネタリーミキサーを用
い、80℃に保つた容器内に塩化ビニル重合体400g及びジ
オクチルフタレート200gを投入し撹拌しながら各時間毎
の混練トルクを記録し混練トルクが低下した点における
混練時間で表示する。トルクの低下する時間が短い程可
塑剤吸収性が早い事を示す。(A) Absorbency of plasticizer Using a planetary mixer connected to a plastograph, add 400 g of vinyl chloride polymer and 200 g of dioctyl phthalate into a container kept at 80 ° C and stir the kneading torque every hour while stirring. The kneading time is recorded and displayed at the point where the kneading torque has decreased. The shorter the time when the torque decreases, the faster the plasticizer absorbability is.
(ロ)熱安定性 軟質用処方 塩化ビニル重合体100部、ジオクチルフタレート50部、
エポキシ系安定剤2部、ステアリン酸カルシウム0.5部
及びステアリン酸亜鉛1部を配合し、150℃のロールで1
0分間混練し成型して得られたシート(膜厚0.1mm、横30
mm×縦45mm)を170℃の熱老化試験機で加熱し、黒化す
るまでの時間で表わす。時間が長い程熱安定性が良い事
を示す。(B) Thermal stability Soft formulation 100 parts vinyl chloride polymer, 50 parts dioctyl phthalate,
Mix 2 parts of epoxy stabilizer, 0.5 part of calcium stearate and 1 part of zinc stearate and roll 1 at 150 ℃.
Sheet obtained by kneading and molding for 0 minutes (film thickness 0.1 mm, width 30
mm x 45 mm) is expressed by the time until it is blackened by heating with a heat aging tester at 170 ° C. The longer the time, the better the thermal stability.
硬質用処方 塩化ビニル重合体100部、ブチル錫メルカプト系安定剤
4部及びステアリン酸カルシウム0.5部を配合し、150℃
のロールで10分間混練し成型して得られたシート(膜厚
0.1mm、横30mm×縦45mm)を190℃の熱老化試験機で加熱
し黒化するまでの時間で表わす。時間が長い程熱安定性
が良い事を示す。Hardener formulation 100 parts of vinyl chloride polymer, 4 parts of butyltin mercapto stabilizer and 0.5 parts of calcium stearate are mixed, and the temperature is 150 ° C.
Sheet (film thickness)
0.1mm, width 30mm x length 45mm) is the time required to heat and blacken with a heat aging tester at 190 ℃. The longer the time, the better the thermal stability.
実施例1〜3、比較例1〜3 内容積200のステンレス製重合器に純水100kg、けん化
度70%のポリビニルアルコール26g、ジ(3−メトキシ
ブチル)パーオキシジカーボネート12g、アセチルシク
ロヘキシルスルホニルパーオキサイド10g、塩化ビニル
モノマー50kgを仕込み撹拌しながら重合温度52℃で重合
した。重合が進み落圧開始後第1表に示す時間後昇温を
開始し第1表に示す設定温度に達した後(その間重合器
内の残存塩化ビニルモノマーは回収しないで)、残存塩
化ビニルモノマーを回収し5kg/cm2Gに達した時点で重合
器よりスラリーを抜き出し脱水し乾燥した。Examples 1 to 3 and Comparative Examples 1 to 3 In a stainless steel polymerization vessel having an internal volume of 200, 100 kg of pure water, 26 g of polyvinyl alcohol having a saponification degree of 70%, 12 g of di (3-methoxybutyl) peroxydicarbonate, acetylcyclohexylsulfonylperoxide 10 g of oxide and 50 kg of vinyl chloride monomer were charged and polymerized at a polymerization temperature of 52 ° C. with stirring. After the polymerization proceeded and the pressure drop started, the temperature was raised after the time shown in Table 1 and the temperature reached the set temperature shown in Table 1 (while the vinyl chloride monomer remaining in the polymerization vessel was not recovered), the residual vinyl chloride monomer Was recovered, and when it reached 5 kg / cm 2 G, the slurry was taken out from the polymerization vessel, dehydrated and dried.
落圧開始後残存塩化ビニルモノマー回収開始迄の時間及
びスラリー抜き出し迄の時間を第1表に示した。又乾燥
塩化ビニル重合体の熱安定性及び可塑剤吸収性をこの表
に示した。Table 1 shows the time from the start of depressurization to the start of recovery of residual vinyl chloride monomer and the time until slurry withdrawal. The thermal stability and plasticizer absorbency of the dry vinyl chloride polymer are also shown in this table.
この表から昇温開始時期が遅すぎると落圧開始後よりス
ラリー抜き出し迄に時間がかかりすぎる事がわかる。又
昇温温度が高すぎれば熱安定性、可塑剤吸収性が悪くな
り、昇温温度が低すぎれば収率が上がらない事がわか
る。 From this table, it can be seen that if the temperature rising start time is too late, it takes too much time to extract the slurry after the pressure drop starts. Further, it is understood that if the temperature rise temperature is too high, the thermal stability and plasticizer absorbency deteriorate, and if the temperature rise temperature is too low, the yield does not increase.
比較例4〜7 実施例1と添加剤等の仕込み及び重合方法は全く同じで
あるが落圧後の操作を第2表の如くにして重合器内圧が
5kg/cm2Gに達した時点で重合器よりスラリーを抜き出し
脱水し乾燥した。Comparative Examples 4 to 7 The procedures for charging additives and the like and for the polymerization method were exactly the same as in Example 1, but the procedure after the pressure drop was as shown in Table 2, and the internal pressure of the polymerization vessel was
When the amount reached 5 kg / cm 2 G, the slurry was taken out from the polymerization vessel, dehydrated and dried.
スラリー抜き出し迄の時間、乾燥塩化ビニル重合体の熱
安定性及び可塑剤吸収性を第2表に示した。Table 2 shows the thermal stability and plasticizer absorbency of the dried vinyl chloride polymer during the time until the slurry was discharged.
この表より昇温してもその間塩化ビニルモノマーを回収
した場合は全く収率があがらない事がわかる。又この時
は昇温設定温度が高くても品質に悪影響を及ぼさない事
もわかる。昇温しない場合は当然の事ながら塩化ビニル
モノマーを回収してもしなくても収率が上がらない事が
わかる。 From this table, it can be seen that even if the temperature is raised, the yield does not increase at all when the vinyl chloride monomer is recovered during that time. Also, at this time, it can be seen that the quality is not adversely affected even if the temperature rise setting temperature is high. It will be understood that the yield does not increase without recovering the vinyl chloride monomer when the temperature is not raised.
比較例8〜10 使用した分散剤をけん化度80%のポリビニルアルコール
とし、使用量を40gとした他は、実施例1〜3と全く同
じ操作を行なつた。その結果を第3表に示す。Comparative Examples 8 to 10 The same operations as in Examples 1 to 3 were performed except that the dispersant used was polyvinyl alcohol having a saponification degree of 80% and the amount used was 40 g. The results are shown in Table 3.
比較例11 昇温開始後塩化ビニルモノマーを回収する以外は比較例
8と全く同じ操作をした。その結果を第3表に示す。Comparative Example 11 The same operation as in Comparative Example 8 was carried out except that the vinyl chloride monomer was recovered after the start of heating. The results are shown in Table 3.
この表よりけん化度80%のポリビニルアルコールを使用
した場合、可塑剤吸収性が悪くなる事がわかる。 From this table, it can be seen that when polyvinyl alcohol having a saponification degree of 80% is used, the plasticizer absorbability is deteriorated.
実施例4〜6、比較例12〜13 内容積200のステンレス製重合器に純水100kg、けん化
度70%のポリビニルアルコール25g、ジ(3−メトキシ
ブチル)パーオキシジカーボネート11g、アセチルシク
ロヘキシルスルホニルパーオキサイド7g、塩化ビニルモ
ノマー50kgを仕込み撹拌しながら重合温度57℃で重合し
た。重合が進み落圧開始後第4表に示す時間後昇温を開
始し第3表に示す温度に達した後(その間重合器内の残
存塩化ビニルモノマーは回収しないで)残存塩化ビニル
モノマーを回収し5kg/cm2Gに達した時点で重合器よりス
ラリーを抜き出し脱水し乾燥した。Examples 4 to 6 and Comparative Examples 12 to 13 In a stainless steel polymerization vessel having an inner volume of 200, 100 kg of pure water, 25 g of polyvinyl alcohol having a saponification degree of 70%, 11 g of di (3-methoxybutyl) peroxydicarbonate, and acetylcyclohexylsulfonylperoxide were used. 7 g of oxide and 50 kg of vinyl chloride monomer were charged and polymerization was carried out at a polymerization temperature of 57 ° C. with stirring. After the polymerization proceeded and the pressure drop started, the temperature was raised after the time shown in Table 4 and the temperature reached shown in Table 3 (while the vinyl chloride monomer in the polymerization vessel was not recovered during that period), the residual vinyl chloride monomer was recovered. When the amount reached 5 kg / cm 2 G, the slurry was taken out from the polymerization vessel, dehydrated and dried.
落圧開始後残存塩化ビニルモノマー回収開始迄の時間及
びスラリー抜き出し迄の時間を第4表に示した。又乾燥
塩化ビニル重合体の熱安定性及び可塑剤吸収性をこの表
に示した。Table 4 shows the time from the start of depressurization to the start of recovery of residual vinyl chloride monomer and the time to withdraw slurry. The thermal stability and plasticizer absorbency of the dry vinyl chloride polymer are also shown in this table.
比較例14 昇温時塩化ビニルモノマーを回収した他は実施例4と同
じ操作を行なつた。その結果を第4表に示す。Comparative Example 14 The same operation as in Example 4 was performed except that the vinyl chloride monomer was recovered at the time of heating. The results are shown in Table 4.
この表より、実施例4〜6は、実施例1〜3と重合温度
が異なるがこれらのケースでも同様な結果が得られるこ
とがわかる。 From this table, it is understood that Examples 4 to 6 are different from Examples 1 to 3 in polymerization temperature, but similar results can be obtained in these cases.
実施例7〜8、比較例15〜16 内容積200のステンレス製重合器に、純水100kg、けん
化度70%のポリビニルアルコール36g、α,α′−アゾ
ビス−2,4−ジメチルバレロニトリル21g、塩化ビニル単
量体40kg及び酢酸ビニル単量体10kgを仕込み撹拌しなが
ら63℃で重合した。重合が進み落圧開始後第5表に示す
時間後昇温を開始し第5表に示す温度に達した後(その
間重合器内の残存塩化ビニルモノマーは回収しないで)
残存塩化ビニルモノマーを回収し、5kg/cm2Gに達した時
点で重合器よりスラリーを抜き出し脱水し乾燥した。Examples 7 to 8 and Comparative Examples 15 to 16 In a stainless steel polymerization vessel having an internal volume of 200, 100 kg of pure water, 36 g of polyvinyl alcohol having a saponification degree of 70%, α, α′-azobis-2,4-dimethylvaleronitrile 21 g, 40 kg of vinyl chloride monomer and 10 kg of vinyl acetate monomer were charged and polymerized at 63 ° C. with stirring. After the polymerization proceeded and the pressure drop started, the temperature started to rise after the time shown in Table 5 and reached the temperature shown in Table 5 (while the residual vinyl chloride monomer in the polymerization vessel was not recovered).
The residual vinyl chloride monomer was recovered, and when it reached 5 kg / cm 2 G, the slurry was taken out from the polymerization vessel, dehydrated and dried.
落圧開始後残存塩化ビニルモノマー回収開始迄の時間及
びスラリー抜き出し迄の時間を第5表に示した。又乾燥
塩化ビニル樹脂の熱安定性(硬質)を第5表に示した。
硬質用途の場合、可塑剤を使用しないので可塑剤吸収性
のテストはしなかつた。Table 5 shows the time from the start of depressurization to the start of recovery of residual vinyl chloride monomer and the time until slurry withdrawal. The thermal stability (hardness) of the dry vinyl chloride resin is shown in Table 5.
For rigid applications, no plasticizer was used, so no test for plasticizer absorption was done.
この表より塩化ビニル・酢酸ビニル共重合体の場合で
も、落圧開始後の昇温温度が高すぎれば熱安定性が悪く
なり、昇温温度が低すぎれば収率が上がらないことがわ
かる。 From this table, it can be seen that even in the case of a vinyl chloride / vinyl acetate copolymer, if the temperature rising temperature after the start of the pressure drop is too high, the thermal stability deteriorates, and if the temperature rising temperature is too low, the yield does not increase.
Claims (1)
含むビニル系単量体混合物を水性媒体中で懸濁重合させ
るにあたり懸濁剤としてけん化度70〜78%の部分けん化
ポリビニルアルコールを用い、該塩化ビニル単量体又は
塩化ビニル単量体を含むビニル系単量体混合物の重合が
進み重合器内圧が下がり始めた時から40分以内に重合体
水分散液(以下「スラリー」という。)の温度を重合器
内圧が下がり始める直前のスラリーの温度より5〜10℃
上げる操作を行ない、所定の温度に上つた時点よりモノ
マーを回収することを特徴とする塩化ビニル重合体の製
造方法。1. A partially saponified polyvinyl alcohol having a saponification degree of 70 to 78% is used as a suspending agent for suspension polymerization of a vinyl chloride monomer or a vinyl-based monomer mixture containing a vinyl chloride monomer in an aqueous medium. The polymer aqueous dispersion (hereinafter referred to as “slurry”) is used within 40 minutes from the time when the polymerization of the vinyl chloride monomer or the vinyl-based monomer mixture containing the vinyl chloride monomer proceeds and the internal pressure of the polymerization reactor starts to decrease. 5) to 10 ° C above the temperature of the slurry just before the internal pressure of the polymerization reactor begins to drop.
A method for producing a vinyl chloride polymer, characterized in that an operation of raising the temperature is carried out, and the monomer is recovered when the temperature rises to a predetermined temperature.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62194092A JPH0696618B2 (en) | 1987-08-03 | 1987-08-03 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62194092A JPH0696618B2 (en) | 1987-08-03 | 1987-08-03 | Method for producing vinyl chloride polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6438410A JPS6438410A (en) | 1989-02-08 |
JPH0696618B2 true JPH0696618B2 (en) | 1994-11-30 |
Family
ID=16318817
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62194092A Expired - Lifetime JPH0696618B2 (en) | 1987-08-03 | 1987-08-03 | Method for producing vinyl chloride polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0696618B2 (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5124686A (en) * | 1974-08-26 | 1976-02-28 | Denki Kagaku Kogyo Kk | Mihannotanryotaino jokyohoho |
JPS5138377A (en) * | 1974-09-30 | 1976-03-31 | Nissan Chemical Ind Ltd | NETSUANTEISEIHORIENKABINIRUNO SEIZOHO |
US4001482A (en) * | 1975-04-30 | 1977-01-04 | Continental Oil Company | Preparation of vinyl halide-containing polymers |
JPS5432668A (en) * | 1977-08-15 | 1979-03-10 | Souhei Torii | Production of ice confectionery |
JPS5435880A (en) * | 1977-08-25 | 1979-03-16 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer for suspension polymerization of vinyl compound |
JPS57212213A (en) * | 1981-06-22 | 1982-12-27 | Kanegafuchi Chem Ind Co Ltd | Preparation of vinyl chloride resin |
JPS5968302A (en) * | 1982-10-12 | 1984-04-18 | Unitika Chem Kk | Dispersion stabilizer for suspension polymerization of vinyl compound |
JPS61152703A (en) * | 1984-12-26 | 1986-07-11 | Mitsubishi Chem Ind Ltd | Production of vinyl chloride polymer |
-
1987
- 1987-08-03 JP JP62194092A patent/JPH0696618B2/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5124686A (en) * | 1974-08-26 | 1976-02-28 | Denki Kagaku Kogyo Kk | Mihannotanryotaino jokyohoho |
JPS5138377A (en) * | 1974-09-30 | 1976-03-31 | Nissan Chemical Ind Ltd | NETSUANTEISEIHORIENKABINIRUNO SEIZOHO |
US4001482A (en) * | 1975-04-30 | 1977-01-04 | Continental Oil Company | Preparation of vinyl halide-containing polymers |
JPS5432668A (en) * | 1977-08-15 | 1979-03-10 | Souhei Torii | Production of ice confectionery |
JPS5435880A (en) * | 1977-08-25 | 1979-03-16 | Nippon Synthetic Chem Ind Co Ltd:The | Dispersion stabilizer for suspension polymerization of vinyl compound |
JPS57212213A (en) * | 1981-06-22 | 1982-12-27 | Kanegafuchi Chem Ind Co Ltd | Preparation of vinyl chloride resin |
JPS5968302A (en) * | 1982-10-12 | 1984-04-18 | Unitika Chem Kk | Dispersion stabilizer for suspension polymerization of vinyl compound |
JPS61152703A (en) * | 1984-12-26 | 1986-07-11 | Mitsubishi Chem Ind Ltd | Production of vinyl chloride polymer |
Also Published As
Publication number | Publication date |
---|---|
JPS6438410A (en) | 1989-02-08 |
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