JPH0676446B2 - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymerInfo
- Publication number
- JPH0676446B2 JPH0676446B2 JP62263574A JP26357487A JPH0676446B2 JP H0676446 B2 JPH0676446 B2 JP H0676446B2 JP 62263574 A JP62263574 A JP 62263574A JP 26357487 A JP26357487 A JP 26357487A JP H0676446 B2 JPH0676446 B2 JP H0676446B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- propionate
- hydroxyphenyl
- polymerization
- butyl
- 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
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- 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、塩化ビニル系重合体の製造方法に関する。更
に詳しくは電気絶縁性の優れた塩化ビニル系重合体の製
造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a vinyl chloride polymer. More specifically, it relates to a method for producing a vinyl chloride polymer having excellent electric insulation.
塩化ビニル系重合体は元来電気絶縁性即ち、体積抵抗率
（以下VRと略記する。）が大きく、又機械特性、難燃性
が良好であり、着色が自由であるという特徴から、家庭
や工場の低圧電線を始めとして、その他の多くの電気絶
縁材料として従来より使用されている。ところで、塩化
ビニル系樹脂成型品の電気絶縁性を支配するのは、塩化
ビニル系重合体、安定剤、着色剤などに含まれる微量の
電解質不純物や塩化ビニル系重合体の熱分解によつて生
成する塩酸などが可塑剤に溶け込んで行なわれるイオン
伝導と考えられる。そこで塩化ビニル系重合体のVRの低
下を解決する為には、従来よりこのような電導性を低下
させる金属イオン等を捕捉する物質を塩化ビニル系重合
体中に含有させる方法が提案されている。Vinyl chloride-based polymers have a large electrical insulation property, that is, a large volume resistivity (abbreviated as VR hereinafter), good mechanical properties and flame retardancy, and are freely colored, so Conventionally used as many other electrical insulation materials, including low voltage wires in factories. By the way, the electrical insulation of vinyl chloride resin moldings is governed by the trace amount of electrolyte impurities contained in vinyl chloride polymers, stabilizers, colorants, etc., and the thermal decomposition of vinyl chloride polymers. It is considered that ionic conduction is carried out by dissolving dissolved hydrochloric acid in the plasticizer. Therefore, in order to solve the decrease in VR of vinyl chloride-based polymers, there has been conventionally proposed a method in which a substance that traps metal ions or the like that lowers the conductivity is contained in the vinyl chloride-based polymer. .
本発明の目的は、従来法と異なり塩化ビニル系重合体自
体のVRの高いものを提供することを目的とする。An object of the present invention is to provide a vinyl chloride polymer itself having a high VR unlike the conventional method.
本発明は、塩化ビニル単量体、又はこれと共重合しうる
単量体と塩化ビニル単量体との混合物を水性媒体中で懸
濁重合法により重合して塩化ビニル系重合体を製造する
に当り、重合開始剤として、下記一般式（Ｉ） （但し、ここにＲ、R1,R2及びR3は何れもアルキル基で
あり、R1,R2及びR3の炭素数の総和は10個であり、又、
Ｒは１〜12個の炭素原子数を有するものである。） で表わされる重合開始剤を使用し、オクタデシル−３−
（3,5−ジターシヤリ−ブチル−４−ヒドロキシフエニ
ル）プロピオネートとトリエチレングリコール−ビス
〔３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシ
フエニル）プロピオネート〕を重合系又は重合反応生成
混合物に添加することにより、塩化ビニル系重合体を製
造する方法を要旨とする。The present invention produces a vinyl chloride polymer by polymerizing a vinyl chloride monomer or a mixture of a monomer copolymerizable therewith and a vinyl chloride monomer in an aqueous medium by a suspension polymerization method. As a polymerization initiator, the following general formula (I) (However, R, R 1 , R 2 and R 3 are all alkyl groups, and the total number of carbon atoms of R 1 , R 2 and R 3 is 10, and
R has 1 to 12 carbon atoms. ) Is used, and octadecyl-3-
Polymerization system or polymerization reaction of (3,5-ditert-butyl-4-hydroxyphenyl) propionate and triethyleneglycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] The gist is a method for producing a vinyl chloride polymer by adding it to a product mixture.
本発明では重合開始剤として前記式（Ｉ）で表わされる
化合物を使用する。この化合物には、例えばターシヤリ
ブチルパーオキシネオデカノエート、ターシヤリアミル
パーオキシネオデカノエート、ターシヤリオクチルパー
オキシネオデカノエート、エチルパーオキシネオデカノ
エート、ｔ−ペンチルパーオキシネオデカノエート、2,
4,4−トリメチルペンチルパーオキシネオデカノエー
ト、ｔ−ヘプチルパーオキシネオデカノエート、ｔ−ノ
ニルパーオキシネオデカノエート、ｔ−ラウロイルパー
オキシネオデカノエート等がある。In the present invention, the compound represented by the above formula (I) is used as a polymerization initiator. Examples of this compound include tert-butyl peroxyneodecanoate, tersialyamylperoxyneodecanoate, tersialyoctyl peroxyneodecanoate, ethylperoxyneodecanoate, and t-pentylperoxyneo. Decanoate, 2,
There are 4,4-trimethylpentyl peroxy neodecanoate, t-heptyl peroxy neodecanoate, t-nonyl peroxy neodecanoate, t-lauroyl peroxy neodecanoate and the like.
添加剤としては、オクタデシル−３−（3,5−ジターシ
ヤリ−ブチル−４−ヒドロキシフエニル）プロピオネー
トとトリエチレングリコール−ビス〔３−（３−ｔ−ブ
チル−５−メチル−４−ヒドロキシフエニル）プロピオ
ネート〕を組み合わせて使用する。それらの添加時期は
オクタデシル−３−（3,5−ジターシヤリ−ブチル−４
−ヒドロキシフエニル）プロピオネートを重合開始前に
添加し、トリエチレングリコール−ビス〔３−（３−ｔ
−ブチル−５−メチル−４−ヒドロキシフエニル）プロ
ピオネート〕を重合終了直後に添加するのが最適であ
る。該添加剤の添加量については２種の添加剤共に仕込
単量体の全量に対して１〜10,000ppmの範囲で使用する
のがよい。使用量が少なすぎるとVRの向上効果が不充分
であり、使用量が多すぎると、VRの向上効果は頭打ちと
なり不経済である。As the additive, octadecyl-3- (3,5-ditersialy-butyl-4-hydroxyphenyl) propionate and triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate are used. ) Propionate] is used in combination. The timing of their addition was octadecyl-3- (3,5-ditersia-butyl-4).
-Hydroxyphenyl) propionate was added before the start of the polymerization and triethylene glycol-bis [3- (3-t
It is optimal to add -butyl-5-methyl-4-hydroxyphenyl) propionate] immediately after completion of the polymerization. Regarding the amount of the additive added, it is preferable to use both of the two additives within the range of 1 to 10,000 ppm based on the total amount of the charged monomers. If the usage amount is too small, the VR improving effect is insufficient, and if the usage amount is too large, the VR improving effect reaches a ceiling and is uneconomical.
本発明に使用する懸濁剤としては、塩化ビニル系重合体
の重合に通常用いられるものならどんなものでも用いて
良く例えば、部分ケン化ポリビニルアルコール、メチル
セルロース、エチルセルロース、ヒドロキシプロピルメ
チルセルロース、ヒドロキシエチルセルロース、ゼラチ
ン等がありこれらは単独もしくは組み合わせて使用でき
る。As the suspending agent used in the present invention, any suspending agent which is usually used for the polymerization of vinyl chloride-based polymers may be used, for example, partially saponified polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, gelatin. Etc., and these can be used alone or in combination.
本発明における重合反応は25℃〜70℃の範囲で行うのが
好ましい。The polymerization reaction in the present invention is preferably carried out in the range of 25 ° C to 70 ° C.
次に本発明の実施例を示すが、これによつて本発明の範
囲が限定されるものではない。Next, examples of the present invention will be shown, but the scope of the present invention is not limited thereby.
尚、本発明方法等で得られたPVCのVRの測定は次の方法
で行なつた。The VR of PVC obtained by the method of the present invention and the like was measured by the following method.
（イ）VRの測定 RVC100重量部、ジオクチルフタレート（DOP）45重量部
とトリベース（三塩基性硫酸鉛）５重量部を150℃のミ
キシングロールで10分間混練した後プレスして1m/m厚さ
のシートとする。このシートに500mVの直流電圧をかけV
R値を測定した（JIS K 6723の方法による）。(A) VR measurement 100 parts by weight of RVC, 45 parts by weight of dioctyl phthalate (DOP) and 5 parts by weight of tribase (tribasic lead sulfate) were kneaded with a mixing roll at 150 ° C for 10 minutes and then pressed to a thickness of 1 m / m. Sheet. Apply a DC voltage of 500 mV to this sheet and V
The R value was measured (by the method of JIS K 6723).
実施例１ 内容積200lのステンレス製オートクレーブに、純水100k
g、懸濁剤として、ケン化度74％、粘度7.5cps（20℃に
おける４％水溶液のヘプラー粘度）のポリビニルアルコ
ール、80g、重合開始剤としてターシヤリブチルパーオ
キシネオデカノエート50g及び添加剤としてオクタデシ
ル−３−（3,5−ジタ−シヤリ−ブチル−４−ヒドロキ
シフエニル）−プロピオネートを仕込単量体の全量に対
して100ppmを仕込み脱酸素操作後、塩化ビニル単量体50
kgを仕込み、攪拌しながら加熱し、重合温度39℃で重合
させた後、添加剤としてトリエチレングリコール−ビス
〔３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシ
フエニル）プロピオネート〕を仕込単量体の全量に対し
て100ppm添加し、その後、未反応単量体を回収し、得ら
れた重合体を脱水乾燥した。Example 1 100 k of pure water was placed in a stainless steel autoclave with an internal volume of 200 l.
g, polyvinyl alcohol having a saponification degree of 74%, a viscosity of 7.5 cps (Hepler viscosity of a 4% aqueous solution at 20 ° C.), 80 g, tert-butyl oxyperoxy neodecanoate as a polymerization initiator, and 50 g of an additive. Octadecyl-3- (3,5-di-sialy-butyl-4-hydroxyphenyl) -propionate was charged as 100 ppm with respect to the total amount of the charged monomers, and after deoxidation operation, vinyl chloride monomer 50
After charging kg, heating while stirring and polymerizing at a polymerization temperature of 39 ° C., triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] was added as an additive. Was added to the total amount of the charged monomers in an amount of 100 ppm, the unreacted monomers were then collected, and the obtained polymer was dehydrated and dried.
比較例１ 前記２種の添加剤、即ちオクタデシル−３−（3,5−ジ
タ−シヤリ−ブチル−４−ヒドロキシフエニル）−プロ
ピオネート及びトリエチレングリコール−ビス〔３−
（３−ｔ−ブチル−５−メチル−４−ヒドロキシフエニ
ル）プロピオネート〕を添加しなかつた以外は、実施例
１と同じ方法で重合を行ない脱水、乾燥した。Comparative Example 1 The above two additives, namely octadecyl-3- (3,5-di-sialy-butyl-4-hydroxyphenyl) -propionate and triethylene glycol-bis [3-
Polymerization was performed in the same manner as in Example 1 except that (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] was not added, and dehydration and drying were performed.
比較例２〜７ 前記２種の添加剤を、第１表に記載の時期に、同表の記
載の量だけ添加した以外は比較例１と同じ方法で重合を
行ない脱水、乾燥した。Comparative Examples 2 to 7 Polymerization was carried out in the same manner as in Comparative Example 1 except that the two kinds of additives were added in the amounts shown in Table 1 at the time shown in Table 1, dehydration and drying were performed.
以上の例で得られた重合体のVRの測定結果を第１表に示
す。Table 1 shows the VR measurement results of the polymers obtained in the above examples.
この結果より、前述の２種の添加剤は、両方共添加され
た時にVRの改良効果が大きいことが判る。 From this result, it is understood that the above-mentioned two additives have a great effect of improving VR when both are added.
実施例2,3;比較例８〜17 前述の２種の添加剤を第２表記載の量添加した以外は、
実施例１と同じ方法で重合を行なつた。その結果を第２
表に示す。Examples 2 and 3; Comparative Examples 8 to 17, except that the two additives described above were added in the amounts shown in Table 2.
Polymerization was carried out in the same manner as in Example 1. The result is the second
Shown in the table.
この結果より、前記２種の添加剤は夫々仕込単量体の全
量に対して１〜10,000ppmの範囲で組み合わせて使用さ
れた時高いVRが得られることが判る。 From this result, it can be seen that the above-mentioned two kinds of additives each have a high VR when used in combination in the range of 1 to 10,000 ppm with respect to the total amount of the charged monomers.
実施例5,6;比較例18,19,20 重合開始剤として、第３表記載の化合物を50g添加した
以外は、実施例３と同じ方法で重合を行なつた。その結
果を第３表に示す。Examples 5, 6; Comparative Examples 18, 19, 20 Polymerization was carried out in the same manner as in Example 3 except that 50 g of the compound shown in Table 3 was added as a polymerization initiator. The results are shown in Table 3.
この結果より、前記２種の添加剤は本発明で限定する開
始剤と組み合わせて使用された時VRの改良効果は大きい
ことが判る。 From these results, it can be seen that the above-mentioned two kinds of additives have a great effect of improving VR when used in combination with the initiators limited in the present invention.
Claims (3)
うる単量体と塩化ビニル単量体との混合物を、水性媒体
中で懸濁重合法により重合して塩化ビニル系重合体を製
造するに当り、重合開始剤として下記一般式（Ｉ） （但し、ここにＲ、R1、R2及びR3は何れもアルキル基で
あり、R1、R2及びR3の炭素数の総和は10個であり、又、
Ｒは１〜12個の炭素原子数を有するものである。） で表わされる重合開始剤を使用し、オクタデシル−３−
（3,5−ジターシヤリーブチル−４−ヒドロキシフエニ
ル）プロピオネートとトリエチレングリコール−ビス
〔３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシ
フエニル）プロピオネート〕を重合系又は重合反応生成
混合物に添加することを特徴とする塩化ビニル系重合体
の製造方法。1. A vinyl chloride polymer obtained by polymerizing a vinyl chloride monomer or a mixture of a monomer copolymerizable therewith and a vinyl chloride monomer in an aqueous medium by a suspension polymerization method. The following general formula (I) is used as a polymerization initiator in the production of (However, R, R 1 , R 2 and R 3 are all alkyl groups, and the total number of carbon atoms of R 1 , R 2 and R 3 is 10, and
R has 1 to 12 carbon atoms. ) Is used, and octadecyl-3-
Polymerization system or polymerization of (3,5-ditertiary butyl-4-hydroxyphenyl) propionate and triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] A method for producing a vinyl chloride polymer, which comprises adding to a reaction product mixture.
ル−３−（3,5−ジターシヤリーブチル−４−ヒドロキ
シフエニル）プロピオネート〕の使用量が仕込単量体の
全量に対して１〜10,000ppm、トリエチレングリコール
−ビス〔３−（３−ｔ−ブチル−５−メチル−４−ヒド
ロキシフエニル）プロピオネート〕の使用量が仕込単量
体の全量に対して１〜10,000ppmであることを特徴とす
る前記方法。2. The method according to claim 1, wherein the amount of octadecyl-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] used is 1 with respect to the total amount of the charged monomers. ~ 10,000 ppm, the amount of triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] used is 1 to 10,000 ppm with respect to the total amount of the charged monomers. The method as described above.
いて重合開始前にオクタデシル−３−（3,5−ジターシ
ヤリーブチル−４−ヒドロキシフエニル）プロピオネー
ト〕を添加し、重合終了直後、トリエチレングリコール
−ビス〔３−（３−ｔ−ブチル−５−メチル−４−ヒド
ロキシフエニル）プロピオネート〕を添加することを特
徴とする前記方法。3. Octadecyl-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] is added before the initiation of polymerization in the method according to (1) or (2), Immediately after completion of the polymerization, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] is added to the above method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62263574A JPH0676446B2 (en) | 1987-10-19 | 1987-10-19 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62263574A JPH0676446B2 (en) | 1987-10-19 | 1987-10-19 | Method for producing vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01104605A JPH01104605A (en) | 1989-04-21 |
| JPH0676446B2 true JPH0676446B2 (en) | 1994-09-28 |
Family
ID=17391443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62263574A Expired - Lifetime JPH0676446B2 (en) | 1987-10-19 | 1987-10-19 | Method for producing vinyl chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0676446B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3165525B2 (en) * | 1992-09-08 | 2001-05-14 | 化薬アクゾ株式会社 | Polymerization method of vinyl monomer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4937989A (en) * | 1972-08-16 | 1974-04-09 | ||
| JPS60149608A (en) * | 1984-01-13 | 1985-08-07 | Mitsui Toatsu Chem Inc | Polymerization of vinyl chloride |
| JPS63218711A (en) * | 1987-03-06 | 1988-09-12 | Shin Etsu Chem Co Ltd | Production of vinyl chloride polymer |
-
1987
- 1987-10-19 JP JP62263574A patent/JPH0676446B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4937989A (en) * | 1972-08-16 | 1974-04-09 | ||
| JPS60149608A (en) * | 1984-01-13 | 1985-08-07 | Mitsui Toatsu Chem Inc | Polymerization of vinyl chloride |
| JPS63218711A (en) * | 1987-03-06 | 1988-09-12 | Shin Etsu Chem Co Ltd | Production of vinyl chloride polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01104605A (en) | 1989-04-21 |
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