JPH10101715A - Production of vinyl chloride polymer - Google Patents
Production of vinyl chloride polymerInfo
- Publication number
- JPH10101715A JPH10101715A JP27759496A JP27759496A JPH10101715A JP H10101715 A JPH10101715 A JP H10101715A JP 27759496 A JP27759496 A JP 27759496A JP 27759496 A JP27759496 A JP 27759496A JP H10101715 A JPH10101715 A JP H10101715A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- degree
- polymerization
- saponification
- polyvinyl alcohol
- 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.)
- Pending
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、塩化ビニル系重合
体の製造法に関する。更に詳しくは多孔性で可塑剤吸収
性と熱安定性に優れ、かつカレンダー加工時のロール粘
着の少ない塩化ビニル系重合体の製造法に関する。The present invention relates to a method for producing a vinyl chloride polymer. More particularly, the present invention relates to a method for producing a vinyl chloride polymer which is porous, has excellent plasticizer absorption and thermal stability, and has little roll adhesion during calendering.
【0002】[0002]
【従来の技術】塩化ビニル系重合体は加工性、物理的性
質並びに価格においてバランスの良い高分子材料である
ことから、硬質から軟質まで広範な分野で使用されてい
る。このうち、軟質の分野では該塩化ビニル系重合体に
可塑剤を比較的多量に配合するため、可塑剤の吸収が速
く、しかも得られる成形品はフィッシュアイが少ないこ
とが望まれる。可塑剤吸収性を向上させるためには、塩
化ビニル系重合体の粒子をより多孔性にしなければなら
ず、これらの要求に応えるために例えば特開昭53−1
36089号公報には、主分散剤として使用される部分
ケン化ポリビニルアルコ−ル(ケン化度70〜90モル
%、平均重合度700〜2600)に、ケン化度60モ
ル%以下、平均重合度500以下の低ケン化度かつ低重
合度の部分ケン化ポリビニルアルコールを二次分散剤と
して併用する方法が提案されている。2. Description of the Related Art Vinyl chloride polymers are used in a wide range of fields from hard to soft because they are well-balanced polymer materials in processability, physical properties and price. Among these, in the field of softness, since a relatively large amount of a plasticizer is added to the vinyl chloride polymer, it is desired that the plasticizer absorbs the plastic at a high rate and that the obtained molded article has less fish eyes. In order to improve the plasticizer absorption, the particles of the vinyl chloride polymer must be made more porous.
No. 36089 discloses that a partially saponified polyvinyl alcohol (saponification degree: 70 to 90 mol%, average polymerization degree: 700 to 2600) used as a main dispersant has a saponification degree of 60 mol% or less and an average polymerization degree. A method has been proposed in which partially saponified polyvinyl alcohol having a low saponification degree and a low polymerization degree of 500 or less is used in combination as a secondary dispersant.
【0003】しかしながら、該二次分散剤量を多量に併
用すると、得られる塩化ビニル系重合体の可塑剤吸収性
は改善されるものの、該塩化ビニル系重合体をカレンダ
ー加工に供すると、溶融樹脂がロールに粘着したり、プ
レートアウトを起こしやすくなり、カレンダー加工性が
悪化するといった問題点がある。However, when a large amount of the secondary dispersant is used in combination, the plasticizer absorption of the obtained vinyl chloride polymer is improved, but when the vinyl chloride polymer is subjected to calendering, the molten resin is However, there is a problem that sticking to the roll or plate-out is likely to occur, and the calenderability is deteriorated.
【0004】[0004]
【発明が解決しようとする課題】本発明者らは、多孔性
で可塑剤吸収性に優れ、かつカレンダー加工時のロール
粘着の少なく、しかも熱安定性に優れた塩化ビニル系重
合体を得るべく鋭意研究した。その結果、特定の平均重
合度とケン化度を有する部分ケン化ポリビニルアルコ−
ル3種類の特定量を分散剤として使用し、かつ特定の高
級アルコ−ル及び/または高級脂肪酸誘導体の特定量の
存在下で塩化ビニル系単合体を懸濁重合すると得られる
重合体が多孔性で可塑剤の吸収性に優れ、カレンダ−加
工時のロ−ル粘着が少なく、しかも熱安定性に優れた塩
化ビニル系重合体が得られることを見い出し、この知見
に基づき、本発明を完成した。以上の記述から明かなよ
うに、本発明の目的は多孔性で可塑剤吸収性に優れ、か
つカレンダ−加工時のロ−ル粘着が少なく、しかも熱安
定性に優れた塩化ビニル系重合体の製造法を提供するこ
とである。DISCLOSURE OF THE INVENTION The present inventors have aimed at obtaining a vinyl chloride polymer which is porous, has excellent plasticizer absorbency, has low roll adhesion during calendering, and has excellent heat stability. Diligently studied. As a result, a partially saponified polyvinyl alcohol having a specific average polymerization degree and saponification degree is obtained.
The polymer obtained by suspension polymerization of a vinyl chloride-based single compound in the presence of a specific higher alcohol and / or a higher fatty acid derivative in the presence of a specific amount of three types of specific alcohols as a dispersing agent is porous. It has been found that a vinyl chloride polymer having excellent plasticizer absorbency, low roll adhesion during calendering, and excellent heat stability can be obtained. Based on this finding, the present invention has been completed. . As apparent from the above description, an object of the present invention is to provide a vinyl chloride polymer which is porous, has excellent plasticizer absorbency, has low roll adhesion during calendar processing, and has excellent heat stability. It is to provide a manufacturing method.
【0005】[0005]
【課題を解決するための手段】本発明は前記問題点を解
決する手段として、塩化ビニル系単量体を油溶性重合開
始剤の存在下に水性媒体中で懸濁重合する際に、塩化ビ
ニル単量体を懸濁分散させるために用いる分散剤とし
て、(A)平均重合度が1000〜3000、かつケン
化度が70〜90モル%の部分ケン化ポリビニルアルコ
ール、(B)平均重合度500〜900、かつケン化度
が70〜80モル%の部分ケン化ポリビニルアルコー
ル、及び(C)平均重合度200〜600、かつケン化
度が20〜55モル%の部分ケン化ポリビニルアルコー
ル、を使用するとともに、高級アルコール及び/又は高
級脂肪酸誘導体の存在下に塩化ビニル系単合体を重合す
ることを特徴とする。According to the present invention, as a means for solving the above-mentioned problems, vinyl chloride monomers are subjected to suspension polymerization in an aqueous medium in the presence of an oil-soluble polymerization initiator. As a dispersant used for suspending and dispersing the monomer, (A) a partially saponified polyvinyl alcohol having an average degree of polymerization of 1000 to 3000 and a degree of saponification of 70 to 90 mol%, and (B) an average degree of polymerization of 500 Using a partially saponified polyvinyl alcohol having a saponification degree of from about 900 to about 900 and a degree of saponification of from 70 to 80 mol%, and (C) a partially saponified polyvinyl alcohol having an average degree of polymerization of from 200 to 600 and a saponification degree of from about 20 to 55 mol%. And polymerizing a vinyl chloride-based single compound in the presence of a higher alcohol and / or a higher fatty acid derivative.
【0006】以下本発明を詳細に説明する。本発明で用
いられる分散剤(A)及び(B)の使用量の重量比
(A)/(B)は9/1〜1/9、好ましくは7/3〜
3/7であって、(A)と(B)の仕込み量の合計は、
単量体100重量部当たり、0.04〜0.2重量部の
割合で使用される。該(A)/(B)の重量比が9/1
を越えると、得られる重合体粒子の可塑剤吸収性が悪下
し、また1/9未満では得られる重合体粒子が微細にな
り粉体取扱いが困難になることがある。また、(A)と
(B)の仕込み量の合計が、仕込み単量体100重量当
たり、0.04重量部に満たないと単量体の分散が不安
定となり、その結果、粒子状の重合体粒子が得られない
か、得られたとしても重合体の粒子が粗大なものとなる
傾向にあり、また、0.2重量部を越えると、得られる
重合体粒子が微細になり粉体取り扱いが困難になる。Hereinafter, the present invention will be described in detail. The weight ratio (A) / (B) of the amounts of the dispersants (A) and (B) used in the present invention is 9/1 to 1/9, preferably 7/3.
3/7, and the total of the charged amounts of (A) and (B) is
It is used in a ratio of 0.04 to 0.2 parts by weight per 100 parts by weight of the monomer. The weight ratio of (A) / (B) is 9/1
If the ratio exceeds, the plasticizer absorption of the obtained polymer particles may be deteriorated. If the ratio is less than 1/9, the obtained polymer particles may be fine and powder handling may be difficult. If the total of the charged amounts of (A) and (B) is less than 0.04 parts by weight per 100 parts by weight of the charged monomer, the dispersion of the monomer becomes unstable, and as a result, the weight of the particles increases. No coalesced particles are obtained, or even if they are obtained, the polymer particles tend to be coarse, and if it exceeds 0.2 parts by weight, the obtained polymer particles become fine and powder handling Becomes difficult.
【0007】本発明の塩化ビニル系重合体の製造法で
は、(A)、(B)の分散剤のほかに、さらに(C)の
分散剤を仕込み単量体100重量部当たり、0.005
〜0.03重量部の範囲で使用する。この(C)の分散
剤のケン化度が20モル%より低いと、得られる重合体
が粗粒子化したり、重合器内にスケールが付着し、ま
た、ケン化度が55モル%より高いか重合度が600を
越えると、得られる重合体の可塑剤吸収性が悪化する。
また、この添加量が0.03重量部を越えると、得られ
る重合体粒子が微細になり粉体取り扱いが困難になる恐
れがある。さらに、該(C)の部分ケン化ポリビニルア
ルコールの添加方法は、特に限定されないが、例えばそ
のまま直接添加してもよく、メタノール、アセトン、酢
酸メチル、酢酸エチル等の溶媒または水/有機溶媒等の
混合溶媒を用いて溶解して使用してもよく、また、水性
エマルジョンにして重合系に添加することもできる。In the method for producing a vinyl chloride polymer according to the present invention, in addition to the dispersants (A) and (B), the dispersant (C) is further added to the mixture at a rate of 0.005 per 100 parts by weight of the monomer.
Used in the range of 0.03 parts by weight. When the degree of saponification of the dispersant (C) is lower than 20 mol%, the obtained polymer may be coarsened, scale may adhere to the polymerization vessel, and the degree of saponification may be higher than 55 mol%. If the degree of polymerization exceeds 600, the resulting polymer will have poor plasticizer absorbency.
On the other hand, if the amount exceeds 0.03 parts by weight, the obtained polymer particles may be fine and handling of the powder may be difficult. Further, the method of adding the partially saponified polyvinyl alcohol (C) is not particularly limited. For example, the partially saponified polyvinyl alcohol may be added directly as it is, or a solvent such as methanol, acetone, methyl acetate, ethyl acetate or a water / organic solvent. It may be used by dissolving it using a mixed solvent, or it may be made into an aqueous emulsion and added to the polymerization system.
【0008】本発明で使用される高級アルコールとして
は、ラウリルアルコール、パルミチルアルコール、ステ
アリルアルコール、セチルアルコール等を挙げることが
でき、高級脂肪酸誘導体としては、ソルビタン酸モノラ
ウレート、ソルビタン酸モノパルミテート、ソルビタン
酸モノステアレート、ソルビタン酸トリラウレート、ソ
ルビタン酸トリパルミテート、ソルビタン酸トリステア
レートやグリセリンモノラウレート、グリセリンモノパ
ルミテート、グリセリンモノステアレート、グリセリン
トリラウレート、グリセリントリパルミテート、グリセ
リントリステアレートなどを挙げることができ、これら
は単独でまたは2種以上組み合わせて使用しても差し支
えない。また、これら添加剤の好ましい使用量は、仕込
み単量体100重量部当たり、0.05〜0.5重量部
であって、0.05部未満では、可塑剤吸収性およびカ
レンダー加工時のロ−ル粘着性を十分に改良できず、ま
た、0.5重量部を越えると、得られる重合体を用いた
成形品の透明性が悪化する。The higher alcohol used in the present invention includes lauryl alcohol, palmityl alcohol, stearyl alcohol, cetyl alcohol and the like. The higher fatty acid derivatives include sorbitanic acid monolaurate and sorbitanic acid monopalmitate Sorbitan monostearate, sorbitan trilaurate, sorbitan tripalmitate, sorbitan tristearate, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin trilaurate, glycerin tripalmitate, glycerin tri Stearate and the like can be mentioned, and these may be used alone or in combination of two or more. Further, the preferred amount of these additives is 0.05 to 0.5 parts by weight per 100 parts by weight of the charged monomers. If the adhesiveness cannot be sufficiently improved, and if the content exceeds 0.5 parts by weight, the transparency of a molded article using the obtained polymer deteriorates.
【0009】上記の添加剤を重合系に添加する場合に
は、重合の開始前に一括して添加するほうが好ましく、
重合の開始後に一括もしくは分割して添加すると、得ら
れる重合体の可塑剤吸収性が向上せず、また、得られた
重合体を用いた成形品の透明性が低下したり、フィッシ
ュアイが増加する。When the above additives are added to the polymerization system, it is preferable to add them all at once before the start of the polymerization.
If added at once or dividedly after the start of polymerization, the plasticizer absorbency of the obtained polymer will not be improved, and the transparency of the molded article using the obtained polymer will decrease or the fish eye will increase. I do.
【0010】本発明で用いられる塩化ビニル系単量体と
しては、塩化ビニル単量体のほかに該塩化ビニル単量体
と共重合しうる片末端にビニル基を有する重合性化合物
と該塩化ビニル単量体との混合物であり、該重合性化合
物としては塩化ビニル単量体と共重合可能なものであれ
ば特に限定しないが、具体的には酢酸ビニルのようなア
ルキルビニルエステル、セチルビニルエーテルのような
アルキルビニルエーテル、エチレンまたはプロピレンな
どのα−モノオレフィン系単量体、アクリル酸メチルの
ようなアクリル酸アルキルエステルまたはメタクリル酸
メチルのようなメタクリル酸アルキルエステル等のコモ
ノマ−を例示することができる。The vinyl chloride monomer used in the present invention includes, in addition to the vinyl chloride monomer, a polymerizable compound having a vinyl group at one end capable of copolymerizing with the vinyl chloride monomer and the vinyl chloride monomer. It is a mixture with a monomer, and the polymerizable compound is not particularly limited as long as it can be copolymerized with a vinyl chloride monomer.Specifically, alkyl vinyl esters such as vinyl acetate and cetyl vinyl ether are used. Examples thereof include alkyl vinyl ethers, α-monoolefin monomers such as ethylene or propylene, and comonomers such as alkyl acrylates such as methyl acrylate or alkyl methacrylates such as methyl methacrylate. .
【0011】本発明に用いる油溶性重合開始剤として
は、ターシャリーブチルパーオキシネオデカノエート、
ターシャリーブチルパーオキシピバレート、α−クミル
パーオキシネオデカノエート等のパーエステル化合物、
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−2−エチルヘキ
シルパーオキシジカーボネート、ビス(4−ターシャリ
ーブチルシクロヘキシル)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、ジ
−3−メトキシ−3−メチルブチルパ−オキシジカ−ボ
ネート、ジセカンダリーブチルパーオキシジカーボネー
ト等のパーカーボネート化合物、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過酸化物、およびα,
α’−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を挙げることができ、これ
らの1種または2種以上を組合せて使用することも可能
である。The oil-soluble polymerization initiator used in the present invention includes tertiary butyl peroxy neodecanoate,
Tertiary butyl peroxypivalate, perester compounds such as α-cumylperoxy neodecanoate,
Diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate,
Di-3-methoxybutylperoxydicarbonate, di-3-methoxy-3-methylbutylperoxydicarbonate, percarbonate compounds such as disi-butylbutylperoxydicarbonate, peroxides such as acetylcyclohexylsulfonyl peroxide, and α,
An azo compound such as α'-azobis-4-methoxy-2-, 4-dimethylvaleronitrile can be mentioned, and one or more of these can be used in combination.
【0012】また、本発明の効果を損なわない範囲で、
通常、懸濁重合に使用される他の添加剤、例えば重合器
内壁等へのスケール付着を防止することのできる安定
剤、酸化防止剤等、平均重合度を調製するための連鎖移
動剤、消泡剤、重合水媒体のpHを調製するpH調製剤
等を添加しても何等差し支えない。[0012] In addition, as long as the effects of the present invention are not impaired,
Usually, other additives used for the suspension polymerization, for example, a chain transfer agent for adjusting the average degree of polymerization, such as a stabilizer capable of preventing scale adhesion to the inner wall of the polymerization vessel, an antioxidant, etc. A foaming agent, a pH adjusting agent for adjusting the pH of the aqueous polymerization medium, or the like may be added without any problem.
【0013】本発明の塩化ビニル系重合体の製造法にあ
っては、例えば、仕込み単量体当たりの水性媒体の使用
量、重合開始剤および塩化ビニル単量体、場合によって
は他のコモノマーなどの使用量とこれらの仕込み方法、
重合温度等は従来公知の条件で行えばよい。In the method for producing a vinyl chloride polymer of the present invention, for example, the amount of an aqueous medium used per charged monomer, a polymerization initiator and a vinyl chloride monomer, and if necessary, other comonomers, etc. Consumption of these and their preparation methods,
The polymerization temperature and the like may be performed under conventionally known conditions.
【0014】本発明で得られる塩化ビニル系重合体に配
合される金属系安定剤としては、有機錫系安定剤の他に
複合金属石けん系安定剤でも十分優れた熱安定性を発揮
できるが有機錫系安定剤を用いた方が本発明の効果がよ
り大きい。As the metal stabilizer to be incorporated in the vinyl chloride polymer obtained in the present invention, not only an organotin stabilizer but also a composite metal soap stabilizer can exhibit sufficiently excellent thermal stability. The effect of the present invention is greater when a tin-based stabilizer is used.
【0015】該有機錫系安定剤としては、通常の塩化ビ
ニル系重合体用有機錫系安定剤が用いられ、特に限定は
ない。また、複合金属石けん系安定剤としては亜鉛の有
機酸塩と、アルカリ金属および/またはアルカリ土類金
属の有機酸塩との組合せでよく、アルカリ金属および/
またはアルカリ土類金属の種類としては、リチウム、ナ
トリウム、カリウム、マグネシウム、カルシウムなどが
例示でき、中でもカルシウムと亜鉛の組合せが好まし
い。有機酸塩としては、例えば、ギ酸、酢酸、プロピオ
ン酸、カプリル酸、ラウリル酸、パルミチン酸、ステア
リル酸などのカルボン酸が挙げられるが、これに限定さ
れるものではない。As the organotin-based stabilizer, an ordinary organotin-based stabilizer for a vinyl chloride polymer is used, and there is no particular limitation. The composite metal soap stabilizer may be a combination of an organic acid salt of zinc and an organic acid salt of an alkali metal and / or an alkaline earth metal.
Alternatively, examples of the kind of the alkaline earth metal include lithium, sodium, potassium, magnesium, calcium and the like, and among them, a combination of calcium and zinc is preferable. Examples of the organic acid salt include, but are not limited to, carboxylic acids such as formic acid, acetic acid, propionic acid, caprylic acid, lauric acid, palmitic acid, and stearyl acid.
【0016】[0016]
【実施例】以下、実施例および比較例を用いて本発明を
具体的に説明するが、本発明はこれによって限定される
ものではない。なお、実施例および比較例で実施したロ
ール粘着性、成形品の熱安定性の評価方法は次の方法に
準じた。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the evaluation method of the roll adhesiveness and the thermal stability of the molded article performed in Examples and Comparative Examples was based on the following methods.
【0017】(1)ロール粘着性評価 ロール粘着温度:塩化ビニル系重合体100重量部、ジ
ブチル錫マレート系安定剤1.2重量部、エポキシ化大
豆油2.5重量部、ステアリン酸0.3重量部を計量し
て、ヘンシェルミキサー(商品名)に入れ、1000r
pmで10分間攪拌してブレンドする。得られた配合物
100gを8インチの電気ロールを用いて、170℃で
巻き付かせた後、昇温スピード1℃/分で200℃へ昇
温しながら混練し、0.5mmのシートがロール表面に
粘着して取り出せない温度を測定した。この温度が高い
程ロールに粘着しにくいことを意味する。(1) Evaluation of Roll Adhesion Roll adhesion temperature: 100 parts by weight of vinyl chloride polymer, 1.2 parts by weight of dibutyltin malate stabilizer, 2.5 parts by weight of epoxidized soybean oil, 0.3 parts of stearic acid Weigh parts by weight, put in Henschel mixer (trade name), 1000r
Stir at pm for 10 minutes to blend. After winding 100 g of the obtained compound at 170 ° C. using an 8-inch electric roll, the mixture is kneaded while heating to 200 ° C. at a heating rate of 1 ° C./min. The temperature at which sticking to the surface was not possible was measured. It means that the higher the temperature is, the harder it is to stick to the roll.
【0018】ロール粘着性:上記組成物100gをロー
ル温度180℃の8インチロールで5分間混練してシー
トを取り出した。次いで新たに上記組成物を使用して同
様に5分間混練してシートを取り出した。シートが8イ
ンチロールに粘着し、そのためシートが切断されて取り
出せなくなるまでこの操作を繰り返し行い、その時の回
数で判定した。判定の基準は下記の通り。 Roll adhesion: 100 g of the above composition was kneaded with an 8-inch roll at a roll temperature of 180 ° C. for 5 minutes, and a sheet was taken out. Next, the composition was newly kneaded for 5 minutes and the sheet was taken out. This operation was repeated until the sheet was stuck to the 8-inch roll and the sheet was cut and could not be taken out, and the number of times at that time was judged. The criteria for judgment are as follows.
【0019】(2)成形体の熱安定性 上記組成物を160℃の8インチロールで5分間混練し
厚さ約0.5mmのシートを作り、それを185℃のオ
ーブンに入れてシートが黒化(炭化)するまで10分毎
に取り出す。これらシートの黒化時間が長い程熱安定性
が良いことを示す。(2) Thermal Stability of Molded Product The above composition was kneaded with an 8-inch roll at 160 ° C. for 5 minutes to form a sheet having a thickness of about 0.5 mm, which was placed in an oven at 185 ° C. and the sheet was blackened. Remove every 10 minutes until carbonization occurs. The longer the blackening time of these sheets, the better the thermal stability.
【0020】(3)成形体の透明性(ヘイズ値) 上記シートを重ね合わせて160℃、100kg/cm2の条
件下でプレスし、厚さ5mmのプレス板を作成した。こ
のプレス板の透明性(ヘイズ値)をスガ試験機株式会社
製のカラーコンピューターを用いて測定した。このヘイ
ズ値が低い程透明性が高いことを意味する。(3) Transparency of molded article (haze value) The above-mentioned sheets were overlaid and pressed under the conditions of 160 ° C and 100 kg / cm 2 to prepare a pressed plate having a thickness of 5 mm. The transparency (haze value) of this press plate was measured using a color computer manufactured by Suga Test Instruments Co., Ltd. The lower the haze value, the higher the transparency.
【0021】(4)可塑剤吸収量 内径25mm、深さ85mmのガラス製容器の底にグラ
スファイバーを詰め、これに試料の塩化ビニル系重合体
10gを採取して投入する。これにジオクチルフタレー
トを20g加え、60分放置してDOPを重合体に充分
に浸透させる。その後、3000rpmで30分間回転
させて過剰のDOPを遠心分離し、重合体に吸収された
DOPの量(重量%)を重合体100重量部当たりの質
量で求める。(4) Amount of plasticizer absorption A glass fiber having an inner diameter of 25 mm and a depth of 85 mm is filled with glass fiber, and 10 g of a sample vinyl chloride polymer is sampled and put into the glass fiber. To this, 20 g of dioctyl phthalate is added, and left for 60 minutes to allow the DOP to sufficiently penetrate into the polymer. Thereafter, the mixture is rotated at 3000 rpm for 30 minutes to centrifuge excess DOP, and the amount (% by weight) of DOP absorbed by the polymer is determined by the mass per 100 parts by weight of the polymer.
【0022】実施例1 内容積0.2m3のステンレス製重合槽に純水100k
gを仕込んでおき、その中へケン化度72モル%、平均
重合度760の部分ケン化ポリビニルアルコール18.
75g(仕込単量体100重量部当たり0.025重量
部)およびケン化度80モル%、平均重合度2600の
部分ケン化ポリビニルアルコール30.00g(仕込単
量体100重量部当たり0.04重量部)をそれぞれ水
に溶解させた水溶液およびケン化度35モル%、平均重
合度250の部分ケン化ポリビニルアルコール15.0
0g(仕込単量体100重量部当たり0.02重量部)
をメチルアルコールと水の混合溶媒(重量1:1)に溶
解させた溶液をそれぞれ仕込み、さらにパルミチルアル
コールを37.5g(仕込単量体100重量部当たり
0.05重量部)仕込んだ後に開始剤として、t−ブチ
ルネオデカノエートを35g添加した。さらに塩化ビニ
ル単量体を75kg仕込み、攪拌しながら該重合槽を6
7℃に昇温し、重合器内圧が9kg/cm2に低下した時点で
反応を停止し、次いで未反応単量体を回収し、重合槽内
の反応物を水洗、脱水、乾燥して塩化ビニル系重合体を
得た。得られた重合体粒子を用いて上述の評価試験を行
い、その結果を第1表に示した。EXAMPLE 1 100 k of pure water was placed in a stainless steel polymerization tank having an inner volume of 0.2 m 3.
g of the partially saponified polyvinyl alcohol having a degree of saponification of 72 mol% and an average degree of polymerization of 760.
75 g (0.025 parts by weight per 100 parts by weight of charged monomer) and 30.00 g of partially saponified polyvinyl alcohol having a degree of saponification of 80 mol% and an average degree of polymerization of 2600 (0.04 part by weight per 100 parts by weight of charged monomer) In water) and a partially saponified polyvinyl alcohol 15.0 having a degree of saponification of 35 mol% and an average degree of polymerization of 250.
0 g (0.02 parts by weight per 100 parts by weight of charged monomer)
Was dissolved in a mixed solvent (weight 1: 1) of methyl alcohol and water, and then 37.5 g of palmityl alcohol (0.05 part by weight per 100 parts by weight of the charged monomer) was started. As an agent, 35 g of t-butyl neodecanoate was added. Further, 75 kg of a vinyl chloride monomer was charged, and the polymerization tank was stirred for 6 hours while stirring.
The temperature was raised to 7 ° C., and when the internal pressure of the polymerization reactor dropped to 9 kg / cm 2 , the reaction was stopped. Then, the unreacted monomer was recovered, and the reactants in the polymerization tank were washed with water, dehydrated, dried, and chlorided. A vinyl polymer was obtained. The above-mentioned evaluation test was performed using the obtained polymer particles, and the results are shown in Table 1.
【0023】実施例2〜3、比較例1〜2 部分ケン化ポリビニルアルコール、高級アルコール、高
級脂肪酸誘導体の種類、組み合わせ量を第1表に示した
条件に変えた以外は実施例1に準拠して、重合を行い、
重合体粒子を得た。得られた重合体粒子を用いて上述の
評価試験を行い、その結果を第1表に示した。Examples 2 to 3 and Comparative Examples 1 to 2 The procedure of Example 1 was repeated except that the types and the amounts of partially saponified polyvinyl alcohol, higher alcohols and higher fatty acid derivatives were changed to the conditions shown in Table 1. And polymerize,
Polymer particles were obtained. The above-mentioned evaluation test was performed using the obtained polymer particles, and the results are shown in Table 1.
【0024】実施例4〜6、比較例3 部分ケン化ポリビニルアルコール、高級アルコール、高
級脂肪酸誘導体の種類、組み合わせ量を第2表に示した
条件に変えた以外は実施例1に準拠して、重合を行い、
重合体粒子を得た。得られた重合体粒子を用いて上述の
評価試験を行い、その結果を第2表に示した。Examples 4 to 6 and Comparative Example 3 The procedure of Example 1 was repeated except that the types and the amounts of partially saponified polyvinyl alcohol, higher alcohols and higher fatty acid derivatives were changed to the conditions shown in Table 2. Perform polymerization,
Polymer particles were obtained. The above evaluation test was performed using the obtained polymer particles, and the results are shown in Table 2.
【0025】比較例4〜8 部分ケン化ポリビニルアルコール、高級アルコール、高
級脂肪酸誘導体の種類、組み合わせ量を第3表に示した
条件に変えた以外は実施例1に準拠して、重合を行い、
重合体粒子を得た。得られた重合体粒子を用いて上述の
評価試験を行い、その結果を第3表に示した。Comparative Examples 4 to 8 Polymerization was carried out in the same manner as in Example 1 except that the kind and combination of partially saponified polyvinyl alcohol, higher alcohol and higher fatty acid derivative were changed to the conditions shown in Table 3.
Polymer particles were obtained. The above-mentioned evaluation test was performed using the obtained polymer particles, and the results are shown in Table 3.
【0026】[0026]
【発明の効果】本発明の製造法によれば、従来の懸濁重
合法で可塑剤吸収性を向上させる方法(比較例1)に比
べて、可塑剤吸収性が高く、しかも懸念されるカレンダ
ー加工時のロール粘着が少なく、かつ熱安定性が良好な
重合体粒子を得ることができる。According to the production method of the present invention, compared with the method of improving the plasticizer absorbency by the conventional suspension polymerization method (Comparative Example 1), the plasticizer absorbability is higher and there is a concern about the calender. It is possible to obtain polymer particles having low roll adhesion during processing and good thermal stability.
【表1】 [Table 1]
【表2】 [Table 2]
【表3】 [Table 3]
Claims (2)
存在下に水性媒体中で懸濁重合させるに際し、分散剤と
して (A)平均重合度が1000〜3000、かつケン化度
が70〜90モル%の部分ケン化ポリビニルアルコー
ル、(B)平均重合度500〜900、かつケン化度が
70〜80モル%の部分ケン化ポリビニルアルコール、
及び(C)平均重合度200〜600、かつケン化度が
20〜55モル%の部分ケン化ポリビニルアルコール
を、単量体100重量部当り、上記成分Aと成分Bとの
仕込み量の合計が0.04〜0.2重量部、(A)/
(B)=1/9〜9/1で、(C)の仕込量が単量体1
00重量部当たり、0.005〜0.03重量部、使用
し、かつ高級アルコールおよび/または高級脂肪酸誘導
体の存在下に重合することを特徴とする塩化ビニル系重
合体の製造法。When a vinyl chloride monomer is subjected to suspension polymerization in an aqueous medium in the presence of an oil-soluble polymerization initiator, the dispersant (A) has an average degree of polymerization of 1,000 to 3,000 and a degree of saponification of 70-90 mol% of partially saponified polyvinyl alcohol, (B) partially saponified polyvinyl alcohol having an average degree of polymerization of 500-900 and a saponification degree of 70-80 mol%,
And (C) a partially saponified polyvinyl alcohol having an average degree of polymerization of 200 to 600 and a degree of saponification of 20 to 55 mol%, and the total amount of the components A and B charged per 100 parts by weight of the monomer is 0.04 to 0.2 parts by weight, (A) /
(B) = 1/9 to 9/1, and the charge amount of (C) is monomer 1
A method for producing a vinyl chloride-based polymer, wherein 0.005 to 0.03 parts by weight per 00 parts by weight is used and polymerization is carried out in the presence of a higher alcohol and / or a higher fatty acid derivative.
が400〜1500の範囲である請求項1記載の塩化ビ
ニル系重合体の製造法。2. The process for producing a vinyl chloride polymer according to claim 1, wherein the average degree of polymerization of the obtained vinyl chloride polymer is in the range of 400 to 1500.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27759496A JPH10101715A (en) | 1996-09-27 | 1996-09-27 | Production of vinyl chloride polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27759496A JPH10101715A (en) | 1996-09-27 | 1996-09-27 | Production of vinyl chloride polymer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10101715A true JPH10101715A (en) | 1998-04-21 |
Family
ID=17585631
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27759496A Pending JPH10101715A (en) | 1996-09-27 | 1996-09-27 | Production of vinyl chloride polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH10101715A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008523232A (en) * | 2004-12-14 | 2008-07-03 | イネオス ビニールズ ユーケイ リミテッド | Polymerization of vinyl chloride monomer |
CN102492066A (en) * | 2011-12-08 | 2012-06-13 | 内蒙古宜化化工有限公司 | Method for preparing polyvinyl chloride by suspension polymerization |
KR20160147806A (en) | 2014-04-09 | 2016-12-23 | 주식회사 쿠라레 | Vinyl resin production method |
-
1996
- 1996-09-27 JP JP27759496A patent/JPH10101715A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008523232A (en) * | 2004-12-14 | 2008-07-03 | イネオス ビニールズ ユーケイ リミテッド | Polymerization of vinyl chloride monomer |
CN102492066A (en) * | 2011-12-08 | 2012-06-13 | 内蒙古宜化化工有限公司 | Method for preparing polyvinyl chloride by suspension polymerization |
KR20160147806A (en) | 2014-04-09 | 2016-12-23 | 주식회사 쿠라레 | Vinyl resin production method |
US9751963B2 (en) | 2014-04-09 | 2017-09-05 | Kuraray Co., Ltd. | Vinyl resin production method |
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