JP3326956B2 - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymerInfo
- Publication number
- JP3326956B2 JP3326956B2 JP06724494A JP6724494A JP3326956B2 JP 3326956 B2 JP3326956 B2 JP 3326956B2 JP 06724494 A JP06724494 A JP 06724494A JP 6724494 A JP6724494 A JP 6724494A JP 3326956 B2 JP3326956 B2 JP 3326956B2
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- Japan
- Prior art keywords
- polymerization
- temperature
- vinyl chloride
- reaction
- polymerization reaction
- Prior art date
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- Polymerisation Methods In General (AREA)
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Description
【０００１】[0001]
【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。詳しくは本発明は成形加工性の改良さ
れた、特に嵩比重が大きく、加工時のゲル化溶融速度が
大きい塩化ビニル系重合体を安定に製造する方法に関す
るものである。The present invention relates to a method for producing a vinyl chloride polymer. More specifically, the present invention relates to a method for stably producing a vinyl chloride-based polymer having improved moldability, particularly having a large bulk specific gravity and a high gelling / melting rate during processing.
【０００２】[0002]
【従来の技術】塩化ビニル系重合体は、通常、塩化ビニ
ル単量体または塩化ビニル単量体を主体とする共重合可
能な単量体の混合物（以下、これらを総称して、「塩化
ビニル系単量体」といい、これらを重合して得られる重
合体を「塩化ビニル系重合体」という。）を重合開始剤
の存在下に、乳化剤または分散剤を含む水性媒体中で乳
化重合または懸濁重合させることにより製造される。2. Description of the Related Art A vinyl chloride polymer is generally a vinyl chloride monomer or a mixture of copolymerizable monomers mainly composed of a vinyl chloride monomer (hereinafter collectively referred to as "vinyl chloride"). A polymer obtained by polymerizing these monomers is referred to as a "vinyl chloride-based polymer") in the presence of a polymerization initiator in an aqueous medium containing an emulsifier or a dispersant. It is produced by suspension polymerization.
【０００３】一般に、塩化ビニル系重合体よりなる塩化
ビニル系樹脂の成形加工性は、粒子形態に強く依存し、
塩化ビニル系樹脂の嵩比重、内部空孔容積及びゲル化溶
融速度を増加させることは、成形加工性の向上にとって
重要な因子である。本発明者らは、以前、塩化ビニル系
樹脂の嵩比重及びゲル化溶融速度を増加させる方法とし
て、塩化ビニル系単量体を水性媒体中で重合反応させて
塩化ビニル系重合体を製造する際、重合反応が進行する
期間全体のうちの５０％以上の期間において重合温度を
上昇させつつ重合を行なう方法（特開昭６１−１２６１
１２号）を提案した。In general, the moldability of a vinyl chloride resin comprising a vinyl chloride polymer strongly depends on the particle morphology.
Increasing the bulk specific gravity, the internal pore volume, and the gelation melting rate of the vinyl chloride resin is an important factor for improving the moldability. As a method of increasing the bulk specific gravity and gelation melting rate of a vinyl chloride resin, the present inventors have previously used a vinyl chloride monomer in a polymerization reaction in an aqueous medium to produce a vinyl chloride polymer. A method in which polymerization is carried out while raising the polymerization temperature in a period of 50% or more of the entire period in which the polymerization reaction proceeds (Japanese Patent Application Laid-Open No. 61-12661)
No. 12).
【０００４】しかし、上記の方法においては重合反応に
おける重合温度の上昇変化幅（以下、「昇温幅」とい
う）を大きくする程、嵩比重、ゲル化溶融速度は大きく
なるが、昇温幅をあまり大きくすると、重合反応末期に
発熱が急激に大きくなりすぎ冷却が困難になったり、重
合開始剤の不足により反応末期に十分な重合反応が行な
われず、所期の時間内に重合反応が完結しないといった
問題があった。[0004] However, in the above method, the larger the change width of the polymerization temperature in the polymerization reaction (hereinafter, referred to as "temperature rise width"), the larger the bulk specific gravity and the gelation melting rate, but the larger the temperature rise width. If it is too large, the heat generation becomes so large at the end of the polymerization reaction that cooling becomes difficult, or the polymerization reaction is not sufficiently performed at the end of the reaction due to a shortage of the polymerization initiator, and the polymerization reaction is not completed within the expected time. There was such a problem.
【０００５】[0005]
【発明が解決しようとする課題】重合反応末期において
も重合が十分に行なわれ、かつ、得られた塩化ビニル系
重合体よりなる樹脂の嵩比重及びゲル化溶融速度が大き
い塩化ビニル系重合体の製造方法を提供することが本発
明の課題である。In the final stage of the polymerization reaction, the polymerization is sufficiently carried out, and the obtained vinyl chloride-based resin has a high bulk specific gravity and a high gelation / melting rate. It is an object of the present invention to provide a manufacturing method.
【０００６】[0006]
【課題を解決するための手段】即ち、本発明の要旨は、
塩化ビニル単量体または塩化ビニル単量体を主体とする
共重合可能な単量体の混合物を水性媒体中で重合反応さ
せて塩化ビニル系重合体を製造する方法において、重合
反応が進行する期間全体の５０％以上の期間において重
合温度を時間とともに上昇させつつ重合反応を行なわせ
ること、その上昇変化幅が１０〜３５℃の範囲にあるこ
と、重合反応を下式（１）〜（５）を満たす２種類の重
合開始剤の存在下で行なわせること、かつ、該２種類の
重合開始剤の重量比が、２０／８０〜８０／２０である
ことを特徴とする塩化ビニル系重合体の製造方法、に存
する。That is, the gist of the present invention is as follows.
In a method for producing a vinyl chloride polymer by polymerizing a vinyl chloride monomer or a mixture of copolymerizable monomers mainly composed of a vinyl chloride monomer in an aqueous medium, a period in which the polymerization reaction proceeds The polymerization reaction is carried out while increasing the polymerization temperature with time in a period of 50% or more of the whole, that the variation in the rise is in the range of 10 to 35 ° C., and the polymerization reaction is performed by the following formulas (1) to (5) Characterized in that the polymerization is carried out in the presence of two kinds of polymerization initiators satisfying the following conditions, and the weight ratio of the two kinds of polymerization initiators is 20/80 to 80/20. Manufacturing method.
【０００７】[0007]
【数２】 ２０℃≦Ｔ1 ＜Ｔ2 ≦８０℃ （１） ３０℃≦ｔ1 ≦５０℃ （２） ４５℃≦ｔ2 ≦６０℃ （３） ｔ1 ＜ｔ2 （４） ただし、 ｔ1 ，ｔ2 ：使用する重量開始剤の１０時間半減期温度
（℃） Ｔ1 ：重合開始温度（℃） Ｔ2 ：重合終了温度（℃） 以下、本発明を更に詳細に説明する。20 ° C. ≦ T 1 <T 2 ≦ 80 ° C. (1) 30 ° C. ≦ t 1 ≦ 50 ° C. (2) 45 ° C. ≦ t 2 ≦ 60 ° C. (3) t 1 <t 2 (4) Here, t 1 , t 2 : 10-hour half-life temperature (° C.) of the weight initiator used T 1 : polymerization start temperature (° C.) T 2 : polymerization end temperature (° C.) Hereinafter, the present invention will be described in more detail. .
【０００８】本発明方法において使用される塩化ビニル
系単量体には、塩化ビニル単量体それ自体のほか、塩化
ビニル単量体を主体とする共重合可能な単量体の混合物
が含まれる。塩化ビニル単量体と共重合可能な単量体と
しては、例えばエチレン、プロピレンなどのオレフィン
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、エチルビニルエーテル、セチルビニルエーテル
などのビニルエーテル類、アクリル酸エステル、マレイ
ン酸またはフマル酸のエステル類及び無水物などの不飽
和カルボン酸誘導体類、アクリロニトリルなどの不飽和
ニトリル類等が挙げられる。該共重合可能な単量体は塩
化ビニル単量体に対し、通常、２０重量％以下の割合で
使用される。The vinyl chloride monomer used in the method of the present invention includes, in addition to the vinyl chloride monomer itself, a mixture of copolymerizable monomers mainly composed of the vinyl chloride monomer. . Monomers copolymerizable with vinyl chloride monomers include, for example, olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl stearate, vinyl ethers such as ethyl vinyl ether and cetyl vinyl ether, and acrylic acid esters. And unsaturated carboxylic acid derivatives such as esters and anhydrides of maleic acid or fumaric acid, and unsaturated nitriles such as acrylonitrile. The copolymerizable monomer is usually used in a proportion of 20% by weight or less based on the vinyl chloride monomer.
【０００９】本発明方法における塩化ビニル系単量体の
重合には、通常知られている塩化ビニル系単量体の水性
媒体中での重合処方が広く採用される。使用される分散
剤、乳化剤などは特殊なものである必要はなく、汎用さ
れている分散剤、乳化剤を用いることができる。例え
ば、分散剤、乳化剤としては、ポリ酢酸ビニルの部分ケ
ン化物、アクリル酸共重合体、無水マレイン酸共重合
体、セルロース誘導体、ゼラチン、デンプンなどのよう
な保護コロイド性の薬剤または天然高分子化合物、高級
脂肪酸と多価アルコールとのエステル類、ポリオキシエ
チレン誘導体などのノニオン系界面活性剤、高級脂肪酸
の金属塩、高級アルコール硫酸エステルのアルカリ塩な
どのアニオン系界面活性剤などが用いられる。これらの
分散剤、乳化剤の使用量には特に制限はなく、その種
類、攪拌効率、重合温度、塩化ビニル単量体と共重合さ
せられる他の単量体の種類と組成、塩化ビニル系重合体
の粒径等によって多少異なるが、一般には塩化ビニル系
単量体の総量に対して０．０１〜２．０重量％、好まし
くは０．０３〜１重量％の範囲内で用いられる。In the polymerization of the vinyl chloride-based monomer in the method of the present invention, a generally known polymerization formulation of a vinyl chloride-based monomer in an aqueous medium is widely used. The dispersant, emulsifier and the like used need not be special ones, and widely used dispersants and emulsifiers can be used. For example, as a dispersant or emulsifier, a partially saponified polyvinyl acetate, an acrylic acid copolymer, a maleic anhydride copolymer, a cellulose derivative, gelatin, a protective colloidal agent such as starch or a natural polymer compound Nonionic surfactants such as esters of higher fatty acids and polyhydric alcohols, polyoxyethylene derivatives and the like, anionic surfactants such as metal salts of higher fatty acids and alkali salts of higher alcohol sulfates, etc. are used. There are no particular restrictions on the amount of these dispersants and emulsifiers used, and their types, stirring efficiency, polymerization temperature, types and compositions of other monomers that can be copolymerized with the vinyl chloride monomer, vinyl chloride polymers Although it varies somewhat depending on the particle size of the vinyl chloride monomer, it is generally used in the range of 0.01 to 2.0% by weight, preferably 0.03 to 1% by weight, based on the total amount of the vinyl chloride monomer.
【００１０】また、本発明において使用される重合開始
剤としては、ｔ−ブチルペルオキシピバレート（１０時
間半減期温度（以下同じ）：５５℃）、ｔ−ヘキシルペ
ルオキシピバレート（５３．２℃）、ｔ−ブチルペルオ
キシネオデカノエート（４６．５℃）、クミルペルオキ
シネオデカノエート（３６．６℃）、ビス（２−エチル
ヘキシル）ペルオキシジカーボネート（４３．５℃）、
ジイソプロピルペルオキシジカーボネート（４０．５
℃、但し初期濃度０．０５ｍｏｌ／ｌ）などの有機過酸
化物、アゾビス（ジメチルバレロニトリル）（５１℃、
但しトルエン溶媒中）などのアゾ化合物等が挙げられ、
このような重合開始剤から重合開始温度及び重合終了温
度に応じ、前記した（２）〜（５）式を満たすような２
種類の重合開始剤を選択して使用する。The polymerization initiator used in the present invention includes t-butyl peroxypivalate (10-hour half-life temperature (the same applies hereinafter): 55 ° C.) and t-hexyl peroxypivalate (53.2 ° C.) , T-butyl peroxy neodecanoate (46.5 ° C), cumyl peroxy neodecanoate (36.6 ° C), bis (2-ethylhexyl) peroxydicarbonate (43.5 ° C),
Diisopropyl peroxydicarbonate (40.5
° C, but an initial concentration of 0.05 mol / l) organic peroxide such as azobis (dimethylvaleronitrile) (51 ° C,
However, azo compounds such as in a toluene solvent) and the like,
According to the polymerization initiation temperature and the polymerization end temperature from such a polymerization initiator, 2 such that the above formulas (2) to (5) are satisfied is satisfied.
A type of polymerization initiator is selected and used.
【００１１】上記重合開始剤の１０間半減期温度は、ベ
ンゼン溶媒中において、初期濃度０．１ｍｏｌ／ｌの重
合開始剤が１０時間でその濃度が１／２となる分解温度
として定義される。本発明方法において用いるＴ1 及び
Ｔ2 は、目的とする塩化ビニル系重合体の平均重合度に
よって選択され、その際に使用する重合開始剤は、１０
時間半減期温度として、前述のように（２）〜（５）式
を満たすものの中から選択するが、特に下式（６）及び
（７）The above-mentioned half-life temperature of the polymerization initiator is defined as a decomposition temperature at which the concentration of the polymerization initiator having an initial concentration of 0.1 mol / l becomes 1/2 in 10 hours in a benzene solvent. T 1 and T 2 used in the method of the present invention are selected according to the average degree of polymerization of the target vinyl chloride polymer, and the polymerization initiator used at that time is 10
The time half-life temperature is selected from those satisfying the expressions (2) to (5) as described above, and in particular, the following expressions (6) and (7)
【００１２】[0012]
【数３】 Ｔ1 −１５≦ｔ1 ≦Ｔ1 −５ （６） Ｔ2 −２０≦ｔ2 ≦Ｔ2 −１０ （７） を満たすものの中から選ぶことが好ましく、このとき、
反応活性と反応制御性とを、共に良好に保つ操作が容易
となる。It is preferable to select from those satisfying T 1 −15 ≦ t 1 ≦ T 1 −5 (6) T 2 −20 ≦ t 2 ≦ T 2 -10 (7)
The operation of maintaining both the reaction activity and the reaction controllability in good condition becomes easy.
【００１３】本発明方法において使用する重合開始剤の
組み合せとしては、１０時間半減期温度の差を１５℃以
上とることができ、また塩化ビニル系樹脂で多く用いら
れる平均重合度範囲（例えば８００〜１３００など）を
カバーする重合温度域に適合しているものが好ましい。
このような重合開始剤の組み合せとしては、例えばｔ−
ヘキシルペルオキシピバレート（以下、「ＨＰＶ」と記
す）とクミルペルオキシネオデカノエート（以下、「Ｃ
ＮＤ」と記す）との組み合せが挙げられる。The combination of the polymerization initiators used in the method of the present invention can be such that the difference in the 10-hour half-life temperature can be 15 ° C. or more, and the average polymerization degree range frequently used for vinyl chloride resins (for example, 800 to 800). 1300) is preferred.
As a combination of such polymerization initiators, for example, t-
Hexyl peroxypivalate (hereinafter referred to as “HPV”) and cumyl peroxy neodecanoate (hereinafter “C”)
ND ").
【００１４】前記（１),（４）式の条件の下で、（２),
（３）及び（５）式を満たさない重合開始剤を使用した
場合、例えば、ｔ1 ＜３０℃となる重合開始剤を使用し
た場合には、重合開始剤の重合反応初期の分解速度が速
く、反応制御性が悪化する。また、６０℃＜ｔ2 となる
場合には、重合開始剤の分解速度が遅く、反応末期の急
激な反応や、あるいは得られた塩化ビニル系重合体中へ
の重合開始剤の残留による熱安定性低下の原因となりや
すい。Under the conditions of the above equations (1) and (4), (2),
When a polymerization initiator that does not satisfy the formulas (3) and (5) is used, for example, when a polymerization initiator that satisfies t 1 <30 ° C. is used, the decomposition rate of the polymerization initiator in the early stage of the polymerization reaction is high. However, the reaction controllability deteriorates. When 60 ° C. <t 2 , the rate of decomposition of the polymerization initiator is low, and a rapid reaction at the end of the reaction or thermal stability due to the residual polymerization initiator in the obtained vinyl chloride polymer. It is easy to cause deterioration of sex.
【００１５】[0015]
【数４】 となる場合は重合反応末期に反応速度が著しく低下した
り、または反応が初期には起きにくく、末期に急激な発
熱を伴う暴走反応となる恐れがある。(Equation 4) In such a case, the reaction rate may be remarkably reduced at the end of the polymerization reaction, or the reaction may hardly occur in the early stage, resulting in a runaway reaction accompanied by rapid heat generation at the end.
【００１６】[0016]
【数５】 となる場合は、重合温度と重合開始剤の分解とにずれが
あり、反応速度が不十分となったり、反応制御性が悪化
したりする傾向となる。(Equation 5) In such a case, there is a difference between the polymerization temperature and the decomposition of the polymerization initiator, and the reaction rate tends to be insufficient or the reaction controllability tends to be deteriorated.
【００１７】これらの重合開始剤の合計使用量は、一般
に使用される量、すなわち塩化ビニル系単量体の総量に
対して０．０１〜１．０重量％の範囲であり、２種類の
重合開始剤の重量比は、［ｔ1 ］／［ｔ2 ］＝２０／８
０〜８０／２０とする（ただし、［ｔ1 ］，［ｔ2 ］は
それぞれ１０時間半減期温度がｔ1 ，ｔ2 である重合開
始剤の配合量を意味するものとする。）。The total amount of these polymerization initiators used is generally in the range of 0.01 to 1.0% by weight based on the amount used, that is, the total amount of vinyl chloride monomers. The weight ratio of the initiator is [t 1 ] / [t 2 ] = 20/8
0 to 80/20 (provided that [t 1 ] and [t 2 ] mean the amounts of the polymerization initiators whose 10-hour half-life temperatures are t 1 and t 2 , respectively).
【００１８】［ｔ1 ］／［ｔ2 ］が２０／８０より小さ
い場合には、反応初期に発熱が小さく、末期に発熱が大
きくなり、重合缶内温を制御できなくなる恐れがあり、
また８０／２０より大きい場合には、反応初期から発熱
するが、反応末期で発熱が微弱となり、反応が緩慢とな
ったり停止したりする恐れがある。また、本発明の重合
反応に際し、一般に知られている重合助剤、例えばトリ
クロルエチレン、ドデシルメルカプタン、２−メルカプ
トエタノール、プロピオンアルデヒド等の連鎖移動剤、
酸化防止剤等を任意に使用することができる。If [t 1 ] / [t 2 ] is less than 20/80, the exotherm is small at the beginning of the reaction and large at the end of the reaction, and the internal temperature of the polymerization reactor may not be controlled.
If it is larger than 80/20, heat is generated from the beginning of the reaction, but the heat is weakened at the end of the reaction, and the reaction may be slow or stopped. In the polymerization reaction of the present invention, generally known polymerization aids, for example, trichloroethylene, dodecyl mercaptan, 2-mercaptoethanol, chain transfer agents such as propionaldehyde,
An antioxidant and the like can be optionally used.
【００１９】本発明方法を実施するにあたり、塩化ビニ
ル系単量体は重合開始前に一括して仕込んでもよいし、
あるいは塩化ビニル系単量体の一部を重合開始前に仕込
み、残部を重合開始後に連続して、または分割して仕込
むこともできる。さて、本発明方法においては、重合反
応が進行する期間全体のうち５０％以上の期間において
重合温度を時間と共に上昇させつつ塩化ビニル系単量体
の重合反応を行なわせる。In carrying out the method of the present invention, the vinyl chloride monomer may be charged at once before the start of polymerization,
Alternatively, a part of the vinyl chloride-based monomer may be charged before the start of the polymerization, and the remaining part may be charged continuously or separately after the start of the polymerization. Now, in the method of the present invention, the polymerization reaction of the vinyl chloride monomer is carried out while increasing the polymerization temperature with time in a period of 50% or more of the entire period in which the polymerization reaction proceeds.
【００２０】上記「重合反応が進行する期間全体」と
は、通常の塩化ビニル系単量体の重合処方に従い、重合
開始剤、その他の添加物の存在下に塩化ビニル系単量体
を重合するに当り、重合反応系の昇温により重合開始剤
が分解を開始して塩化ビニル系単量体の重合が開始する
時点から、目的とする重合率に達して重合反応を終了さ
せる時点までの期間全体を意味する。The above "whole period during which the polymerization reaction proceeds" means that the vinyl chloride monomer is polymerized in the presence of a polymerization initiator and other additives in accordance with the usual polymerization recipe of the vinyl chloride monomer. The period from the point when the polymerization initiator starts to decompose due to the temperature rise of the polymerization reaction system and the polymerization of the vinyl chloride monomer starts, and the point when the polymerization reaction reaches the target degree of polymerization and ends the polymerization reaction Means the whole.
【００２１】従って、従来、重合反応器内に原料の仕込
みを行なった後、重合反応が開始するまで、即ち、重合
開始剤が分解を開始して発熱反応が始まるまでは、例え
ば、重合反応器に取り付けたジャケットに温水を循環さ
せる等の通常の加熱方法で加熱して、急速に昇温させ、
次いで重合反応が開始した時点から重合反応を終了させ
る時点までの期間、即ち、重合反応が進行する期間内
は、発熱による温度の大幅な上昇をジャケットに冷却水
を循環させる等の方法によりおさえて一定温度に保持し
て所定の重合度の重合体を得ていたのに対して、本発明
方法では、特にこの重合反応が進行する期間全体のうち
５０％以上の期間について、重合温度を時間と共に適当
な速度で上昇させるように冷却の程度を調節しながら重
合反応を行なわせるのである。Therefore, conventionally, after the raw materials are charged into the polymerization reactor, until the polymerization reaction starts, that is, until the polymerization initiator starts to decompose and the exothermic reaction starts, for example, Heating by a normal heating method such as circulating warm water to the jacket attached to the
Next, during the period from the start of the polymerization reaction to the end of the polymerization reaction, that is, during the period in which the polymerization reaction proceeds, a large increase in temperature due to heat generation is suppressed by a method such as circulating cooling water through a jacket. In contrast to obtaining a polymer having a predetermined degree of polymerization while maintaining a constant temperature, in the method of the present invention, the polymerization temperature is increased with time, particularly for 50% or more of the entire period in which the polymerization reaction proceeds. The polymerization reaction is carried out while controlling the degree of cooling so as to increase the temperature at an appropriate rate.
【００２２】「重合反応が進行する期間全体の５０％未
満」での急速な昇温は、残存する、１０時間半減期温度
がｔ1 である重合開始剤（以下、「低温活性の重合開始
剤」という）の急速な分解により、反応温度が制御不能
となるか、または低温活性の重合開始剤の殆どが分解し
た後に昇温しなければならないために反応発熱の不均一
が生じるので反応制御が難しく、また重合反応器の除熱
能力も大きなものが必要となり、生産性が低くなる。The rapid temperature rise in the "polymerization reaction is less than 50% of the total period of progression" is the remaining 10-hour half-life temperature t 1 at which the polymerization initiator (hereinafter, the polymerization initiator "low-temperature activity )), The reaction temperature becomes uncontrollable, or the reaction must be heated after most of the low temperature active polymerization initiator has decomposed, resulting in non-uniform reaction exotherm. It is difficult and requires a large heat removal capability of the polymerization reactor, which lowers productivity.
【００２３】次に、従来の、重合反応系を一定温度に保
持して重合反応を行なわせる方法（以下、「定温反応
法」という）と本発明方法とを対比すると、重合温度に
ついて、前者がその「高さ」のみによって律せられてい
たのに対し、後者はその「高さ」及び「昇温幅」の両者
によって律せられているという相違がある。しかして本
発明方法における重合温度の「高さ」及び「昇温幅」の
設定は、本質的には目的とする塩化ビニル系重合体が得
られるように実験的に定められるものであるが、具体的
には一定の指針に従って決めて行くことができる。Next, a comparison between the conventional method in which the polymerization reaction is carried out while maintaining the polymerization reaction system at a constant temperature (hereinafter, referred to as "constant temperature reaction method") and the method of the present invention shows that the polymerization temperature is the former. The difference is that the latter is governed only by its "height", whereas the latter is governed by both its "height" and "temperature rise width". Thus, the setting of the “height” and “temperature increase width” of the polymerization temperature in the method of the present invention is essentially determined experimentally so as to obtain the intended vinyl chloride polymer, Specifically, it can be determined according to certain guidelines.
【００２４】即ち、先ず、定温反応法において生成する
塩化ビニル系重合体の重合度が重合温度の「高さ」によ
って支配されることが知られているが、これは本発明方
法においても本質的に同様である。従って例えば、本発
明方法において重合温度の変化域に基づいて重合温度の
「平均的高さ」を考えれば、該「平均的高さ」を、定温
反応法において目的とする重合度の生成物を得るための
重合温度の「高さ」の近傍に設定すれば、ほぼ目的とす
る重合度の生成物を得ることができる。無論、「定温反
応法」と本発明のいわば「昇温反応法」とは同一ではな
く、後者はその昇温パターンによっても影響を受ける。
即ち、得られる全重合体の平均重合度は、その昇温過程
の各時点で生成する重合体の重合度の、その際の重合体
の生成量による加重平均となるのであり、その生成量は
昇温パターンの選択によっても影響を受けるのである。
従って、正確な「平均的高さ」の設定は、昇温パターン
を決定した上で実験的に行なうのが望ましい。That is, first, it is known that the degree of polymerization of the vinyl chloride polymer produced in the constant temperature reaction method is governed by the "height" of the polymerization temperature, which is also essential in the method of the present invention. The same applies to Therefore, for example, if the `` average height '' of the polymerization temperature is considered based on the change range of the polymerization temperature in the method of the present invention, the `` average height '' is determined as the product having the desired degree of polymerization in the constant temperature reaction method. If the temperature is set near the "height" of the polymerization temperature, a product having a substantially desired degree of polymerization can be obtained. Needless to say, the "constant temperature reaction method" is not the same as the so-called "temperature rising reaction method" of the present invention, and the latter is affected by the temperature rising pattern.
That is, the average degree of polymerization of all the obtained polymers is the weighted average of the degree of polymerization of the polymer generated at each point in the temperature raising process, and the amount of the polymer generated at that time, and the amount of the generation is It is also affected by the choice of heating pattern.
Therefore, it is desirable to set the accurate “average height” experimentally after determining the heating pattern.
【００２５】次に重合温度の「昇温幅」は主として本発
明方法における連続昇温の効果を支配するものである。
本発明においては、該「昇温幅」は、１０〜３５℃、好
ましくは１５〜３０℃の範囲である。「変化幅」が１０
℃より小さいと、本発明の製造方法による改良効果が十
分ではなく、従来の方法により得られた塩化ビニル系重
合体に比べ嵩比重及びゲル化溶融速度が大きい塩化ビニ
ル系重合体を得ることは困難となる。また、３５℃より
大きいと、重合反応末期に発熱が急激に大きくなりすぎ
冷却が困難になる恐れがある。Next, the "temperature increase width" of the polymerization temperature mainly governs the effect of continuous temperature increase in the method of the present invention.
In the present invention, the “temperature increase width” is in the range of 10 to 35 ° C., preferably 15 to 30 ° C. "Change width" is 10
When the temperature is lower than ℃, the improvement effect of the production method of the present invention is not sufficient, and it is difficult to obtain a vinyl chloride polymer having a higher bulk specific gravity and a higher gelation melting rate than the vinyl chloride polymer obtained by the conventional method. It will be difficult. On the other hand, if the temperature is higher than 35 ° C., the heat generation may be too large at the end of the polymerization reaction, and cooling may be difficult.
【００２６】重合温度の「平均的高さ」及び「昇温幅」
の好適値は具体的な反応系、主として単量体組成及び重
合開始剤の性能によっても影響を受けるので、これらを
も含めた具体的は反応系について経験的に選択されるの
が望ましい。具体的な重合温度の変化域、即ち重合温度
域での昇温開始温度及び昇温終了温度の決定は、例えば
次のように行なうことができる。"Average height" and "heating range" of polymerization temperature
Is also affected by the specific reaction system, mainly the monomer composition and the performance of the polymerization initiator. Therefore, it is desirable that the specific value including these factors be selected empirically for the reaction system. The specific change range of the polymerization temperature, that is, the temperature rise start temperature and the temperature rise end temperature in the polymerization temperature range can be determined, for example, as follows.
【００２７】即ち、モデル的に、全昇温範囲にわたり、
重合反応速度を一定とし、かつ、重合反応の全期間を昇
温期間とする場合を考えると、定温反応法において所望
の重合度の塩化ビニル系重合体を得るのに必要な重合温
度をｔ0 （℃）、昇温反応法における温度上昇幅を２Δ
ｔ（℃）としたとき、昇温開始温度を（ｔ0 −Δｔ）、
昇温終了温度を（ｔ0 ＋Δｔ）、従って重合温度範囲をThat is, modelly, over the entire heating range,
Considering the case where the polymerization reaction rate is kept constant and the entire period of the polymerization reaction is set to be a heating period, the polymerization temperature required to obtain a vinyl chloride polymer having a desired degree of polymerization in the constant temperature reaction method is t 0. (° C.), and the temperature increase width in the temperature raising reaction method is 2Δ
When t (° C.), the temperature rise start temperature is (t 0 −Δt),
The temperature at the end of the temperature rise is (t 0 + Δt), and thus the polymerization temperature range is
【００２８】[0028]
【数６】（ｔ0 −Δｔ）〜（ｔ0 ＋Δｔ） とするのである。## EQU6 ## (t 0 −Δt) to (t 0 + Δt)
【００２９】なお上記の説明は最も一般的な直線的昇温
パターンを前提としたものであり、この場合にはほぼ予
想通りの結果を得ることができるが、前述の通り、本発
明の「昇温反応法」の反応結果はその昇温パターンによ
っても影響を受けるので、特に非直線的な昇温パターン
を採用する場合には、目的とする生成物に応じて実験的
に多少の修正をするのが望ましい。The above description is based on the most general linear heating pattern. In this case, almost the expected results can be obtained. The reaction results of the "temperature reaction method" are also affected by the heating pattern, so if you use a non-linear heating pattern, make some experimental corrections depending on the target product. It is desirable.
【００３０】本発明方法における重合温度の昇温速度は
重合温度の上昇温度幅と昇温期間とから一義的に求めら
れる昇温速度とすること（即ち、直線的昇温パターンと
すること）が最も簡便であり、良い結果を与える。例え
ば、重合温度範囲を５０〜６０℃とし、全重合反応時間
を８時間とし、そのうち５時間を昇温期間とした場合に
は、２℃／ｈｒの昇温速度とすればよい。また、昇温速
度を昇温の途中で変えること、即ち、昇温パターンに屈
曲点を設けることは、その点での過大な加熱または冷却
能力を必要とされることとなり一般的には好ましいこと
ではないが、温度制御上許容される程度の変動はその結
果に大きな影響を与えないので、本発明の実施態様の一
つとして許容し得るものである。例えば、反応中に昇温
速度を１．５℃／ｈｒから０．５℃／ｈｒに変更した
り、或いはその前後に一定温度に維持する期間を設けた
りする等の方法も、昇温期間の合計が全重合反応期間の
５０％以上であるようにしておけば、本発明の一実施態
様として許容され得るものである。本発明方法における
重合温度の昇温速度は通常１０℃／ｈｒ以下であるのが
反応制御性の点から望ましい。In the method of the present invention, the rate of temperature rise of the polymerization temperature is set to a rate uniquely determined from the temperature range and the temperature rise period of the polymerization temperature (that is, a linear temperature rise pattern). It is the simplest and gives good results. For example, when the polymerization temperature range is 50 to 60 ° C., the total polymerization reaction time is 8 hours, and 5 hours is the heating period, the heating rate may be 2 ° C./hr. Also, changing the heating rate in the course of the heating, that is, providing a bending point in the heating pattern requires an excessive heating or cooling capacity at that point, which is generally preferable. However, the degree of fluctuation allowed for temperature control does not significantly affect the result, and is thus acceptable as one of the embodiments of the present invention. For example, a method of changing the heating rate from 1.5 ° C./hr to 0.5 ° C./hr during the reaction or providing a period for maintaining a constant temperature before and after the reaction is also available. If the total is 50% or more of the total polymerization reaction period, it is acceptable as one embodiment of the present invention. In the method of the present invention, the rate of temperature rise of the polymerization temperature is usually preferably 10 ° C./hr or less from the viewpoint of reaction controllability.
【００３１】本発明方法における重合反応の制御は、滑
らかな昇温を可能とするような制御方法であれば特に制
限されるものではないが、例えばコンピュータを採り入
れたフィードバック制御、フィードフォワード制御等が
生産性、制御性、安定性の面で好適である。本発明方法
は、水性媒体中での塩化ビニル系単量体の重合であれば
どのような方法についても採用可能であるが、特に油溶
性重合開始剤を用いる懸濁重合法に適用するのが、工業
的に最も有用であり、価値が高い。The control of the polymerization reaction in the method of the present invention is not particularly limited as long as it is a control method capable of smoothly raising the temperature. For example, feedback control using a computer, feed forward control, etc., may be used. It is suitable in terms of productivity, controllability, and stability. The method of the present invention can be applied to any method as long as it is a method for polymerizing a vinyl chloride monomer in an aqueous medium, but it is particularly applicable to a suspension polymerization method using an oil-soluble polymerization initiator. The most useful and industrially valuable.
【００３２】[0032]
【実施例】次に本発明を実施例により更に具体的に説明
するが、本発明は、その要旨を越えない限り、以下の実
施例によって限定されるものではない。なお、得られる
塩化ビニル系重合体の物性評価は下記の物性測定方法に
より行なった。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. The physical properties of the obtained vinyl chloride polymer were evaluated by the following physical property measuring methods.
【００３３】物性測定方法 平均重合度及び嵩比重 ＪＩＳ Ｋ−６７２１に示される方法に準じて求めた。 ゲル化時間 ＰＶＣ１００重量部、鉛系粉末安定剤３重量部及びバリ
ウム系粉末安定剤０．５重量部をブレンドした試料６０
ｇを、ブラベンダー・プラスチコーダー（１８７℃、４
５ｒｐｍ）で混練し、最大トルクを示すまでの時間を測
定した。Methods for measuring physical properties Average polymerization degree and bulk specific gravity Determined according to the method described in JIS K-6721. Gelation time Sample 60 prepared by blending 100 parts by weight of PVC, 3 parts by weight of a lead-based powder stabilizer and 0.5 parts by weight of a barium-based powder stabilizer.
g at a temperature of 187 ° C.
The mixture was kneaded at 5 rpm) and the time until the maximum torque was shown was measured.
【００３４】実施例１〜２ 内容積４００リットルの攪拌機及びジャケット付のステ
ンレス製重合容器に塩化ビニル単量体１００ｋｇ、脱イ
オン水１５０ｋｇ、ポリ酢酸ビニル部分ケン化物（日本
合成化学工業（株）製、ゴーセノールＫＨ−１７、平均
重合度２３００、ケン化度８８．５％）６０ｇおよび表
−１に示す重合開始剤を仕込んだ。仕込みが終了した
後、ジャケットに温水を循環させ、表−１に示す昇温開
始温度まで急速に加熱して重合反応を開始させた。その
後、連続的に昇温を行ない、表−１に示した温度で昇温
を終了し、以後目的とする反応転化率（８０％）に達す
るまで、この温度を保持した。このようにして得られた
塩化ビニル系重合体（以下「ＰＶＣ」と記す）の物性評
価を行なった結果を表−２に示した。 Examples 1 and 2 100 kg of vinyl chloride monomer, 150 kg of deionized water, partially saponified polyvinyl acetate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were placed in a stainless steel polymerization vessel equipped with a stirrer and jacket having a capacity of 400 liters. , Gohsenol KH-17, average polymerization degree 2300, saponification degree 88.5%), and 60 g of the polymerization initiator shown in Table 1. After the charging was completed, warm water was circulated through the jacket, and the polymerization reaction was started by rapidly heating to the temperature at which the temperature started to rise as shown in Table 1. Thereafter, the temperature was raised continuously, the temperature was raised at the temperature shown in Table 1, and the temperature was maintained until the desired reaction conversion (80%) was reached. Table 2 shows the results of evaluation of the physical properties of the thus obtained vinyl chloride polymer (hereinafter referred to as “PVC”).
【００３５】比較例１〜１０ 重合開始剤及びその使用量をそれぞれ表−１に示すよう
に変化させたこと以外は実施例１と同様にして仕込みを
行なった。次いで表−１に示す反応条件で重合反応を行
なったこと以外は実施例１と同様にして目的とする反応
転化率（８０％）に達するまで、昇温終了温度を保持し
た。このようにして得られたＰＶＣの物性評価を行なっ
た結果をそれぞれ表−２に示した。 Comparative Examples 1 to 10 Preparation was carried out in the same manner as in Example 1 except that the polymerization initiator and the amount used were changed as shown in Table 1. Next, the temperature-raising end temperature was maintained until the target reaction conversion (80%) was reached in the same manner as in Example 1 except that the polymerization reaction was carried out under the reaction conditions shown in Table 1. Table 2 shows the results of the evaluation of the physical properties of the PVC thus obtained.
【００３６】比較例１〜３では、昇温幅が小さいため実
施例と比較し、ゲル化溶融速度及び嵩比重が小さいＰＶ
Ｃが得られた。比較例４では、反応末期に反応速度が著
しく低下し、所期の反応率を達成できず、反応を途中で
取り止めた。比較例５〜７では、反応初期にはほとんど
発熱がなかったにもかかわらず、反応末期に急激な発熱
が生じ、反応制御が著しく困難となった。また比較例８
〜１０の場合、反応初期〜中期にかけて、限界冷却能力
に近いかなりの発熱があったにもかかわらず、反応末期
には発熱がとまり、目的とする反応転化率（８０％）に
至らなかった。In Comparative Examples 1 to 3, since the temperature rise width was small, compared to the Examples, the gelation melting rate and the PV having a low bulk specific gravity were compared.
C was obtained. In Comparative Example 4, the reaction rate was remarkably reduced at the end of the reaction, the desired reaction rate could not be achieved, and the reaction was stopped halfway. In Comparative Examples 5 to 7, although little heat was generated at the beginning of the reaction, a sudden heat was generated at the end of the reaction, and the control of the reaction became extremely difficult. Comparative Example 8
In the case of -10 to 10, the exotherm ceased at the end of the reaction from the early stage to the middle stage of the reaction even though the exotherm was close to the critical cooling capacity, and did not reach the target reaction conversion (80%).
【００３７】比較例１１ 重合開始剤及びその使用量を表−１に示すように変化さ
せたこと以外は実施例１と同様にして仕込みを行なっ
た。次いで表−１に示す反応条件で重合反応を行ない、
反応転化率６０％にて反応温度を４８℃から６８℃に３
０分間で昇温したが、残存するクミルペルオキシネオデ
カノエート（ＣＮＤ）が急激に分解し、発熱が大きくな
り、反応制御が著しく困難となった。 Comparative Example 11 Preparation was carried out in the same manner as in Example 1 except that the polymerization initiator and the amount used were changed as shown in Table 1. Next, a polymerization reaction was carried out under the reaction conditions shown in Table 1,
The reaction temperature was increased from 48 ° C to 68 ° C at a reaction conversion of 60% by 3
Although the temperature was raised in 0 minutes, the remaining cumyl peroxyneodecanoate (CND) was rapidly decomposed, the heat generation increased, and the reaction control became extremely difficult.
【００３８】比較例１２ 重合開始剤の使用量を表−１に示すように変化させたこ
と以外は比較例１１と同様にして仕込み及び重合反応を
行なった。反応転化率が６０％に至る前にＣＮＤ量が不
足したためか反応速度が低下したので、３０分間かけて
４８℃から６８℃に昇温した。その結果、反応速度が著
しく増大して、冷却負荷が極めて大きくなり反応制御が
著しく困難であった。 Comparative Example 12 A charging and polymerization reaction were carried out in the same manner as in Comparative Example 11 except that the amount of the polymerization initiator used was changed as shown in Table 1. Before the conversion of the reaction reached 60%, the reaction rate slowed down, possibly due to an insufficient amount of CND. Therefore, the temperature was raised from 48 ° C. to 68 ° C. over 30 minutes. As a result, the reaction rate was significantly increased, the cooling load was extremely increased, and the reaction control was extremely difficult.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【表２】 [Table 2]
【００４１】[0041]
【発明の効果】本発明によれば、従来の方法によって得
られたＰＶＣと比較して、ゲル化溶融速度が著しく大き
く、かつ、嵩比重も大きく、成形加工性の優れたＰＶＣ
を安定に製造することができる。According to the present invention, compared to PVC obtained by a conventional method, a PVC having a remarkably high gelling melting rate, a large bulk specific gravity, and excellent moldability.
Can be manufactured stably.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 2/00 - 2/60 C08F 4/38,14/06 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C08F 2/00-2/60 C08F 4 / 38,14 / 06
Claims (2)
体を主体とする共重合可能な単量体の混合物（以下、こ
れらを総称して「塩化ビニル系単量体」という）を水性
媒体中で重合反応させて塩化ビニル系重合体を製造する
方法において、重合反応が進行する期間全体の５０％以
上の期間において重合温度を時間とともに上昇させつつ
重合反応を行なわせること、その上昇変化幅が１０〜３
５℃の範囲にあること、重合反応を下式（１）〜（５）
を満たす２種類の重合開始剤の存在下で行なわせるこ
と、かつ、該２種類の重合開始剤の重量比が、２０／８
０〜８０／２０であることを特徴とする塩化ビニル系重
合体の製造方法。 【数１】 ２０℃≦Ｔ1 ＜Ｔ2 ≦８０℃ （１） ３０℃≦ｔ1 ≦５０℃ （２） ４５℃≦ｔ2 ≦６０℃ （３） ｔ1 ＜ｔ2 （４） ただし、 ｔ1 ，ｔ2 ：使用する重量開始剤の１０時間半減期温度
（℃） Ｔ1 ：重合開始温度（℃） Ｔ2 ：重合終了温度（℃）An aqueous medium containing a vinyl chloride monomer or a mixture of copolymerizable monomers mainly composed of a vinyl chloride monomer (hereinafter, these are collectively referred to as “vinyl chloride monomers”). In the method for producing a vinyl chloride polymer by a polymerization reaction in a reactor, the polymerization reaction is carried out while increasing the polymerization temperature with time in a period of 50% or more of the entire period in which the polymerization reaction proceeds, Is 10-3
In the range of 5 ° C., the polymerization reaction is carried out by the following formulas (1) to (5).
And the weight ratio of the two polymerization initiators is 20/8.
A method for producing a vinyl chloride polymer, which is from 0 to 80/20. 20 ° C. ≦ T 1 <T 2 ≦ 80 ° C. (1) 30 ° C. ≦ t 1 ≦ 50 ° C. (2) 45 ° C. ≦ t 2 ≦ 60 ° C. (3) t 1 <t 2 (4) Here, t 1 , t 2 : 10-hour half-life temperature (° C.) of the weight initiator used T 1 : polymerization start temperature (° C.) T 2 : polymerization end temperature (° C.)
ルオキシピバレート及びクミルペルオキシネオデカノエ
ートである請求項１に記載の塩化ビニル系重合体の製造
方法。2. The method for producing a vinyl chloride polymer according to claim 1, wherein the two kinds of polymerization initiators are t-hexyl peroxypivalate and cumyl peroxy neodecanoate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06724494A JP3326956B2 (en) | 1994-04-05 | 1994-04-05 | Method for producing vinyl chloride polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06724494A JP3326956B2 (en) | 1994-04-05 | 1994-04-05 | Method for producing vinyl chloride polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07278207A JPH07278207A (en) | 1995-10-24 |
| JP3326956B2 true JP3326956B2 (en) | 2002-09-24 |
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ID=13339320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06724494A Expired - Fee Related JP3326956B2 (en) | 1994-04-05 | 1994-04-05 | Method for producing vinyl chloride polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3326956B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200424217A (en) * | 2003-05-01 | 2004-11-16 | Akzo Nobel Nv | Increased polymerization reactor output by using a specific initiating system |
| JP6058347B2 (en) * | 2012-10-15 | 2017-01-11 | 大洋塩ビ株式会社 | Method for producing vinyl chloride polymer having excellent moldability |
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1994
- 1994-04-05 JP JP06724494A patent/JP3326956B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07278207A (en) | 1995-10-24 |
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