JP2004115821A - Dispersion stabilizing agent for suspension polymerization of vinyl compound - Google Patents
Dispersion stabilizing agent for suspension polymerization of vinyl compound Download PDFInfo
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本発明はビニル系化合物の懸濁重合用分散安定剤に関する。さらに詳しくは消泡効果に著しく優れた塩化ビニルなどのビニル系化合物の懸濁重合用分散安定剤に関する。 The present invention relates to a dispersion stabilizer for suspension polymerization of a vinyl compound. More particularly, the present invention relates to a dispersion stabilizer for suspension polymerization of a vinyl compound such as vinyl chloride, which has an excellent defoaming effect.
工業的に塩化ビニル系樹脂などのビニル系重合体を製造する場合には、水性媒体中で分散安定剤の存在下で塩化ビニルなどのビニル系化合物を分散させ、油溶性触媒を用いて重合を行う懸濁重合が広く実施されている。一般に、ビニル系重合体の品質を支配する因子としては、重合率、水−モノマー比、重合温度、触媒の種類および量、重合槽の型式、撹拌速度あるいは分散安定剤の種類などが挙げられるが、なかでも分散安定剤の種類による影響が非常に大きい。 When industrially producing a vinyl polymer such as a vinyl chloride resin, a vinyl compound such as vinyl chloride is dispersed in an aqueous medium in the presence of a dispersion stabilizer, and the polymerization is carried out using an oil-soluble catalyst. The suspension polymerization performed is widely practiced. In general, factors that control the quality of the vinyl polymer include a polymerization rate, a water-monomer ratio, a polymerization temperature, a type and amount of a catalyst, a type of a polymerization tank, a stirring speed, and a type of a dispersion stabilizer. In particular, the influence of the type of the dispersion stabilizer is very large.
ビニル系化合物の懸濁重合用分散安定剤に要求される性能としては、（１）得られるビニル系重合体粒子の粒径分布をできるだけシャープにする働きのあること、（２）可塑剤の吸収速度を大きくして加工性を容易にし、重合体粒子中に残存する塩化ビニルなどのモノマーの除去を容易にし、かつ成形品中のフィッシュアイなどの生成を防止するために、各重合体粒子を多孔性にする働きがあること、（３）充填比重の大きい重合体粒子を形成する働きがあることなどが挙げられる。従来、ビニル系化合物の懸濁重合用分散安定剤としては、メチルセルロース、カルボキシメチルセルロースなどのセルロース誘導体あるいは部分けん化ポリビニルアルコールなどが単独または組み合わせて使用されている。しかしながら、従来の分散安定剤は上記（１）〜（３）の要求性能を満たしていないという問題があった。 The performance required of the dispersion stabilizer for suspension polymerization of vinyl compounds is as follows: (1) the function of sharpening the particle size distribution of the obtained vinyl polymer particles as much as possible; and (2) the absorption of the plasticizer. In order to increase the speed and facilitate processability, to facilitate removal of monomers such as vinyl chloride remaining in the polymer particles, and to prevent the formation of fish eyes and the like in molded products, And (3) a function of forming polymer particles having a high filling specific gravity. Conventionally, as a dispersion stabilizer for suspension polymerization of a vinyl compound, a cellulose derivative such as methylcellulose or carboxymethylcellulose, or partially saponified polyvinyl alcohol, or the like has been used alone or in combination. However, there is a problem that the conventional dispersion stabilizer does not satisfy the above-mentioned requirements (1) to (3).
塩化ビニルなどのビニル系化合物の懸濁重合は、通常バッチ式で行われ、重合器中に水性媒体、分散安定剤、重合開始剤およびビニル系化合物などを仕込み、さらに必要とされる添加剤を加えた後、昇温して重合反応を行わせるという方法が一般的である。最近では、生産性を向上させるために重合１バッチに要する時間を短縮することが求められており、ビニル系化合物の懸濁重合においてリフラックスコンデンサー等を設置して重合熱の除熱効率を高めたり、あらかじめ加熱した水性媒体を仕込む方法（ホットチャージ法）により昇温時間を短縮する方法が用いられている。しかしながら、従来のビニル系化合物の懸濁重合用分散安定剤を用いた場合には、重合中における発泡が激しいことから重合器内の有効容積が減少して生産性が低下したり、リフラックスコンデンサー付重合器を用いると温度コントロールができなくなったり、ホットチャージ法を用いるとビニル系重合体粒子の多孔性が低下するという致命的欠点があった。一方、発泡を防止するために消泡剤等を添加すると、生成するビニル系重合体粒子の熱安定性が低下するという問題があった。 Suspension polymerization of vinyl compounds such as vinyl chloride is usually performed in a batch system, and an aqueous medium, a dispersion stabilizer, a polymerization initiator and a vinyl compound are charged into a polymerization vessel, and further necessary additives are added. After the addition, a general method is to raise the temperature to cause a polymerization reaction. Recently, it has been required to shorten the time required for one batch of polymerization in order to improve productivity. For example, in a suspension polymerization of vinyl compounds, a reflux condenser or the like is installed to increase the efficiency of removing heat of polymerization. A method of shortening the temperature raising time by a method of charging a pre-heated aqueous medium (hot charge method) is used. However, when a conventional dispersion stabilizer for suspension polymerization of a vinyl compound is used, the foaming during the polymerization is severe, so that the effective volume in the polymerization vessel is reduced and the productivity is reduced. The use of a polymerization reactor has a fatal drawback in that the temperature cannot be controlled, and the use of a hot charge method results in a decrease in the porosity of the vinyl polymer particles. On the other hand, if an antifoaming agent or the like is added to prevent foaming, there is a problem that the thermal stability of the resulting vinyl polymer particles is reduced.
（非特許文献１）には、塩化ビニルの懸濁重合用分散安定剤として、重合度２０００、けん化度８０モル％のポリビニルアルコールおよび重合度７００〜８００、けん化度７０モル％のポリビニルアルコールが記載されている。（特許文献１）には、アミノ基、アンモニウム基、カルボキシル基またはスルホン酸基を末端に有する重合度１００以上、けん化度５０〜９０モル％のポリビニルアルコールからなるビニル系化合物の懸濁重合用分散安定剤が記載されている。しかしながら、（非特許文献１）および（特許文献１）に記載された分散安定剤は、重合中における発泡性が激しいという欠点があった。（特許文献２）には、けん化度３０〜６０モル％のポリ酢酸ビニルからなる塩化ビニルの懸濁重合用分散助剤が記載されている。（特許文献３）には、末端にメルカプト基を有する水不溶性の重合体からなるビニル系化合物の懸濁重合用分散助剤が記載されており、該水不溶性の重合体として末端にメルカプト基を有するけん化度５０モル％以下のポリビニルエステル系重合体が例示されている。しかしながら（特許文献２）および（特許文献３）に記載された分散助剤は単独で使用した場合には、ビニル系化合物の懸濁重合の安定性が確保できない。また該分散助剤を従来の部分けん化ポリビニルアルコールと組み合わせて使用した場合には、重合器内における発泡性が激しいという問題があった。（非特許文献２）には、重合度１５００、けん化度８８モル％の末端にメルカプト基を有するポリビニルアルコールを保護コロイドに用いて、メタクリル酸エステルまたはスチレンを乳化重合することが記載されている。しかしながら（非特許文献２）に記載された乳化重合においては、水溶性開始剤が用いられ、得られた重合体は粒子径が０．１〜２μｍ程度の水性エマルジョンの形態であることから、重合体を溶融成形に供するために該水性エマルジョンから粉体状の重合体を得るのは難しいという問題があった。 Non-Patent Document 1 describes, as dispersion stabilizers for suspension polymerization of vinyl chloride, polyvinyl alcohol having a polymerization degree of 2,000 and a saponification degree of 80 mol% and polyvinyl alcohol having a polymerization degree of 700 to 800 and a saponification degree of 70 mol%. Have been. (Patent Literature 1) discloses a dispersion for suspension polymerization of a vinyl compound composed of polyvinyl alcohol having an amino group, an ammonium group, a carboxyl group, or a sulfonic acid group at the terminal and having a degree of polymerization of 100 or more and a degree of saponification of 50 to 90 mol%. Stabilizers are described. However, the dispersion stabilizers described in (Non-Patent Document 1) and (Patent Document 1) have a drawback that foamability during polymerization is severe. (Patent Document 2) describes a dispersion aid for suspension polymerization of vinyl chloride composed of polyvinyl acetate having a degree of saponification of 30 to 60 mol%. (Patent Document 3) describes a dispersion aid for suspension polymerization of a vinyl compound composed of a water-insoluble polymer having a mercapto group at a terminal, and a mercapto group at a terminal as the water-insoluble polymer. A polyvinyl ester polymer having a saponification degree of 50 mol% or less is exemplified. However, when the dispersion aids described in (Patent Document 2) and (Patent Document 3) are used alone, the stability of suspension polymerization of the vinyl compound cannot be ensured. Further, when the dispersing aid is used in combination with a conventional partially saponified polyvinyl alcohol, there is a problem that foamability in the polymerization vessel is severe. Non-Patent Document 2 describes that methacrylic acid ester or styrene is emulsion-polymerized using polyvinyl alcohol having a polymerization degree of 1500 and a saponification degree of 88 mol% and having a mercapto group at a terminal as a protective colloid. However, in the emulsion polymerization described in (Non-Patent Document 2), a water-soluble initiator is used, and the obtained polymer is in the form of an aqueous emulsion having a particle diameter of about 0.1 to 2 μm. There is a problem that it is difficult to obtain a powdery polymer from the aqueous emulsion in order to subject the coalesced to melt molding.
本発明の目的は、従来の一般的なビニル系化合物の懸濁重合方法である常温の水性媒体を重合器内に仕込む方法（コールドチャージ法）および重合器内のジャケットまたはコイルにより重合温度のコントロールを行う方法はもとより、コンデンサー付重合器を使用する方法、ホットチャージ法およびコンデンサー付重合器を用いたホットチャージ法においても、重合器内の消泡効果が著しく優れており、かつ前記（１）〜（３）の要求特性を同時に満たす分散安定剤を提供することにある。 It is an object of the present invention to prepare a conventional aqueous suspension polymerization method for vinyl compounds by charging an aqueous medium at room temperature into a polymerization vessel (cold charge method) and to control the polymerization temperature by a jacket or coil in the polymerization vessel. In addition to the above method, the defoaming effect in the polymerization vessel is remarkably excellent in the method using a polymerization vessel with a condenser, the hot charge method, and the hot charge method using a polymerization vessel with a condenser. An object of the present invention is to provide a dispersion stabilizer which simultaneously satisfies the required characteristics of (3).
本発明者らは上記課題を解決するために鋭意検討を重ねた結果、けん化度６０モル％以上の末端にメルカプト基を有するポリビニルアルコール系重合体（Ａ）からなるビニル系化合物の懸濁重合用分散安定剤を見出し、本発明を完成するに到った。 The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, the suspension polymerization of a vinyl-based compound comprising a polyvinyl alcohol-based polymer (A) having a mercapto group at the terminal having a degree of saponification of 60 mol% or more is used. They have found a dispersion stabilizer and have completed the present invention.
本発明の分散安定剤は、従来の分散安定剤に比べて、重合中における発泡挙動が極めて小さいことから重合器内の有効容積が増加して生産性が向上し、リフラックスコンデンサー付重合器を用いた懸濁重合、ホットチャージ法による懸濁重合、またはリフラックスコンデンサー付重合器を用いたホットチャージ法による懸濁重合において、重合器の温度コントロールが容易となる。また本発明の懸濁重合用分散安定剤を用いた場合には、得られたビニル系重合体粒子は、粒子径が大きく、その分布がシャープで、取扱い時の飛散が少なく、かつ成形機などへのくい込み性が良好であり、ビニル系重合体粒子の多孔性が向上し、可塑剤吸収速度が大きく、しかも充填比重の高いことから工業的な評価が極めて高い。 Compared with the conventional dispersion stabilizer, the dispersion stabilizer of the present invention has an extremely small foaming behavior during polymerization, so the effective volume in the polymerization vessel is increased and the productivity is improved. In the suspension polymerization used, the suspension polymerization by a hot charge method, or the suspension polymerization by a hot charge method using a polymerization vessel with a reflux condenser, the temperature control of the polymerization vessel becomes easy. When the dispersion stabilizer for suspension polymerization of the present invention is used, the obtained vinyl polymer particles have a large particle size, a sharp distribution, small scattering during handling, and a molding machine. It has good penetration into fibers, improves the porosity of vinyl polymer particles, has a high plasticizer absorption rate, and has a high filling specific gravity.
本発明に用いられるポリビニルアルコール系重合体（Ａ）は、けん化度６０モル％以上の末端に（好ましくは片末端に）メルカプト基を有するポリビニルアルコール系重合体（Ａ）である。ポリビニルアルコール系重合体（Ａ）のけん化度は６０モル％以上であり、６５モル％〜９５モル％が好ましく、６８〜８０モル％がさらに好ましい。ポリビニルアルコール系重合体（Ａ）の粘度平均重合度（以下、重合度と略記する）については特に制限はないが、２００〜３５００以下が好ましく、６００〜１５００がさらに好ましく、６８０〜１０００がさらにより好ましい。本発明に用いられるポリビニルアルコール系重合体（Ａ）はイオン基等を導入することにより水溶性を高めても良く、この場合のけん化度はビニルエステル基とビニルアルコール基から求められ、導入されたイオン基のけん化度は含まれない。本発明におけるポリビニルアルコール系重合体（Ａ）は、単独で用いた場合においてもビニル系化合物の懸濁重合を安定に行うことが可能なものであり、５〜１００℃（好ましくは１０〜９０℃）の水に対して水溶性であることが好ましい。 ポ リ ビ ニ ル The polyvinyl alcohol polymer (A) used in the present invention is a polyvinyl alcohol polymer (A) having a mercapto group at the terminal (preferably at one terminal) having a degree of saponification of 60 mol% or more. The degree of saponification of the polyvinyl alcohol-based polymer (A) is at least 60 mol%, preferably from 65 mol% to 95 mol%, more preferably from 68 to 80 mol%. The viscosity average degree of polymerization of the polyvinyl alcohol polymer (A) (hereinafter, abbreviated as degree of polymerization) is not particularly limited, but is preferably 200 to 3500 or less, more preferably 600 to 1500, and still more preferably 680 to 1000. preferable. The polyvinyl alcohol-based polymer (A) used in the present invention may have increased water solubility by introducing an ionic group or the like. In this case, the degree of saponification is determined from the vinyl ester group and the vinyl alcohol group, and is introduced. The degree of saponification of the ionic group is not included. The polyvinyl alcohol polymer (A) in the present invention is capable of stably performing suspension polymerization of a vinyl compound even when used alone, and is 5 to 100 ° C (preferably 10 to 90 ° C). ) Is preferably water-soluble in water.
本発明に用いられるポリビニルアルコール系重合体（Ａ）の製造方法には特に制限はないが、ビニルエステル単量体をラジカル重合する際に、チオールカルボン酸、あるいは２−アセチルチオエタンチオール、１０−アセチルチオデカンチオールなどの分子内にチオエステルとチオール基とを含有する化合物の共存下に重合し、得られた重合体を水酸化ナトリウムやアンモニアなどのアルカリで処理してビニルエステル重合体をけん化すると共に、末端のチオエステルをけん化することにより、末端にチオール基を有する重合体を得る方法が簡便で効率的である。ビニルエステルとしては、例えばギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリル酸ビニル、ラウリル酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、オレイン酸ビニルなどが挙げられる。本発明に用いるポリビニルアルコール系重合体は、アンモニウム基、カルボキシル基、スルホン基等のイオン基、ノニオン基または（長鎖）アルキル基等を１０モル％以下導入しても良い。ポリビニルアルコール系重合体（Ａ）の製造方法は特開昭５８−６１７４６号において詳述されている。 The method for producing the polyvinyl alcohol-based polymer (A) used in the present invention is not particularly limited. However, when a vinyl ester monomer is subjected to radical polymerization, thiolcarboxylic acid or 2-acetylthioethanethiol, 10- Polymerization is performed in the presence of a compound containing a thioester and a thiol group in the molecule such as acetylthiodecanethiol, and the resulting polymer is treated with an alkali such as sodium hydroxide or ammonia to saponify the vinyl ester polymer. At the same time, a method for obtaining a polymer having a thiol group at the terminal by saponifying the terminal thioester is simple and efficient. Vinyl esters include, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl caprylate, vinyl laurate, vinyl palmitate , Vinyl stearate, vinyl oleate and the like. In the polyvinyl alcohol-based polymer used in the present invention, an ionic group such as an ammonium group, a carboxyl group or a sulfone group, a nonionic group or a (long chain) alkyl group may be introduced in an amount of 10 mol% or less. The method for producing the polyvinyl alcohol polymer (A) is described in detail in JP-A-58-61746.
前記ポリビニルアルコール系重合体（Ａ）は、ポリビニルエステル系重合体（Ｂ）と併用して用いることもできる。本発明においては、分散安定剤である前記ポリビニルアルコール系重合体（Ａ）にポリビニルエステル系重合体（Ｂ）が分散助剤として併用された形態も、分散剤安定剤という。前記ポリビニルエステル系重合体（Ｂ）のけん化度は６０モル％未満であることが好ましく、２０〜５５モル％がより好ましく、２５〜４５モル％がさらに好ましい。成分（Ａ）と成分（Ｂ）の重量比（Ａ）／（Ｂ）は４０／６０〜９５／５であり、５０／５０〜９０／１０がより好ましく、６０／４０〜８０／２０がさらにより好ましい。成分（Ａ）と成分（Ｂ）の重量比（Ａ）／（Ｂ）が９５／５より大きい場合にはポロシティー改善効果が見られない場合があり、４０／６０未満の場合には重合の安定性が失われる場合がある。前記ポリビニルエステル系重合体（Ｂ）の重合度については特に制限はないが、１０００以下が好ましく、２００〜５５０がより好ましく、２３０〜４００がさらにより好ましい。 The polyvinyl alcohol-based polymer (A) can be used in combination with the polyvinyl ester-based polymer (B). In the present invention, a form in which the polyvinyl alcohol-based polymer (A), which is a dispersion stabilizer, is used in combination with the polyvinyl ester-based polymer (B) as a dispersion aid is also referred to as a dispersant stabilizer. The degree of saponification of the polyvinyl ester polymer (B) is preferably less than 60 mol%, more preferably 20 to 55 mol%, even more preferably 25 to 45 mol%. The weight ratio (A) / (B) of component (A) to component (B) is 40/60 to 95/5, preferably 50/50 to 90/10, and more preferably 60/40 to 80/20. More preferred. When the weight ratio (A) / (B) of the component (A) and the component (B) is more than 95/5, the porosity improvement effect may not be observed, and when the weight ratio is less than 40/60, the polymerization may not be effected. Stability may be lost. The degree of polymerization of the polyvinyl ester polymer (B) is not particularly limited, but is preferably 1,000 or less, more preferably 200 to 550, and still more preferably 230 to 400.
前記ポリビニルエステル系重合体（Ｂ）は、水不溶性あるいは水分散性であり、イオン基等を導入することにより、自己乳化性が付与されたものでも良い。前記ポリビニルエステル系重合体（Ｂ）の製造方法には特に制限はなく、従来公知のものが好適に用いられる。例えば、特開平１−９５１０３号に記載された側鎖にイオン基を有するポリビニルエステル系重合体、ＷＯ９１／１５５１８に記載された末端にイオン性基を有するポリビニルエステル系重合体、公知のノニオン基または（長鎖）アルキル基を１０モル％以下有するポリビニルエステル系重合体が好適に用いられる。 The polyvinyl ester polymer (B) may be water-insoluble or water-dispersible, and may have self-emulsifying properties by introducing an ionic group or the like. The method for producing the polyvinyl ester-based polymer (B) is not particularly limited, and conventionally known ones are suitably used. For example, a polyvinyl ester polymer having an ionic group in a side chain described in JP-A-1-95103, a polyvinyl ester polymer having an ionic group at a terminal described in WO 91/15518, a known nonionic group or A polyvinyl ester polymer having a (long chain) alkyl group of 10 mol% or less is suitably used.
次に本発明の分散安定剤を用いたビニル系化合物の懸濁重合によるビニル系重合体の製造方法について説明する。ビニル系重合体の製造方法において用いる水性媒体の温度は特に制限はなく、２０℃程度の冷水はもとより、９０℃以上の温水も好適に用いられる。この加熱水性媒体を構成する媒体は、純粋な水のほかに、各種の添加成分を含有する水溶液あるいは他の有機溶剤を含む水性媒体が挙げることができる。また、加熱水性媒体を重合反応系に仕込む際の供給量は、重合反応系を充分に加温できる量であればよい。また除熱効率を高めるためにリフラックスコンデンサー付重合器も好適に用いられる。ビニル系重合体の製造方法において、分散安定剤の使用量は特に制限はないが、通常ビニル系化合物１００重量部に対して５重量部以下であり、０．０１〜１重量部が好ましく、０．０２〜０．２重量部がさらにより好ましい。本発明の分散安定剤は単独で使用しても良いが、塩化ビニルなどのビニル系化合物を水性媒体中で懸濁重合する際に通常使用されるポリビニルアルコール、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロースなどの水溶性セルロースエーテル、ゼラチンなどの水溶性ポリマー、ソルビタンモノラウレート、ソルビタントリオレート、グリセリントリステアレート、エチレンオキシドプロピレンオキシドブロックコポリマーなどの油溶性乳化剤、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレングリセリンオレート、ラウリン酸ナトリウムなどの水溶性乳化剤などを併用しても良い。その添加量については特に制限はないが、塩化ビニルなどのビニル系化合物１００重量部当たり０．０１〜１．０重量部が好ましい。 Next, a method for producing a vinyl polymer by suspension polymerization of a vinyl compound using the dispersion stabilizer of the present invention will be described. The temperature of the aqueous medium used in the method for producing a vinyl polymer is not particularly limited, and cold water of about 20 ° C. and hot water of 90 ° C. or more are suitably used. The medium constituting the heated aqueous medium may be an aqueous medium containing various additive components or an aqueous medium containing another organic solvent in addition to pure water. The supply amount when the heated aqueous medium is charged into the polymerization reaction system may be an amount that can sufficiently heat the polymerization reaction system. In order to enhance the heat removal efficiency, a polymerization vessel equipped with a reflux condenser is also preferably used. In the method for producing a vinyl polymer, the amount of the dispersion stabilizer is not particularly limited, but is usually 5 parts by weight or less, preferably 0.01 to 1 part by weight, and more preferably 0.01 to 1 part by weight based on 100 parts by weight of the vinyl compound. 0.02 to 0.2 part by weight is even more preferred. Although the dispersion stabilizer of the present invention may be used alone, polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, which is usually used when suspension-polymerizing a vinyl compound such as vinyl chloride in an aqueous medium, Water-soluble cellulose ethers such as hydroxypropyl methylcellulose, water-soluble polymers such as gelatin, sorbitan monolaurate, sorbitan triolate, glycerin tristearate, oil-soluble emulsifiers such as ethylene oxide propylene oxide block copolymer, polyoxyethylene sorbitan monolaurate, A water-soluble emulsifier such as polyoxyethylene glycerin oleate and sodium laurate may be used in combination. The amount added is not particularly limited, but is preferably 0.01 to 1.0 part by weight per 100 parts by weight of a vinyl compound such as vinyl chloride.
その他各種添加剤も必要に応じて加えることができる。各種添加剤としては、例えばアセトアルデヒド、ブチルアルデヒド、トリクロロエチレン、パークロロエチレンあるいはメルカプタン類などの重合度調節剤、フェノール化合物、イオウ化合物、Ｎ−オキシド化合物などの重合禁止剤などが挙げられる。また、ｐＨ調整剤、スケール防止剤、架橋剤などを加えることも任意であり、上記の添加剤を複数併用しても差し支えない。一方、重合開始剤も、従来塩化ビニルなどのビニル系化合物の重合に使用されているものでよく、これには例えばジイソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネートなどのパーカーボネート化合物、ｔ−ブチルパーオキシネオデカネート、α−クミルパーオキシネオデカネート、ｔ−ブチルパーオキシネオデカネートなどのパーエステル化合物、アセチルシクロヘキシルスルホニルパーオキシド、２，４，４−トリメチルペンチル−２−パーオキシフェノキシアセテートなどの過酸化物、２，２′−アゾビスイソブチロニトリル、アゾビス−２，４−ジメチルバレロニトリル、アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）などのアゾ化合物などが挙げられ、さらにはこれらに過硫酸カリウム、過硫酸アンモニウム、過酸化水素などを組み合わせて使用することもできる。 Other various additives can be added as needed. Examples of the various additives include polymerization degree regulators such as acetaldehyde, butyraldehyde, trichloroethylene, perchloroethylene, and mercaptans, and polymerization inhibitors such as phenol compounds, sulfur compounds, and N-oxide compounds. It is also optional to add a pH adjuster, a scale inhibitor, a crosslinking agent, and the like, and a plurality of the above additives may be used in combination. On the other hand, the polymerization initiator may be any of those conventionally used for the polymerization of vinyl compounds such as vinyl chloride. Examples thereof include diisopropyl peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, and diethoxyethyl percarbonate. Percarbonate compounds such as oxydicarbonate, perester compounds such as t-butylperoxyneodecanate, α-cumylperoxyneodecanate, t-butylperoxyneodecanate, acetylcyclohexylsulfonyl peroxide, 2,4 Peroxide such as 2,4-trimethylpentyl-2-peroxyphenoxyacetate, 2,2'-azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobis (4-methoxy-2,4- Azo such as dimethylvaleronitrile) Compounds and the like, and further can be used in combination of potassium persulfate thereto, ammonium persulfate, hydrogen peroxide and the like.
本発明の分散安定剤を用いて懸濁重合することのできるビニル系化合物としては、具体的には塩化ビニル単独のほか、塩化ビニルを主体とする単量体混合物（塩化ビニル５０重量％以上）が包含され、この塩化ビニルと共重合されるコモノマーとしては、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル、（メタ）アクリル酸メチル、（メタ）アクリル酸エチルなどの（メタ）アクリル酸エステル、エチレン、プロピレンなどのオレフィン、無水マレイン酸、アクリロニトリル、イタコン酸、スチレン、塩化ビニリデン、ビニルエーテル、その他塩化ビニルと共重合可能な単量体が例示される。さらには、塩化ビニルを含まない上記ビニル系化合物の単独重合や共重合に当たっても、本発明の分散安定剤を用いることができる。本発明の分散安定剤を用いて懸濁重合するに当たって、各成分の仕込み割合、重合温度などは、従来塩化ビニルなどのビニル系化合物の懸濁重合で採用されている条件に準じて定めればよい。また、ビニル系化合物、重合開始剤、分散安定剤、加熱水性媒体およびその他添加物の仕込み順序や比率については、なんら制限されない。また、温水を用いると同時に、ビニル系化合物を重合器に仕込む前にビニル系化合物を加熱しておく方法も好適に用いられる。 Specific examples of the vinyl compound that can be subjected to suspension polymerization using the dispersion stabilizer of the present invention include, in addition to vinyl chloride alone, a monomer mixture mainly composed of vinyl chloride (vinyl chloride 50% by weight or more). Comonomers copolymerized with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate, (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, and ethylene. And olefins such as propylene, maleic anhydride, acrylonitrile, itaconic acid, styrene, vinylidene chloride, vinyl ether, and other monomers copolymerizable with vinyl chloride. Further, the dispersion stabilizer of the present invention can be used for homopolymerization or copolymerization of the above-mentioned vinyl compound containing no vinyl chloride. In the suspension polymerization using the dispersion stabilizer of the present invention, the charge ratio of each component, the polymerization temperature and the like may be determined according to the conditions conventionally used in suspension polymerization of vinyl compounds such as vinyl chloride. Good. The order and ratio of the vinyl compound, the polymerization initiator, the dispersion stabilizer, the heated aqueous medium and other additives are not limited at all. In addition, a method in which warm water is used and the vinyl compound is heated before the vinyl compound is charged into the polymerization vessel is also preferably used.
以下、実施例をあげて本発明をさらに詳しく説明するが、本発明はこれらの実施例によってなんら限定されるものではない。なお、以下の実施例において「％」および「部」は特に断りのない限り、「重量％」および「重量部」を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples, “%” and “parts” mean “% by weight” and “parts by weight” unless otherwise specified.
製造例〔末端にメルカプト基を有するポリビニルアルコール系重合体〕
酢酸ビニル（以下ＶＡｃと略記する）２８００部、メタノール６７０部を反応容器にとり、内部を充分に窒素置換した後、外温を６５℃にあげ、内温が６０℃に達したところで、あらかじめ窒素置換したチオ酢酸０．２４３部を含むメタノール１０部を加えた後、２，２′−アゾビスイソブチロニトリル１部を含むメタノール溶液２０部を加え直ちにチオ酢酸１．８部を含むメタノール溶液１８部を４時間にわたって加えた。５時間後の重合率は６４．７％であった。５時間後に容器を冷却し、減圧下に残留するＶＡｃをメタノールとともに系外へ追出す操作をメタノールを追加しながら行ない、ポリビニルエステル（以下ＰＶＡｃと略記する）のメタノール溶液を得た（濃度６２％）。このメタノール溶液の一部をとり、ＰＶＡｃ濃度３０％、含水率３％、〔ＮａＯＨ〕／〔ＶＡｃ〕＝０．０２（モル比）となるように、ＮａＯＨのメタノール溶液を加え、４０℃で１時間けん化した後、酢酸を加えて残存するＮａＯＨを中和し、けん化反応を停止した。けん化度を測定すると７２モル％であった。次に同様のけん化方法で〔ＮａＯＨ〕／〔ＶＡｃ〕＝０．０５（モル比）でけん化を行い、得られたポリビニルアルコール（ＰＶＡ）をメタノールによるソックレー洗浄によって精製した後、けん化度を測定すると９８．９モル％であった。また、水中３０℃で極限粘度を測定し、重合度を計算したところ８２０であった。次に、この精製したＰＶＡを用いて、ＰＶＡ中に含まれるメルカプト基（以下ＳＨ基と略記する）の含有量をヨウ素酸化による方法で求めたところ、４．０×１０−５当量／ｇ−ＰＶＡのＳＨ基の存在が確認された。また、この精製したＰＶＡを常法により再酢化して再酢化ＰＶＡｃを得た後、ＴＨＦ系４０℃でポリスチレンを標準物質としてＧＰＣ測定をしたところＰｗ／Ｐｎ＝２．１であった。同様の方法により調製した本発明の分散安定剤であるポリビニルアルコール系重合体（Ａ）を表１に示す。これらの分散安定剤は全て、水あるいは温水に可溶であった。
Production Example [Polyvinyl alcohol polymer having a mercapto group at the terminal]
After 2800 parts of vinyl acetate (hereinafter abbreviated as VAc) and 670 parts of methanol were placed in a reaction vessel and the inside was sufficiently purged with nitrogen, the external temperature was raised to 65 ° C. 10 parts of methanol containing 0.243 parts of thioacetic acid are added, and 20 parts of a methanol solution containing 1 part of 2,2'-azobisisobutyronitrile are added, and immediately a methanol solution 18 containing 1.8 parts of thioacetic acid is added. Parts were added over 4 hours. The polymerization rate after 5 hours was 64.7%. After 5 hours, the vessel was cooled, and the remaining VAc was removed from the system together with methanol under reduced pressure while adding methanol to obtain a methanol solution of polyvinyl ester (hereinafter abbreviated as PVAc) (concentration: 62%). ). A portion of this methanol solution is taken, a methanol solution of NaOH is added thereto so that the PVAc concentration is 30%, the water content is 3%, and [NaOH] / [VAc] = 0.02 (molar ratio). After saponification for an hour, acetic acid was added to neutralize the remaining NaOH, and the saponification reaction was stopped. The measured degree of saponification was 72 mol%. Next, saponification is performed by the same saponification method at [NaOH] / [VAc] = 0.05 (molar ratio), the obtained polyvinyl alcohol (PVA) is purified by Soxhlet washing with methanol, and the degree of saponification is measured. 98.9 mol%. The intrinsic viscosity was measured at 30 ° C. in water, and the degree of polymerization was calculated to be 820. Next, using this purified PVA, the content of mercapto groups (hereinafter abbreviated as SH groups) contained in the PVA was determined by a method based on iodine oxidation, whereupon 4.0 × 10 −5 equivalents / g − The presence of SH groups in PVA was confirmed. Further, the purified PVA was re-acetylated by a conventional method to obtain a re-acetylated PVAc, and GPC measurement was performed at 40 ° C. in a THF system using polystyrene as a standard substance, whereby Pw / Pn = 2.1. Table 1 shows the polyvinyl alcohol-based polymer (A) which is a dispersion stabilizer of the present invention prepared by the same method. All of these dispersion stabilizers were soluble in water or hot water.
〔塩化ビニルの重合〕
リフラックスコンデンサー付のグラスライニング製オートクレーブに、表（表１：実施例１〜１０、表２：実施例１１〜２１、表３：比較例１〜７）に示した分散安定剤を溶かした脱イオン水１部およびジイソプロピルパーオキシジカーボネートの７０％トルエン溶液０．０４部を仕込み、オートクレーブ内を５０ｍｍＨｇとなるまで脱気して酸素を除いたのち、撹拌下で８０℃の温水３９部および塩化ビニルモノマー３０部を同時に仕込んだ。仕込みが終了した時点での液面は重合器の底面から６０％の高さであり、内温は５０℃であった。その後内温を５０℃保ち重合を継続した。重合開始時、オートクレーブ内の圧力は７．０ｋｇ／ｃｍ２Ｇであったが、重合開始６時間後に４．０ｋｇ／ｃｍ２Ｇとなった時点で重合を停止し、未反応の塩化ビニルモノマーをパージし、内容物を取り出し脱水乾燥した。得られた塩化ビニル樹脂の性能を下記の方法により評価し、その結果を表に示す。塩化ビニル重合体の重合収率は８５％であり、平均重合度は１３００であった。
(Polymerization of vinyl chloride)
In a glass-lined autoclave equipped with a reflux condenser, the dispersion stabilizer shown in the table (Table 1: Examples 1 to 10, Table 2: Examples 11 to 21, and Table 3: Comparative Examples 1 to 7) was dissolved. Ion water (1 part) and 0.04 part of a 70% toluene solution of diisopropyl peroxydicarbonate were charged, and the inside of the autoclave was degassed until the pressure became 50 mmHg to remove oxygen. 30 parts of a vinyl monomer were simultaneously charged. The liquid level at the end of the charging was 60% above the bottom of the polymerization vessel, and the internal temperature was 50 ° C. Thereafter, the internal temperature was kept at 50 ° C. to continue the polymerization. At the start of polymerization, the pressure in the autoclave was 7.0 kg / cm 2 G, polymerization initiator 6 hours after the polymerization was stopped at the time point when 4.0 kg / cm 2 G, the vinyl chloride monomer unreacted After purging, the contents were taken out and dehydrated and dried. The performance of the obtained vinyl chloride resin was evaluated by the following methods, and the results are shown in the table. The polymerization yield of the vinyl chloride polymer was 85%, and the average degree of polymerization was 1,300.
（１）可塑剤吸収性
プラストグラフに接続されたプラネタリーミキサーに、得られた塩化ビニル重合体粉末４００ｇを入れ、６０ｒｐｍで撹拌しながら予熱（４分）して８８℃としたのち、これにジオクチルフタレートを２００ｇ添加し、添加時からトルクの下降した時点まで時間を可塑剤吸収性（分）とした。
（２）ＣＰＡ（ＣｏｌｄＰｌａｓｔｉｃｉｚｅｒＡｂｓｏｒｐｔｉｏｎ：冷可塑剤吸収量）
ＡＳＴＭ−Ｄ３３６７−７５に記載された方法より、２３℃におけるジオクチルフタレートの吸収量を測定した。
（３）発泡性評価
重合終了時に重合器内の発泡状態を目視により観察し、以下の記号で示す。
◎：発泡なし
○：重合器の底面から６２〜６５％の高さにまで泡が認められた。
△：重合器の底面から６６〜７０％の高さにまで泡が認められた。
▲：重合器の底面から９０〜１００％の高さにまで泡が認められた。
×：重合器の底面から１００％の高さにまで泡が認められ、さらにリフラックスコンデンサーに泡が詰まっていた。
(1) Absorbency of plasticizer 400 g of the obtained vinyl chloride polymer powder was put into a planetary mixer connected to a plastograph, preheated (4 minutes) with stirring at 60 rpm to 88 ° C. 200 g of dioctyl phthalate was added, and the time from the time of addition to the time when the torque decreased was defined as plasticizer absorbency (minutes).
(2) CPA (Cold Plasticizer Absorption: cold plasticizer absorption amount)
The absorption amount of dioctyl phthalate at 23 ° C. was measured by the method described in ASTM-D3367-75.
(3) Evaluation of foaming property At the end of the polymerization, the foaming state in the polymerization vessel was visually observed and indicated by the following symbols.
：: no foaming ：: foaming was observed up to a height of 62 to 65% from the bottom of the polymerization vessel.
Δ: Bubbles were observed up to a height of 66 to 70% from the bottom of the polymerization vessel.
：: Bubbles were observed up to a height of 90 to 100% from the bottom of the polymerization vessel.
×: Bubbles were observed up to a height of 100% from the bottom of the polymerization vessel, and bubbles were clogged in the reflux condenser.
Claims (6)
The method for producing a vinyl polymer according to any one of claims 3 to 5, wherein the vinyl compound is vinyl chloride.
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| JP2004012711A Expired - Fee Related JP3898696B2 (en) | 2004-01-21 | 2004-01-21 | Method for producing vinyl chloride polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017094698A1 (en) | 2015-12-04 | 2017-06-08 | 日本酢ビ・ポバール株式会社 | Dispersion assis5tant for suspension polymerization, method for producing vinyl polymer in which said assistant is used, and vinyl chloride resin |
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2004
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017094698A1 (en) | 2015-12-04 | 2017-06-08 | 日本酢ビ・ポバール株式会社 | Dispersion assis5tant for suspension polymerization, method for producing vinyl polymer in which said assistant is used, and vinyl chloride resin |
| US10731032B2 (en) | 2015-12-04 | 2020-08-04 | Japan Vam & Poval Co., Ltd. | Dispersion assistant for suspension polymerization, method for producing vinyl-based polymer using the same, and vinyl chloride resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3898696B2 (en) | 2007-03-28 |
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