JP2531569B2 - Method for producing vinyl chloride polymer by suspension polymerization - Google Patents
Method for producing vinyl chloride polymer by suspension polymerizationInfo
- Publication number
- JP2531569B2 JP2531569B2 JP5083801A JP8380193A JP2531569B2 JP 2531569 B2 JP2531569 B2 JP 2531569B2 JP 5083801 A JP5083801 A JP 5083801A JP 8380193 A JP8380193 A JP 8380193A JP 2531569 B2 JP2531569 B2 JP 2531569B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polymerization
- parts
- vinyl
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Polymerisation Methods In General (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はポロシティが高く可塑剤
吸収性に優れた塩化ビニル系重合体を効率よく製造する
方法に関する。FIELD OF THE INVENTION The present invention relates to a method for efficiently producing a vinyl chloride polymer having high porosity and excellent plasticizer absorbability.
【０００２】[0002]
【従来の技術】塩化ビニル系重合体のポロシティを高め
てその可塑剤吸収性を向上させようという試みは従来か
ら色々提案されているが、未だ充分に満足のゆく方法は
見出されていない。一方、米国特許第４，２０５，１４
９号明細書には、塩化ビニル１００重量部当たり５重量
部以下のプロパンまたはブタンを添加してに塩化ビニル
を塊状、乳化または懸濁重合させて、塩化ビニルモノマ
ー残量の少ない塩化ビニル系重合体を製造する方法が記
載されており、この方法で製造された塩化ビニル系重合
体はプロパンまたはブタンを添加せずに製造した塩化ビ
ニル系重合体に比べて、そのポロシティが多少向上して
いる。2. Description of the Related Art Various attempts have been made so far to increase the porosity of a vinyl chloride polymer to improve its plasticizer absorbability, but a sufficiently satisfactory method has not yet been found. Meanwhile, U.S. Pat. No. 4,205,14
No. 9 describes that vinyl chloride based vinyl chloride-based monomer having a small residual amount of vinyl chloride monomer is obtained by adding 5 parts by weight or less of propane or butane to 100 parts by weight of vinyl chloride, and subjecting vinyl chloride to bulk, emulsion or suspension polymerization. A method for producing a coalesce is described, and the porosity of the vinyl chloride polymer produced by this method is slightly improved as compared with the vinyl chloride polymer produced without adding propane or butane. .
【０００３】しかし、上記の米国特許明細書に記載され
た方法で得られた塩化ビニル系重合体は、そのポロシテ
ィが未だ充分高いとは言えず、しかも実際にはプロパン
またはブタンを重合の開始時に一括して添加しているた
め、重合遅延作用が大きく、生産性が大幅に低下する。
そして、本発明者らがこの方法を追試実験するに当たっ
て、その生産性を上げるために重合開始剤量を多くした
ところ、得られる塩化ビニル系重合体の熱安定性が大き
く低下するという問題があることが判明した。However, the porosity of the vinyl chloride-based polymer obtained by the method described in the above-mentioned US patent is not yet high enough, and in fact, propane or butane is added at the start of the polymerization. Since they are added all at once, they have a large effect of delaying the polymerization and the productivity is significantly reduced.
Then, when the inventors of the present invention carry out a follow-up experiment of this method, when the amount of the polymerization initiator is increased in order to increase the productivity, there is a problem that the thermal stability of the obtained vinyl chloride-based polymer is significantly reduced. It has been found.
【０００４】[0004]
【発明が解決しようとする課題】本発明の課題は、ポロ
シティが高く可塑剤吸収性が良好で、しかも熱安定性な
どの物性にも優れた塩化ビニル系重合体を、重合の遅延
などを招くことなく、高い生産性で効率よく製造する方
法を提供することである。An object of the present invention is to delay the polymerization of a vinyl chloride polymer having a high porosity, a good plasticizer absorbability, and excellent physical properties such as thermal stability. It is an object of the present invention to provide a method for efficiently producing a product with high productivity.
【０００５】[0005]
【課題を解決するための手段】本発明者らが上記の課題
を解決すべく研究を重ねた結果、塩化ビニルの懸濁重合
に際して、その重合率が４０〜８０％の間に特定量のエ
タン、プロパンまたはブタンを添加すると、ポロシティ
が高く且つ熱安定性等の物性にも優れた塩化ビニル系重
合体を重合の遅延を生じずに、効率よく製造し得ること
を見出して本発明を完成した。Means for Solving the Problems As a result of the inventors' studies to solve the above-mentioned problems, as a result of suspension polymerization of vinyl chloride, a specific amount of ethane was obtained when the polymerization rate was 40 to 80%. The present invention has been completed by finding that the addition of propane or butane can efficiently produce a vinyl chloride-based polymer having high porosity and excellent physical properties such as thermal stability without delaying the polymerization. .
【０００６】すなわち、本発明は、塩化ビニル１００重
量部および他の共重合性ビニル単量体０〜３０重量部
を、懸濁剤および重合開始剤を含む水性媒体中で懸濁重
合して塩化ビニル系重合体を製造するに際し、塩化ビニ
ルおよび他の共重合性ビニル単量体の重合率が４０〜８
０％の間に、塩化ビニル１００重量部当たり、エタン、
プロパンおよびブタンから選ばれる化合物の少なくとも
１種を５重量部を超え２０重量部以下の割合で添加する
ことを特徴とする塩化ビニル系重合体の製造方法であ
る。That is, according to the present invention, 100 parts by weight of vinyl chloride and 0 to 30 parts by weight of another copolymerizable vinyl monomer are suspension-polymerized in an aqueous medium containing a suspending agent and a polymerization initiator to form a chloride. When producing a vinyl polymer, the polymerization rate of vinyl chloride and other copolymerizable vinyl monomers is 40 to 8
Between 0% and 100% by weight of vinyl chloride, ethane,
In the method for producing a vinyl chloride polymer, at least one compound selected from propane and butane is added in a proportion of more than 5 parts by weight and 20 parts by weight or less.
【０００７】本発明の方法では、塩化ビニルを単独で使
用して塩化ビニルの単独重合体を製造しても、または塩
化ビニルと他の共重合性ビニル単量体を使用して塩化ビ
ニルと他のビニル単量体との共重合体を製造してもよ
く、したがって上記本発明における「塩化ビニル系重合
体」とは塩化ビニル単独重合体および塩化ビニル共重合
体の両方をいう。In the method of the present invention, vinyl chloride may be used alone to produce a vinyl chloride homopolymer, or vinyl chloride and other copolymerizable vinyl monomers may be used to form vinyl chloride and other copolymers. May be produced. Therefore, the “vinyl chloride polymer” in the present invention refers to both a vinyl chloride homopolymer and a vinyl chloride copolymer.
【０００８】塩化ビニルと他のビニル単量体との共重合
体を製造する場合は、塩化ビニル１００重量部当たり他
のビニル単量体を３０重量部以下で使用する（以下「重
量部」を部という）。他のビニル単量体としては、例え
ばエチレン、プロピレン、１−ブテン、１−ペンテン、
１−ヘキセン等の炭素数２〜３０のα−オレフィン類、
アクリル酸およびそのエステル類、メタクリル酸および
そのエステル類、酢酸ビニル、プロピオン酸ビニル、ア
ルキルビニルエステル類等を挙げることができ、これら
の他のビニル単量体は単独で使用しても、２種以上を併
用してもよい。When a copolymer of vinyl chloride and another vinyl monomer is produced, 30 parts by weight or less of another vinyl monomer is used per 100 parts by weight of vinyl chloride (hereinafter, "parts by weight"). Called department). Examples of other vinyl monomers include ethylene, propylene, 1-butene, 1-pentene,
Α-olefins having 2 to 30 carbon atoms such as 1-hexene,
Acrylic acid and its esters, methacrylic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl esters and the like can be mentioned. These other vinyl monomers can be used alone or in combination of two kinds. You may use together the above.
【０００９】また、懸濁剤の種類は特に限定されず塩化
ビニルの懸濁重合において通常使用される懸濁剤のいず
れも使用可能であり、好ましい懸濁剤の例としてはケン
化度６５〜７９％の中ケン化度ポリビニルアルコール、
ケン化度８０〜９５％の部分ケン化ポリビニルアルコー
ル、ヒドロキシプロピルメチルセルロース、ヒドロキシ
プロピルセルロースなどの各種セルロース誘導体などを
挙げることができ、これらの懸濁剤は１種類のみを使用
しても、または２種以上を併用してもよい。また、上記
した懸濁剤と共に、ケン化度３０〜６０％の低ケン化度
ポリビニルアルコールを必要に応じて使用してもよい。
懸濁剤の使用量も特に限定されないが、一般に塩化ビニ
ルおよび他の共重合性ビニル単量体の合計重量に基づい
て、約０．０１〜０．５０重量％の割合で使用するのが
よい。The type of the suspending agent is not particularly limited, and any of the suspending agents usually used in the suspension polymerization of vinyl chloride can be used, and a preferable suspending agent is, for example, a saponification degree of 65 to 65. 79% medium saponification degree polyvinyl alcohol,
Examples thereof include partially saponified polyvinyl alcohol having a saponification degree of 80 to 95%, various cellulose derivatives such as hydroxypropylmethyl cellulose, hydroxypropyl cellulose, and the like, and these suspending agents may be used alone, or You may use together 1 or more types. In addition, a low saponification degree polyvinyl alcohol having a saponification degree of 30 to 60% may be used as necessary together with the above-mentioned suspending agent.
Although the amount of the suspending agent used is not particularly limited, it is generally preferable to use it in a ratio of about 0.01 to 0.50% by weight based on the total weight of vinyl chloride and other copolymerizable vinyl monomers. .
【００１０】更に、重合開始剤としては、塩化ビニル系
重合体の製造に用いられている公知の油溶性ラジカル開
始剤のいずれもが使用できその種類は制限されず、例え
ばジ−２−エチルヘキシルパーオキシジカーボネートな
どのパーオキシカーボネート類、ラウロイルパーオキサ
イド、３，５，５−トリメチルヘキサノイルパーオキサ
イドなどのジアシルパーオキサイド類、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
トなどのパーオキシエステル類、２，２’−アゾビスイ
ソブチロニトリルなどのアゾ化合物を使用することがで
き、これらの重合開始剤は単独で使用しても２種以上を
併用してもよい。また、重合開始剤の使用量も特に限定
されず従来公知の範囲で使用できるが、通常、塩化ビニ
ルおよび他の共重合性ビニル単量体の合計重量に基づい
て約０．０１〜０．１５重量％の割合で使用するのがよ
い。Further, as the polymerization initiator, any of the known oil-soluble radical initiators used in the production of vinyl chloride-based polymers can be used, and the kind thereof is not limited. For example, di-2-ethylhexylper Peroxycarbonates such as oxydicarbonate, lauroyl peroxide, diacyl peroxides such as 3,5,5-trimethylhexanoyl peroxide, permeates such as cumyl peroxyneodecaneate and t-butylperoxyneodecanate. Azo compounds such as oxyesters and 2,2′-azobisisobutyronitrile can be used, and these polymerization initiators may be used alone or in combination of two or more kinds. The amount of the polymerization initiator used is not particularly limited and can be used within a conventionally known range, but is usually about 0.01 to 0.15 based on the total weight of vinyl chloride and other copolymerizable vinyl monomers. It is advisable to use it in a weight percentage.
【００１１】そして、本発明では、塩化ビニルおよび必
要に応じて他の共重合性ビニル単量体を、懸濁剤および
重合開始剤を含む水性媒体中で懸濁重合するに際して、
エタン、プロパンおよびブタンから選ばれる化合物（以
下３者をまとめて「Ｃ2〜4飽和脂肪属炭化水素」という
ことがある）の少なくとも１種を、塩化ビニルおよび他
の共重合性ビニル単量体の重合率が４０〜８０％、好ま
しくは５０〜７０％の間に、塩化ビニル１００部当たり
５部を超え２０部以下、好ましくは５部を超え１５部以
下の割合で添加することが必要である。ここで、本発明
でいう「重合率」とは、塩化ビニル単独重合体を製造す
る場合は得られた塩化ビニル単独重合体の重量を重合に
使用した塩化ビニル単量体の重量で除して１００を掛け
た値をいい、塩化ビニル共重合体を製造する場合は得ら
れた塩化ビニル共重合体の重量を重合に使用した塩化ビ
ニル単量体および他の共重合性ビニル単量体の合計重量
で除して１００を掛けた時の値をいう。In the present invention, when suspension polymerization of vinyl chloride and optionally other copolymerizable vinyl monomer in an aqueous medium containing a suspending agent and a polymerization initiator,
At least one compound selected from ethane, propane and butane (hereinafter sometimes collectively referred to as “C 2-4 saturated aliphatic hydrocarbon”) is vinyl chloride and another copolymerizable vinyl monomer. It is necessary to add at a ratio of more than 5 parts and not more than 20 parts, preferably more than 5 parts and not more than 15 parts per 100 parts of vinyl chloride, while the polymerization rate is 40 to 80%, preferably 50 to 70%. is there. Here, the term "polymerization rate" as used in the present invention means that when a vinyl chloride homopolymer is produced, the weight of the obtained vinyl chloride homopolymer is divided by the weight of the vinyl chloride monomer used for the polymerization. A value multiplied by 100. In the case of producing a vinyl chloride copolymer, the weight of the obtained vinyl chloride copolymer is the sum of the vinyl chloride monomer and other copolymerizable vinyl monomers used for the polymerization. It is the value when multiplied by 100 divided by the weight.
【００１２】重合率が４０％に達しない時点でＣ2〜4飽
和脂肪属炭化水素を添加すると重合の遅延を招き生産性
が低下し、一方重合率が８０％を超えた時点でＣ2〜4飽
和脂肪属炭化水素を添加してもポロシティの向上が達成
されない。また、重合率が４０〜８０％の間に添加する
場合であっても、Ｃ2〜4飽和脂肪属炭化水素の添加量が
上記した５部以下であるとポロシティの高い塩化ビニル
系重合体が得られず、一方２０部を超えると塩化ビニル
系重合体のかさ比重が低下する。When C 2-4 saturated aliphatic hydrocarbon is added at a time when the polymerization rate does not reach 40%, the polymerization is delayed and the productivity is lowered. On the other hand, when the polymerization rate exceeds 80%, C 2- 4 Addition of saturated aliphatic hydrocarbons does not improve porosity. Even when the polymerization rate is added between 40% and 80%, a vinyl chloride polymer having a high porosity is obtained when the amount of the C 2-4 saturated aliphatic hydrocarbon added is 5 parts or less as described above. If the amount exceeds 20 parts, the bulk specific gravity of the vinyl chloride polymer decreases.
【００１３】本発明の方法によってポロシティが高く可
塑剤吸収性の良好な塩化ビニル系重合体が得られる機構
は明らかでないが、重合の終了時に重合装置の内圧解放
する際に塩化ビニル系重合体粒子内に含有されていたＣ
2〜4飽和脂肪属炭化水素が揮散して粒子内の空孔を押し
広げるためであると推定される。The mechanism by which a vinyl chloride polymer having high porosity and good plasticizer absorbability can be obtained by the method of the present invention is not clear. However, vinyl chloride polymer particles are released when the internal pressure of the polymerization apparatus is released at the end of the polymerization. C contained in
It is presumed that this is because 2 to 4 saturated aliphatic hydrocarbons volatilize to spread the pores in the particles.
【００１４】Ｃ2〜4飽和脂肪属炭化水素としては、エタ
ン、プロパンおよびブタンのうちの１種類のみを単独で
使用しても、任意の２種を組み合わせて使用しても、ま
たは３者のすべてを併用してもよい。As the C 2-4 saturated aliphatic hydrocarbon, only one kind of ethane, propane and butane may be used alone, any two kinds may be used in combination, or three kinds thereof may be used. You may use all together.
【００１５】重合温度は特に制限されないが、一般に３
０〜７０℃の温度で重合を行うのが、重合の遅延を招か
ず、目的とする塩化ビニル系重合体を高い生産性で効率
よく製造することができ好ましい。また、本発明の方法
を実施するに当たっては、上記した成分以外にも塩化ビ
ニルの懸濁重合において使用し得ることが知られている
任意の添加剤や成分を必要に応じて使用することができ
る。更に、重合装置も特に限定されず、塩化ビニルの懸
濁重合において使用される既知の重合装置のいずれもが
使用できる。The polymerization temperature is not particularly limited, but is generally 3
It is preferable to carry out the polymerization at a temperature of 0 to 70 ° C., because the polymerization is not delayed and the desired vinyl chloride polymer can be efficiently produced with high productivity. Further, in carrying out the method of the present invention, in addition to the above-mentioned components, any additive or component known to be usable in the suspension polymerization of vinyl chloride can be used if necessary. . Further, the polymerization apparatus is not particularly limited, and any known polymerization apparatus used in suspension polymerization of vinyl chloride can be used.
【００１６】そして、上記した本発明の重合方法を行う
ことによって、ポロシティが高くて可塑剤吸収性に優
れ、しかも熱安定性の良好な粒度の揃った塩化ビニル系
重合体が重合の遅延を招くことなく、高い生産性で効率
よく製造される。By carrying out the above-described polymerization method of the present invention, a vinyl chloride polymer having a high porosity, an excellent plasticizer absorbability, a good thermal stability and a uniform particle size causes a delay in the polymerization. Without being produced, it is efficiently manufactured with high productivity.
【００１７】[0017]
【実施例】以下に本発明を実施例などにより具体的に説
明するが、本発明はそれにより限定されない。以下の例
において、重合率、得られた塩化ビニル系重合体の粒
度、かさ比重、ポロシティ、可塑剤吸収性および熱安定
性は、次のようにして測定または評価した。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, the polymerization rate, the particle size, bulk specific gravity, porosity, plasticizer absorbency and thermal stability of the obtained vinyl chloride polymer were measured or evaluated as follows.
【００１８】重合率：最終的に回収された塩化ビニル系
重合体の重量を測定し、最初に重合缶に仕込んだ塩化ビ
ニルおよび他の共重合性ビニル単量体の合計重量に対す
る割合（％）として求めた。 Polymerization rate : The weight of the vinyl chloride polymer finally recovered is measured, and the ratio (%) to the total weight of vinyl chloride and other copolymerizable vinyl monomers initially charged in the polymerization vessel. Sought as.
【００１９】粒 度：得られた塩化ビニル系重合体をＪ
ＩＳ規格の６０メッシュ篩および２００メッシュ篩を用
いて分級して、６０メッシュ篩の未通過量および２００
メッシュ通過量を測定し、分級に使用した塩化ビニル重
合体重量に対する割合（％）で表示した。 Granularity : The vinyl chloride polymer thus obtained is
Classifying using IS standard 60 mesh sieve and 200 mesh sieve, the unpassed amount of the 60 mesh sieve and 200
The amount of passing through the mesh was measured and expressed as a ratio (%) to the weight of the vinyl chloride polymer used for classification.
【００２０】かさ比重：ＪＩＳ規格Ｋ−６７２１に従っ
て測定した。 Bulk specific gravity : Measured according to JIS standard K-6721.
【００２１】ポロシティ：水銀圧入式ポロシメーター
（湯浅アニオニクス社製；「オートスキャン６０」）を
用いて測定し、累積細孔容積（ｍｌ／ｇ）で表示した。 Porosity : Measured using a mercury press-in type porosimeter (manufactured by Yuasa Anionix; "Autoscan 60"), and displayed as cumulative pore volume (ml / g).
【００２２】可塑剤吸収性：９０℃に加熱したプラネタ
リーミキサーに塩化ビニル系重合体４００部およびジオ
クチルフタレート３２０部を投入して撹拌し、撹拌に要
するエネルギーをトルクで表示し、トルクが安定するま
でに要した時間を可塑剤吸収時間（分）として表示し
た。 Plasticizer absorbency : 400 parts of vinyl chloride polymer and 320 parts of dioctyl phthalate are put into a planetary mixer heated to 90 ° C. and stirred, and the energy required for stirring is displayed in torque to stabilize the torque. The time required until this time was indicated as the plasticizer absorption time (minutes).
【００２３】熱安定性：塩化ビニル系重合体１００部に
Ｂａ−Ｚｎ系安定剤２部を混合し、１５５℃のミキシン
グロールで５分間混練してシートを作製する、このシー
トを５ｃｍ×５ｃｍの大きさに裁断して１８０℃のギャ
ーオーブン中に吊して、シートの面積の半分が黒化する
までの時間を測定した。 Thermal stability : 100 parts of a vinyl chloride polymer is mixed with 2 parts of a Ba-Zn stabilizer and kneaded with a mixing roll at 155 ° C for 5 minutes to prepare a sheet. This sheet has a size of 5 cm x 5 cm. It was cut into a size and hung in a Gar oven at 180 ° C., and the time until half of the area of the sheet was blackened was measured.
【００２４】《予備実験例 １》(重合時間と重合率の
関係の把握：塩化ビニル単独重合体) 撹拌機を装備した重合缶に、イオン交換水１５０ｋｇ、
懸濁剤としてポリビニルアルコールＫＨ−１７（日本合
成化学社製）７０ｇおよびヒドロキシプロピルメチルセ
ルロース（信越化学社製；「メトローズ６０ＳＨ−５
０」）３０ｇおよび重合開始剤としてジ−２−エチルヘ
キシルパーオキシジカーボネート４０ｇを仕込み、真空
脱気後、塩化ビニル１００ｋｇを仕込んで、５８℃に昇
温して重合を開始した。重合開始後１時間して重合を止
め、重合缶内の塩化ビニル重合体を回収して秤量するこ
とにより重合率を求めたところ１１％であった。同様に
して求めた重合開始後２時間、３時間、４時間、５時間
および６時間の重合率はそれぞれ２７％、４６％、６３
％、７７％および８８％であった。<< Preliminary Experimental Example 1 >> (Understanding the relationship between the polymerization time and the polymerization rate: vinyl chloride homopolymer) In a polymerization can equipped with a stirrer, 150 kg of ion-exchanged water,
Polyvinyl alcohol KH-17 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 70 g and hydroxypropylmethyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd .; “Metroses 60SH-5”) as a suspending agent.
0 ") and 30 g of di-2-ethylhexyl peroxydicarbonate as a polymerization initiator were charged, vacuum degassing was performed, 100 kg of vinyl chloride was charged, and the temperature was raised to 58 ° C. to start polymerization. The polymerization was stopped 1 hour after the initiation of the polymerization, and the vinyl chloride polymer in the polymerization vessel was recovered and weighed to obtain a polymerization rate of 11%. Similarly, the polymerization rates of 2 hours, 3 hours, 4 hours, 5 hours and 6 hours after the initiation of the polymerization were 27%, 46% and 63%, respectively.
%, 77% and 88%.
【００２５】《実施例 １》撹拌機を装備した重合缶
に、イオン交換水１５０ｋｇ、懸濁剤としてポリビニル
アルコールＫＨ−１７を７０ｇおよびヒドロキシプロピ
ルメチルセルロース（信越化学社製；「メトローズ６０
ＳＨ−５０」）３０ｇおよび重合開始剤としてジ−２−
エチルヘキシルパーオキシジカーボネート４０ｇを仕込
み、真空脱気後、塩化ビニル１００ｋｇを仕込んで、５
８℃に昇温して重合を開始した。重合開始３．０時間後
に、プロパン７ｋｇを重合缶に圧入した。重合開始から
７時間後に重合缶内圧を開放して未反応塩化ビニルおよ
びプロパンを除き、脱水・乾燥して塩化ビニル重合体を
回収して重合率を測定すると共に、得られた塩化ビニル
重合体の粒度、かさ比重、ポロシティ、可塑剤吸収性お
よび熱安定性重合を上記した方法により調べた。その結
果を下記の表１に示す。Example 1 A polymerization vessel equipped with a stirrer was charged with 150 kg of ion-exchanged water, 70 g of polyvinyl alcohol KH-17 as a suspending agent and hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .; "Metroze 60").
SH-50 ") 30 g and di-2-
Charge 40 g of ethylhexyl peroxydicarbonate, degas under vacuum and charge 100 kg of vinyl chloride.
The temperature was raised to 8 ° C. to initiate polymerization. 3.0 hours after the start of polymerization, 7 kg of propane was press-fitted into the polymerization vessel. After 7 hours from the initiation of polymerization, the pressure inside the polymerization vessel was released to remove unreacted vinyl chloride and propane, dehydrated and dried to recover the vinyl chloride polymer, and the polymerization rate was measured. Particle size, bulk specific gravity, porosity, plasticizer absorbency and heat stable polymerization were investigated by the methods described above. The results are shown in Table 1 below.
【００２６】《実施例 ２》実施例１と同様の操作を経
て重合を開始して３．５時間後にプロパン１５ｋｇを重
合缶に圧入した。重合開始から７時間後に重合缶内圧を
開放して未反応塩化ビニルおよびプロパンを除き、脱水
・乾燥して塩化ビニル重合体を回収して重合率を測定す
ると共に、得られた塩化ビニル重合体の粒度、かさ比
重、ポロシティ、可塑剤吸収性および熱安定性を上記し
た方法により調べた。その結果を下記の表１に示す。Example 2 Polymerization was initiated in the same manner as in Example 1 and, after 3.5 hours, 15 kg of propane was injected under pressure into the polymerization vessel. After 7 hours from the initiation of polymerization, the pressure inside the polymerization vessel was released to remove unreacted vinyl chloride and propane, dehydrated and dried to recover the vinyl chloride polymer, and the polymerization rate was measured. Particle size, bulk specific gravity, porosity, plasticizer absorbency and thermal stability were investigated by the methods described above. The results are shown in Table 1 below.
【００２７】《実施例 ３》実施例１と同様の操作を経
て重合を開始して３．２時間後にブタン１０ｋｇを重合
缶に圧入した。重合開始から７時間後に重合缶内圧を開
放して未反応塩化ビニルおよびプロパンを除き、脱水・
乾燥して塩化ビニル重合体をして回収して重合率を測定
すると共に、得られた塩化ビニル重合体の粒度、かさ比
重、ポロシティ、可塑剤吸収性および熱安定性重合を上
記した方法により調べた。その結果を下記の表１に示
す。Example 3 The polymerization was initiated in the same manner as in Example 1 and 3.2 hours after the start of polymerization, 10 kg of butane was injected under pressure into the polymerization vessel. Seven hours after the initiation of polymerization, the pressure inside the polymerization vessel is released to remove unreacted vinyl chloride and propane, and dehydration /
The vinyl chloride polymer is dried and recovered to measure the polymerization rate, and the particle size, bulk specific gravity, porosity, plasticizer absorbency and heat stable polymerization of the obtained vinyl chloride polymer are investigated by the above-mentioned method. It was The results are shown in Table 1 below.
【００２８】《予備実験例 ２》(重合時間と重合率の
関係の把握：塩ビ／酢ビ共重合体) 撹拌機を装備した重合缶に、イオン交換水１５０ｋｇ、
懸濁剤としてポリビニルアルコールＫＨ−１７を１００
ｇおよびヒドロキシプロピルメチルセルロース（信越化
学社製；「メトローズ６０ＳＨ−５０」）５０ｇおよび
重合開始剤としてジ−２−エチルヘキシルパーオキシジ
カーボネート４５ｇを仕込み、真空脱気後、塩化ビニル
１００ｋｇおよび酢酸ビニル１０ｋｇを仕込んで、５８
℃に昇温して重合を開始した。重合開始後１時間して重
合を止め、重合缶内の塩化ビニル／酢酸ビニル共重合体
を回収して秤量することにより重合率を求めたところ１
３％であった。同様にして求めた重合開始後２時間、３
時間、４時間、５時間および６時間の重合率はそれぞれ
２９％、４７％、６６％、７９％および９１％であっ
た。<< Preliminary Experimental Example 2 >> (Understanding the relationship between the polymerization time and the polymerization rate: vinyl chloride / vinyl acetate copolymer) In a polymerization vessel equipped with a stirrer, 150 kg of ion-exchanged water,
100% polyvinyl alcohol KH-17 as a suspending agent
g and hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .; "Metroze 60SH-50") and 45 g of di-2-ethylhexyl peroxydicarbonate as a polymerization initiator were charged, and after vacuum deaeration, 100 kg of vinyl chloride and 10 kg of vinyl acetate were charged. Prepared, 58
The temperature was raised to ℃ and the polymerization was started. The polymerization was stopped 1 hour after the initiation of the polymerization, and the vinyl chloride / vinyl acetate copolymer in the polymerization vessel was recovered and weighed to obtain the polymerization rate.
It was 3%. 2 hours after initiation of polymerization, which was determined in the same manner, 3
Polymerization rates at hours, 4 hours, 5 hours and 6 hours were 29%, 47%, 66%, 79% and 91%, respectively.
【００２９】《実施例 ４》撹拌機を装備した重合缶
に、イオン交換水１５０ｋｇ、懸濁剤としてポリビニル
アルコールＫＨ−１７を１００ｇおよびヒドロキシプロ
ピルメチルセルロース（信越化学社製；「メトローズ６
０ＳＨ−５０」）５０ｇおよび重合開始剤としてジ−２
−エチルヘキシルパーオキシジカーボネート４５ｇを仕
込み、真空脱気後、塩化ビニル１００ｋｇおよび酢酸ビ
ニル１０ｋｇを仕込んで、５８℃に昇温して重合を開始
した。重合開始３．５時間後に、エタン１０ｋｇを重合
缶に圧入した。重合開始から７時間後に重合缶内圧を開
放して未反応の塩化ビニル、酢酸ビニルおよびプロパン
を除き、脱水・乾燥して塩化ビニル／酢酸ビニル共重合
体を回収して重合率を測定すると共に、得られた塩化ビ
ニル／酢酸ビニル共重合体の粒度、かさ比重、ポロシテ
ィ、可塑剤吸収性および熱安定性重合を上記した方法に
より調べた。その結果を下記の表１に示す。Example 4 A polymerization vessel equipped with a stirrer was charged with 150 kg of ion-exchanged water, 100 g of polyvinyl alcohol KH-17 as a suspending agent and hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .; “Metroze 6”).
0SH-50 ") 50 g and di-2 as a polymerization initiator.
After charging 45 g of ethylhexyl peroxydicarbonate and degassing under vacuum, 100 kg of vinyl chloride and 10 kg of vinyl acetate were charged, and the temperature was raised to 58 ° C. to start polymerization. 3.5 hours after the initiation of polymerization, 10 kg of ethane was press-fitted into the polymerization vessel. After 7 hours from the start of the polymerization, the pressure inside the polymerization vessel is released to remove unreacted vinyl chloride, vinyl acetate and propane, and dehydration / drying is performed to collect the vinyl chloride / vinyl acetate copolymer and measure the polymerization rate. The particle size, bulk specific gravity, porosity, plasticizer absorbency and heat stable polymerization of the resulting vinyl chloride / vinyl acetate copolymer were investigated by the methods described above. The results are shown in Table 1 below.
【００３０】《比較例 １》プロパンを圧入しなかった
以外は実施例１と全く同様の操作を経て塩化ビニル重合
体を製造し、その際の重合率を測定すると共に得られた
塩化ビニル重合体の粒度、かさ比重、ポロシティ、可塑
剤吸収性および熱安定性重合を上記した方法により調べ
た。その結果を下記の表１に示す。Comparative Example 1 A vinyl chloride polymer was produced by the same procedure as in Example 1 except that propane was not injected under pressure, the polymerization rate at that time was measured, and the obtained vinyl chloride polymer was obtained. The particle size, bulk specific gravity, porosity, plasticizer absorbency and heat stable polymerization of were investigated by the methods described above. The results are shown in Table 1 below.
【００３１】《比較例 ２》プロパンの圧入添加量を２
ｋｇとした以外は実施例１と全く同様の操作を経て塩化
ビニル重合体を製造し、その際の重合率を測定すると共
に得られた塩化ビニル重合体の粒度、かさ比重、ポロシ
ティ、可塑剤吸収性および熱安定性重合を上記した方法
により調べた。その結果を下記の表１に示す。<< Comparative Example 2 >> The press-fit addition amount of propane was 2
A vinyl chloride polymer was produced in the same manner as in Example 1 except that the weight was changed to kg, and the polymerization rate at that time was measured, and the particle size, bulk specific gravity, porosity, and plasticizer absorption of the obtained vinyl chloride polymer were measured. Sexual and thermostable polymerizations were investigated by the methods described above. The results are shown in Table 1 below.
【００３２】 《比較例 ３》 撹拌機を装備した重合
缶に、イオン交換水１５０ｋｇ、懸濁剤としてポリビニ
ルアルコールＫＨ−１７を７０ｇおよびヒドロキシプロ
ピルメチルセルロース（信越化学社製；「メトローズ６
０ＳＨ−５０」）３０ｇおよび重合開始剤としてジ−２
−エチルヘキシルパーオキシジカーボネート３００ｇを
仕込み、真空脱気後、塩化ビニル１００ｋｇおよびプロ
パン１５ｋｇを仕込んで、５８℃に昇温して重合を開始
した。重合開始から７時間後に重合缶内圧を開放して未
反応塩化ビニルおよびプロパンを除き、脱水・乾燥して
塩化ビニル重合体を回収して重合率を測定すると共に、
得られた塩化ビニル重合体の粒度、かさ比重、ポロシテ
ィ、可塑剤吸収性および熱安定性重合を上記した方法に
より調べた。その結果を下記の表１に示す。Comparative Example 3 In a polymerization vessel equipped with a stirrer, 150 kg of ion-exchanged water, 70 g of polyvinyl alcohol KH-17 as a suspending agent and hydroxypropylmethylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd .; “Metroze 6”).
0SH-50 ") 30 g and di-2 as a polymerization initiator.
-Ethylhexyl peroxydicarbonate (300 g) was charged, vacuum degassed, 100 kg of vinyl chloride and 15 kg of propane were charged, and the temperature was raised to 58 ° C to initiate polymerization. After 7 hours from the start of the polymerization, the pressure inside the polymerization vessel is released to remove unreacted vinyl chloride and propane, dehydrated and dried to collect the vinyl chloride polymer, and the polymerization rate is measured.
The particle size, bulk specific gravity, porosity, plasticizer absorbency and heat stable polymerization of the resulting vinyl chloride polymer were investigated by the methods described above. The results are shown in Table 1 below.
【００３３】《比較例 ４》重合開始剤であるジ−２−
エチルヘキシルパーオキシジカーボネートの添加量を４
０ｇとした以外は比較例３と同様の操作を経て塩化ビニ
ル重合体の製造を行ったところ、表１に示すように、他
の実施例や比較例に比べて同じ重合時間で到達する重合
率が極めて低く、重合が大幅に遅延していることがわか
る。Comparative Example 4 Di-2-, which is a polymerization initiator
Add ethylhexyl peroxydicarbonate to 4
A vinyl chloride polymer was produced in the same manner as in Comparative Example 3 except that it was 0 g, and as shown in Table 1, the polymerization rate reached in the same polymerization time as in other Examples and Comparative Examples. Is extremely low, and it can be seen that the polymerization is significantly delayed.
【００３４】 《比較例 ５》 ブタン１０ｋｇを重合
開始後６時間後に圧入した以外は実施例３と同様の操作
を経て塩化ビニル重合体を製造し、その際の重合率を測
定すると共に得られた塩化ビニル重合体の粒度、かさ比
重、ポロシティ、可塑剤吸収性および熱安定性重合を上
記した方法により調べた。その結果を下記の表１に示
す。Comparative Example 5 A vinyl chloride polymer was produced in the same manner as in Example 3 except that 10 kg of butane was injected 6 hours after the initiation of the polymerization, and the polymerization rate at that time was measured and obtained. The particle size, bulk specific gravity, porosity, plasticizer absorbency and heat stable polymerization of vinyl chloride polymers were investigated by the methods described above. The results are shown in Table 1 below.
【００３５】《比較例 ６》エタンを圧入添加しなかっ
た以外は実施例４と同様の操作を経て塩化ビニル／酢酸
ビニル共重合体を製造してその重合率を測定すると共
に、得られた共重合体の粒度、かさ比重、ポロシティ、
可塑剤吸収性および熱安定性重合を上記した方法により
調べた。その結果を下記の表１に示す。Comparative Example 6 A vinyl chloride / vinyl acetate copolymer was produced in the same manner as in Example 4 except that ethane was not added under pressure, and the polymerization rate was measured. Polymer particle size, bulk specific gravity, porosity,
Plasticizer absorbency and thermostable polymerization were investigated by the methods described above. The results are shown in Table 1 below.
【００３６】《比較例 ７》エタンの圧入量を３０ｋｇ
とした以外は実施例４と同様の操作を経て塩化ビニル／
酢酸ビニル共重合体を製造してその重合率を測定すると
共に、得られた共重合体の粒度、かさ比重、ポロシテ
ィ、可塑剤吸収性および熱安定性重合を上記した方法に
より調べた。その結果を下記の表１に示す。<Comparative Example 7> The press-fitting amount of ethane is 30 kg.
Vinyl chloride /
A vinyl acetate copolymer was prepared and its polymerization rate was measured, and the particle size, bulk specific gravity, porosity, plasticizer absorbency and heat stable polymerization of the obtained copolymer were examined by the above-mentioned methods. The results are shown in Table 1 below.
【００３７】[0037]
【表１】 [Table 1]
【００３８】上記の表１の結果から、塩化ビニルおよび
他の共重合性ビニル単量体の重合率が４０〜８０％の間
に、エタン、プロパンまたはブタン（Ｃ2〜4飽和脂肪属
炭化水素）を塩化ビニル１００部当たり５部を超え２０
部以下の割合で添加して懸濁重合を行っている本発明の
実施例１〜４では、８９％以上の高い重合率で重合の遅
延を生ずることなく、ポロシティが高くて可塑剤吸収性
に優れた、熱安定性の良好な塩化ビニル系重合体が得ら
れることがわかる。From the results shown in Table 1 above, while the polymerization rate of vinyl chloride and other copolymerizable vinyl monomers was 40 to 80%, ethane, propane or butane (C 2-4 saturated aliphatic hydrocarbon) was obtained. ) Over 5 parts per 100 parts vinyl chloride 20
In Examples 1 to 4 of the present invention in which the suspension polymerization is carried out by adding at a ratio of not more than 1 part, the porosity is high and the plasticizer absorbability is high at a high polymerization rate of 89% or more without delaying the polymerization. It can be seen that an excellent vinyl chloride polymer having good thermal stability can be obtained.
【００３９】また、表１の結果から、Ｃ2〜4飽和脂肪属
炭化水素の添加量が５部よりも少ない比較例１〜２およ
び比較例６、並びにＣ2〜4飽和脂肪属炭化水素を重合率
が８０％を超えてから添加している比較例５の場合には
得られる塩化ビニル系重合体のポロシティが極めて低く
可塑剤吸収性に劣ること、またＣ2〜4飽和脂肪属炭化水
素を重合の当初に添加している比較例３の場合はポロシ
ティの高い塩化ビニル系重合体が得られるがその熱安定
性が著しく低いこと、更にＣ2〜4飽和脂肪属炭化水素を
２０部を超えて添加している比較例６の場合は得られる
塩化ビニル系重合体のかさ比重が極めて低いことがわか
る。From the results shown in Table 1, Comparative Examples 1 and 2 and Comparative Example 6 in which the amount of C 2-4 saturated aliphatic hydrocarbon added was less than 5 parts, and C 2-4 saturated aliphatic hydrocarbon were selected In the case of Comparative Example 5 which is added after the polymerization rate exceeds 80%, the porosity of the obtained vinyl chloride polymer is extremely low and the absorbability of the plasticizer is poor, and C 2-4 saturated aliphatic hydrocarbons are also used. In the case of Comparative Example 3 in which is added at the beginning of the polymerization, a vinyl chloride polymer having high porosity can be obtained, but its thermal stability is remarkably low, and 20 parts of C 2-4 saturated aliphatic hydrocarbon is further added. In the case of Comparative Example 6 in which the addition amount exceeds the above, it is understood that the bulk specific gravity of the obtained vinyl chloride polymer is extremely low.
【００４０】[0040]
【発明の効果】本発明の方法により、ポロシティが高く
可塑剤吸収性が良好で、しかも熱安定性などの物性にも
優れた塩化ビニル系重合体を、重合の遅延などを招くこ
となく、高い生産性で効率よく製造することができる。EFFECT OF THE INVENTION According to the method of the present invention, a vinyl chloride polymer having high porosity, good plasticizer absorbability and excellent physical properties such as thermal stability can be obtained without delaying the polymerization. It can be manufactured efficiently with high productivity.
フロントページの続き (72)発明者 立花 博光 兵庫県高砂市高砂町宮前町１番８号 鐘 淵化学工業株式会社内 (72)発明者 林 宣行 千葉県市原市五井南海岸６番地 電気化 学工業株式会社内 (72)発明者 浅田 直則 愛知県名古屋市港区船見町１番−１ 東 亞合成化学工業株式会社内 (72)発明者 益子 誠一 大阪府高石市高砂１丁目６番地 三井東 圧化学株式会社内Front page continued (72) Inventor Hiromitsu Tachibana 1-8 Miyamae-cho, Takasago-cho, Takasago-shi, Hyogo Kane Fuchi Chemical Industry Co., Ltd. Incorporated (72) Inventor Nasunori Asada 1-1, Funami-cho, Minato-ku, Nagoya, Aichi Toagosei Chemical Industry Co., Ltd. (72) Inventor Seiichi Masuko 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Chemical Within the corporation
Claims (1)
合性ビニル単量体０〜３０重量部を、懸濁剤および重合
開始剤を含む水性媒体中で懸濁重合して塩化ビニル系重
合体を製造するに際し、塩化ビニルおよび他の共重合性
ビニル単量体の重合率が４０〜８０％の間に、塩化ビニ
ル１００重量部当たり、エタン、プロパンおよびブタン
から選ばれる化合物の少なくとも１種を５重量部を超え
２０重量部以下の割合で添加することを特徴とする塩化
ビニル系重合体の製造方法。1. A vinyl chloride polymer obtained by suspension polymerization of 100 parts by weight of vinyl chloride and 0 to 30 parts by weight of another copolymerizable vinyl monomer in an aqueous medium containing a suspending agent and a polymerization initiator. At the time of producing vinyl chloride, at least one compound selected from ethane, propane and butane is added to 100 parts by weight of vinyl chloride while the polymerization rate of vinyl chloride and other copolymerizable vinyl monomer is 40 to 80%. A method for producing a vinyl chloride-based polymer, which comprises adding at a ratio of more than 5 parts by weight and 20 parts by weight or less.
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|---|---|---|---|
| JP5083801A JP2531569B2 (en) | 1993-03-19 | 1993-03-19 | Method for producing vinyl chloride polymer by suspension polymerization |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5083801A JP2531569B2 (en) | 1993-03-19 | 1993-03-19 | Method for producing vinyl chloride polymer by suspension polymerization |
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| Publication Number | Publication Date |
|---|---|
| JPH06271610A JPH06271610A (en) | 1994-09-27 |
| JP2531569B2 true JP2531569B2 (en) | 1996-09-04 |
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ID=13812767
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|---|---|---|---|---|
| JP4939251B2 (en) * | 2007-02-14 | 2012-05-23 | 電気化学工業株式会社 | Organochlorine polymer particles and method for producing the same |
| CN105153457B (en) * | 2015-07-24 | 2018-08-24 | 华侨大学 | A kind of cellular PVC foam ball and preparation method thereof |
| CN114478883A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Preparation method of high-porosity low-involucra HPVC resin |
-
1993
- 1993-03-19 JP JP5083801A patent/JP2531569B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06271610A (en) | 1994-09-27 |
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