JP2005314471A5 - - Google Patents
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- JP2005314471A5 JP2005314471A5 JP2004131215A JP2004131215A JP2005314471A5 JP 2005314471 A5 JP2005314471 A5 JP 2005314471A5 JP 2004131215 A JP2004131215 A JP 2004131215A JP 2004131215 A JP2004131215 A JP 2004131215A JP 2005314471 A5 JP2005314471 A5 JP 2005314471A5
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Description
この様な連続塊状重合ラインを用いてメタクリル系重合体を製造する際、一個以上の管状反応器からなる非循環重合ライン（ＩＩ）に流出せずに、管状反応器からなる循環重合ライン（Ｉ）内を還流する混合溶液の流量をＦ１（リットル／時間）とし、循環重合ライン（Ｉ）から非循環重合ライン（ＩＩ）に流出する混合溶液の流量Ｆ２（リットル／時間）とした場合の、還流比（Ｒ＝Ｆ１／Ｆ２）は６〜１５の範囲が好ましい。 When a methacrylic polymer is produced using such a continuous bulk polymerization line, it does not flow into the non-circulation polymerization line (II) consisting of one or more tubular reactors, but the circulation polymerization line (I ) When the flow rate of the mixed solution refluxing inside is F1 (liter / hour) and the flow rate of the mixed solution F2 (liter / hour) flowing out from the circulation polymerization line (I) to the non-circulation polymerization line (II), reflux ratio (R = F1 / F2) in the range of 6-15 are preferred.
次に、上記連続塊状重合ラインを用いたメタクリル系重合体の重合方法を、図１の工程図により説明する。プランジャーポンプ（１）によって、原料モノマーとラジカル開始剤及び溶剤を静的ミキシングエレメントを有する管状反応器（２），（３）および（４）とギアポンプ（５）とを有する循環重合ライン（Ｉ）に送られる。循環重合ライン（Ｉ）内で、重合液は循環しながら重合が進み、その一部の重合液は、次の非循環重合ライン（ＩＩ）へ送られる。ここで、循環重合ライン（Ｉ）内を循環する重合液の流量と、非循環重合ライン（ＩＩ）へ流出する重合液の流量との比、還流比Ｒは、非循環重合ライン（ＩＩ）に流出せずに循環重合ライン（Ｉ）内を還流する混合溶液の流量をＦ１（リットル／時間）とし、循環重合ライン（Ｉ）から非循環重合ライン（ＩＩ）に流出する混合溶液の流量Ｆ２（リットル／時間）とした場合、通常Ｒ＝Ｆ１／Ｆ２が６〜１５の範囲であることが好ましい。また、該循環重合ライン（Ｉ）での重合は、該循環重合ライン（Ｉ）出口での全モノマーの合計の重合転化率が、通常３０〜７０質量％、好ましくは３５〜６５質量％になる様に重合させる。重合温度としては１１５〜１４０℃が適している。さらに、該循環重合ライン（Ｉ）から非循環重合ライン（ＩＩ）に向かう接続部分の位置にあるサイドライン（６）から連鎖移動剤を導入して重合物の分子量を大きく制御させる。非循環重合ライン（ＩＩ）での重合温度は、通常１４０〜１６０℃の重合温度であり、重合転化率６０〜９０質量％となるまで連続的に重合される。
次に、この混合溶液はギアポンプ（１０）により予熱器、次いで脱揮発槽に送られ、減圧下にて未反応単量体および溶剤などを除去した後、ペレット化することにより目的とする重合体が得られる。
Next, a method for polymerizing a methacrylic polymer using the continuous bulk polymerization line will be described with reference to the process diagram of FIG. A circulation polymerization line (I) having tubular reactors (2), (3) and (4) having a static mixing element and a gear pump (5) is fed by a plunger pump (1) with raw monomer, radical initiator and solvent. ). In the circulation polymerization line (I), the polymerization proceeds while the polymerization solution is circulated, and a part of the polymerization solution is sent to the next non-circulation polymerization line (II). Here, the ratio of the flow rate of the polymerization liquid circulating in the circulation polymerization line (I) and the flow rate of the polymerization liquid flowing out to the non-circulation polymerization line (II), and the reflux ratio R are set in the non-circulation polymerization line (II). The flow rate of the mixed solution refluxed in the circulation polymerization line (I) without flowing out is defined as F1 (liter / hour), and the flow rate F2 of the mixed solution flowing out from the circulation polymerization line (I) into the non-circulation polymerization line (II) ( In general, R = F1 / F2 is preferably in the range of 6 to 15. In addition, in the polymerization in the circulation polymerization line (I), the total polymerization conversion rate of all monomers at the outlet of the circulation polymerization line (I) is usually 30 to 70% by mass, preferably 35 to 65% by mass. Polymerize in the same manner. A polymerization temperature of 115 to 140 ° C. is suitable. Further, a chain transfer agent is introduced from the side line (6) located at the connecting portion from the circulation polymerization line (I) to the non-circulation polymerization line (II) to greatly control the molecular weight of the polymer. The polymerization temperature in the non-circulation polymerization line (II) is usually a polymerization temperature of 140 to 160 ° C., and the polymerization is continuously performed until the polymerization conversion rate is 60 to 90% by mass.
Next, this mixed solution is sent to a preheater and then to a devolatilization tank by means of a gear pump (10), and after removing unreacted monomers and solvent under reduced pressure, it is pelletized to give the desired polymer. Is obtained.
上記方法で得られた重合体は、揮発分としてのダイマーが１０００ｐｐｍ以下で、残存モノマーが３０００ｐｐｍ以下、残存メルカプタン量が１００ｐｐｍ以下にすることが好ましい。この条件範囲で制御することにより、熱変形温度の低下や成形不良、成形加工時の加熱による着色などを防止することが可能である。 The polymer obtained by the above method preferably has a dimer as a volatile component of 1000 ppm or less, a residual monomer of 3000 ppm or less, and a residual mercaptan amount of 100 ppm or less. By controlling within this condition range, it is possible to prevent a decrease in heat distortion temperature, molding defects, coloring due to heating during molding, and the like.
上記方法で得られた重合体の分子量は、機械的強度を低下させることなく、良好な成形
加工性を得るためには、重量平均分子量が６万〜１４万であることが好ましい。
The molecular weight of the polymer obtained by the above method preferably has a weight average molecular weight of 60,000 to 140,000 in order to obtain good moldability without reducing mechanical strength.
本発明の重合体は、成形加工性に優れ、また、工業的にも効率良く生産可能である。か
かる重合体を成形する際、高級脂肪酸エステルや高級アルコールなどの滑剤も添加可能で
あり、必要があれば帯電防止剤、着色剤、熱安定剤、紫外線吸収剤なども添加することも
可能である。
本発明のメタクリル系重合体の用途として、照明機器関連部材や看板、光学材料関連
などあらゆる分野で使用可能である。
The polymer of the present invention is excellent in moldability and can be produced industrially efficiently. When molding such a polymer, lubricants such as higher fatty acid esters and higher alcohols can be added, and if necessary, antistatic agents, colorants, heat stabilizers, ultraviolet absorbers, etc. can also be added. .
And a methacrylic polymer of application of the present invention, the lighting device associated member and signs, can be used in various fields such as optical materials related.
（連続塊状重合装置）
本実施例で得られるメタクリル系重合体は、図１に示すように配列された装置により得られる。モノマー及び溶媒などを含む混合溶液を、プランジャーポンプ（１）により循環重合ライン（Ｉ）へ送る。循環重合ライン（Ｉ）は入口から順に内径２．５インチ管状反応器（スイス国ゲブリューター・ズルツァー社製ＳＭＸ型スタティックミキサー・静的ミキシングエレメント３０個内蔵）、（２）、（３）及び（４）と混合溶液を循環させるためのギアポンプ（５）から構成されている。管状反応器（４）とギアポンプ（５）の間には非循環重合ライン（ＩＩ）が連結されており、入口から順に上記と同様の管状反応器（７）、（８）及び（９）とギアポンプ（１０）が直結されている。また循環重合ライン（Ｉ）と非循環重合ライン（ＩＩ）の間にサイドライン（６）が接続されている。
(Continuous block polymerization equipment)
The methacrylic polymer obtained in this example is obtained by an apparatus arranged as shown in FIG. The mixed solution containing the monomer and the solvent is sent to the circulation polymerization line (I) by the plunger pump (1). The circulation polymerization line (I) has a 2.5-inch inner diameter tubular reactor in order from the inlet (30 built-in SMX type static mixer and 30 static mixing elements manufactured by Gebrüter Sulzer, Switzerland), (2), (3) and ( 4) and a gear pump (5) for circulating the mixed solution. A non-circulating polymerization line (II) is connected between the tubular reactor (4) and the gear pump (5). The tubular reactors (7), (8) and (9) are the same as described above in order from the inlet. The gear pump (10) is directly connected. A side line (6) is connected between the circulation polymerization line (I) and the non-circulation polymerization line (II).
表１から、生産性が高く、成形加工性に優れるメタクリル系重合体が効率良くできることが明らかである。 From Table 1, it is clear that a methacrylic polymer having high productivity and excellent moldability can be efficiently produced.
Claims (5)
前記連続管状反応器が、初期重合のための循環ライン（Ｉ）と、この循環ライン（Ｉ）から続く、サイドラインを有する非循環重合ライン（ＩＩ）とを有する重合装置であって、
前記循環ライン（Ｉ）における反応温度が１１５〜１４０℃であり、
前記循環ライン（Ｉ）を還流する混合溶液の流量Ｆ１（リットル／時間）と前記非循環重合ライン（ＩＩ）へ流出する混合溶液の流量Ｆ２（リットル／時間）との比である還流比Ｒ＝Ｆ１／Ｆ２が６〜１５の範囲であり、
且つ前記サイドラインから連鎖移動剤を反応溶液中に導入することを特徴とするメタクリル系重合体の製造方法。 A methacrylic polymer produced continuously by bulk polymerization of methyl methacrylate alone or a mixture of methyl methacrylate and at least one selected from alkyl acrylate, alkyl methacrylate other than methyl methacrylate, and styrene using a continuous tubular reactor. Manufacturing method ,
The continuous tubular reactor is a polymerization apparatus having a circulation line (I) for initial polymerization and a non-circulation polymerization line (II) having a side line continuing from the circulation line (I),
The reaction temperature in the circulation line (I) is 115 to 140 ° C.,
A reflux ratio R = a ratio of a flow rate F1 (liter / hour) of the mixed solution refluxing the circulation line (I) and a flow rate F2 (liter / hour) of the mixed solution flowing out to the non-circulation polymerization line (II). F1 / F2 is in the range of 6-15,
A method for producing a methacrylic polymer, wherein a chain transfer agent is introduced into the reaction solution from the side line.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004131215A JP4325475B2 (en) | 2004-04-27 | 2004-04-27 | Methacrylic polymer and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004131215A JP4325475B2 (en) | 2004-04-27 | 2004-04-27 | Methacrylic polymer and process for producing the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2005314471A JP2005314471A (en) | 2005-11-10 |
| JP2005314471A5 true JP2005314471A5 (en) | 2007-05-31 |
| JP4325475B2 JP4325475B2 (en) | 2009-09-02 |
Family
ID=35442234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004131215A Expired - Fee Related JP4325475B2 (en) | 2004-04-27 | 2004-04-27 | Methacrylic polymer and process for producing the same |
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| Country | Link |
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| JP (1) | JP4325475B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009041693A1 (en) * | 2007-09-28 | 2009-04-02 | Denki Kagaku Kogyo Kabushiki Kaisha | Copolymer for polyglutarimide, and process for production thereof |
| DE102008000914A1 (en) * | 2008-04-01 | 2009-10-08 | Evonik Röhm Gmbh | Process for the synthesis of improved binders and modified tacticity |
| JP5840355B2 (en) * | 2009-10-22 | 2016-01-06 | 旭化成ケミカルズ株式会社 | Acrylic resin and molded body |
| US20170298157A1 (en) * | 2014-09-30 | 2017-10-19 | Kuraray Co., Ltd. | Method for producing (meth)acrylic resin |
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