JPH06192403A - Method of continuous batch polymerization of liquid crystalline polyester - Google Patents
Method of continuous batch polymerization of liquid crystalline polyesterInfo
- Publication number
- JPH06192403A JPH06192403A JP34462492A JP34462492A JPH06192403A JP H06192403 A JPH06192403 A JP H06192403A JP 34462492 A JP34462492 A JP 34462492A JP 34462492 A JP34462492 A JP 34462492A JP H06192403 A JPH06192403 A JP H06192403A
- Authority
- JP
- Japan
- Prior art keywords
- crystalline polyester
- liquid crystalline
- polymerization
- polymer
- structural unit
- 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.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【0001】[0001]
【産業上の利用分野】本発明は高品質の液晶性ポリエス
テルを得るためのバッチ式連続重合法に関する。FIELD OF THE INVENTION This invention relates to a batch continuous polymerization process for obtaining high quality liquid crystalline polyester.
【0002】[0002]
【従来の技術】近年プラスチックの高性能化に対する要
求がますます高まり、種々の新規機能を有するポリマが
数多く開発され、市場に供されているが、中でも分子鎖
の平行な配列を特徴とする光学異方性の液晶性ポリエス
テルが優れた流動性と機械的特質を有する点で注目され
ている。2. Description of the Related Art In recent years, the demand for higher performance of plastics has increased, and many polymers having various new functions have been developed and put on the market. Among them, optics characterized by parallel arrangement of molecular chains Anisotropic liquid crystalline polyester has been attracting attention because of its excellent fluidity and mechanical properties.
【0003】液晶性ポリエステルを大量に製造する方法
としてバッチ式連続重合法が知られている。A batch continuous polymerization method is known as a method for producing a large amount of liquid crystalline polyester.
【0004】この方法は、例えば脱酢酸重縮合反応を例
にとると、反応缶と重合缶の2個の反応容器を連通可能
にしておき、第1回目の液晶性ポリエステル原料を反応
缶でアセチル化を主体とした反応を行い、反応後、その
反応物を重合缶に移して重合を開始する。そして第2回
目の液晶性ポリエステル原料を空になった前記反応缶に
投入し、アセチル化を主体とした反応を行なう。次に重
合缶で重合を完了した第1回目の液晶性ポリエステルは
重合缶の吐出口から吐出される。重合缶からの吐出が終
了したのち、アセチル化を主体とした反応が終了した第
2回目の反応物を反応缶から重合缶に移す。このよう
に、バッチ重合を押出式に連続して行なうものである。In this method, for example, in the case of a deacetic acid polycondensation reaction, two reaction containers, a reaction can and a polymerization can, are allowed to communicate with each other, and the first liquid crystalline polyester material is acetylated in the reaction can. After the reaction, the reaction product is transferred to a polymerization vessel to start the polymerization. Then, the second time the liquid crystalline polyester raw material is charged into the empty reaction can to carry out a reaction mainly based on acetylation. Next, the first liquid crystalline polyester which has completed the polymerization in the polymerization container is discharged from the discharge port of the polymerization container. After the discharge from the polymerization container is completed, the second reaction product in which the reaction mainly composed of acetylation is completed is transferred from the reaction container to the polymerization container. Thus, batch polymerization is continuously carried out by an extrusion method.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、バッチ
式連続重合法における重合は最初は低温で、次第に高温
で反応する、いわゆる昇温重合であるため、1バッチ終
了後、ポリマを吐出した後、次のバッチの重合を開始す
るために缶内温度を冷却する必要がある。However, since the polymerization in the batch type continuous polymerization method is a so-called temperature rising polymerization in which the reaction is initially performed at a low temperature and gradually at a high temperature, after completion of one batch, after discharging the polymer, It is necessary to cool the temperature in the can in order to start the polymerization of the batch.
【0006】従来のバッチ式連続重合法で得られる液晶
性ポリエステルには前のバッチの缶残ポリマが冷却時お
よび昇温時において高結晶化し、これが異物となって混
入していることが多かった。In the liquid crystalline polyester obtained by the conventional batch type continuous polymerization method, the residual polymer of the previous batch was highly crystallized at the time of cooling and at the time of heating, and this was often mixed as a foreign substance. .
【0007】本発明は、この異物が混入していない高品
質の液晶性ポリエステルを得るためのバッチ式連続重合
法を提供することを課題とする。An object of the present invention is to provide a batch type continuous polymerization method for obtaining a high quality liquid crystalline polyester free from the inclusion of foreign matter.
【0008】[0008]
【課題を解決するための手段】即ち本発明は、原料投入
口または移液口、重合体吐出口、撹拌装置およびジャケ
ットを有する重合缶内で液晶性ポリエステルを溶融重合
し、溶融ポリマを吐出した後、次回の原料を同じ重合缶
に投入して重合を繰り返すバッチ式連続重合法におい
て、ポリマを吐出する際、缶残ポリマ量を重合缶の内容
積1m3 当り30kg以下にし、その後、次回の原料を
投入することを特徴とする液晶性ポリエステルのバッチ
式連続重合法を提供するものである。That is, according to the present invention, liquid crystalline polyester is melt-polymerized in a polymerization can having a raw material charging port or liquid transfer port, a polymer discharging port, a stirrer and a jacket, and a molten polymer is discharged. After that, in the batch type continuous polymerization method in which the next raw material is charged into the same polymerization vessel and polymerization is repeated, when the polymer is discharged, the residual polymer amount is set to 30 kg or less per 1 m 3 of the internal volume of the polymerization vessel, and then the next The present invention provides a batch type continuous polymerization method for a liquid crystalline polyester, which comprises charging raw materials.
【0009】本発明における缶残ポリマ量とは仕込量よ
り求められる理論ポリマ量より実際に得られたポリマ量
を差し引いたものである。The residual polymer amount in the present invention is obtained by subtracting the actually obtained polymer amount from the theoretical polymer amount obtained from the charged amount.
【0010】本発明におけるバッチ式連続重合とは、反
応容器中で所定時間重合を行い、重合物を吐出した後、
また次の原料をその反応容器に移し、重合を開始するこ
とを繰り返し行なう重合法のことを言う。The batch type continuous polymerization in the present invention means that the polymerization is carried out in a reaction vessel for a predetermined period of time and the polymer is discharged.
It also refers to a polymerization method in which the following raw materials are transferred to the reaction vessel and polymerization is repeated.
【0011】反応容器は1個でも複数個でもよいが、少
なくともその中の1個の容器(重合缶)は原料投入口ま
たは移液口、重合体吐出口、撹拌装置およびジャケット
を備えたものである。The number of reaction vessels may be one or more, but at least one vessel (polymerization can) is equipped with a raw material inlet or liquid transfer port, a polymer outlet, a stirrer and a jacket. is there.
【0012】液晶性ポリエステルを製造する工程として
は、脱酢酸重縮合反応を例にとると1個の容器内でアセ
チル化を主体とした反応および重合を行なってもよい
し、第1の容器内でアセチル化を主体とした反応を行
い、この反応物を移液口を通して重合缶に移し、重合缶
内で重合を行なう方式でもよい。As a process for producing the liquid crystalline polyester, for example, deacetic acid polycondensation reaction may be carried out by carrying out the reaction and polymerization mainly in acetylation in one container, or in the first container. It is also possible to carry out a reaction mainly involving acetylation, transfer the reaction product to a polymerization vessel through a liquid transfer port, and carry out polymerization in the polymerization vessel.
【0013】なお、撹拌機の回転方向は撹拌機により内
容物が掻き下げになる方向であることが好ましい。掻き
上げ方向ではポリマが撹拌翼の上部や缶壁の上部に付着
し缶残ポリマが増えるので好ましくない。The rotating direction of the stirrer is preferably such that the contents are scraped down by the stirrer. In the scraping direction, the polymer adheres to the upper part of the stirring blade and the upper part of the can wall to increase the residual polymer, which is not preferable.
【0014】重合缶および撹拌翼の形状は通常のポリエ
ステル重合に使われるものならなんでもよいが缶残ポリ
マを少なくする意味ではヘリカル翼が好ましい。The polymerization can and the stirring blade may have any shape as long as they are used in ordinary polyester polymerization, but a helical blade is preferable in the sense that the polymer remaining in the can is reduced.
【0015】本発明で得られる液晶性ポリエステルは芳
香族オキシカルボキシレート単位、芳香族ジオキシ単
位、芳香族ジカルボニル単位、エチレンジオキシ単位な
どから選ばれた単位からなるポリエステルのうち溶融異
方性を示すポリエステルであり、 好ましくは、下記構
造単位(I) 、(II)、(IV)または(I) 、(III) 、(IV)ある
いは(I) 、(II)、(III) 、(IV)の構造単位からなる液晶
性ポリエステルであり、さらに好ましくは下記構造単位
(I) 、(III) 、(IV)あるいは(I) 、(II)、(III)、(IV)
からなる液晶性ポリエステルである。The liquid crystalline polyester obtained by the present invention has a melt anisotropy among polyesters composed of units selected from aromatic oxycarboxylate units, aromatic dioxy units, aromatic dicarbonyl units, ethylenedioxy units and the like. Polyester shown, preferably the following structural unit (I), (II), (IV) or (I), (III), (IV) or (I), (II), (III), (IV) Is a liquid crystalline polyester comprising the structural unit of
(I), (III), (IV) or (I), (II), (III), (IV)
It is a liquid crystalline polyester consisting of.
【0016】[0016]
【化4】 (ただし、式中R1 は[Chemical 4] (However, in the formula, R 1 is
【化5】 から選ばれた一種以上の基を示し、R2 は[Chemical 5] R 1 represents one or more groups selected from
【化6】 から選ばれた一種以上の基を示す。また式中Xは水素原
子または塩素原子を示し、構造単位[(II)+(III) ]と
構造単位(IV)は実質的に等モルである)。[Chemical 6] Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)] and the structural unit (IV) are substantially equimolar).
【0017】上記構造単位(I) はp−ヒドロキシ安息香
酸から生成したポリエステルの構造単位であり、構造単
位(II)は4,4´−ジヒドロキシビフェニル、3,3
´,5,5´−テトラメチル−4,4´−ジヒドロキシ
ビフェニル、ハイドロキノン、t−ブチルハイドロキノ
ン、フェニルハイドロキノン、2,6−ジヒドロキシナ
フタレン、2,7−ジヒドロキシナフタレン、2,2−
ビス(4−ヒドロキシフェニル)プロパンおよび4,4
´−ジヒドロキシジフェニルエーテルから選ばれた芳香
族ジヒドロキシ化合物から生成した構造単位を、構造単
位(III) はエチレングリコールから生成した構造単位
を、構造単位(IV)はテレフタル酸、イソフタル酸、4,
4´−ジフェニルジカルボン酸、2,6−ナフタレンジ
カルボン酸、1,2−ビス(フェノキシ)エタン−4,
4´−ジカルボン酸、1,2−ビス(2−クロルフェノ
キシ)エタン−4,4´−ジカルボン酸およびジフェニ
ルエーテルジカルボン酸から選ばれた芳香族ジカルボン
酸から生成した構造単位を各々示す。これらのうち上記
構造単位(I) 、(II)、(III) 、(IV)からなる共重合体の
場合R1 が、The structural unit (I) is a polyester structural unit produced from p-hydroxybenzoic acid, and the structural unit (II) is 4,4'-dihydroxybiphenyl, 3,3.
′, 5,5′-Tetramethyl-4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-
Bis (4-hydroxyphenyl) propane and 4,4
A structural unit produced from an aromatic dihydroxy compound selected from ′ -dihydroxydiphenyl ether, a structural unit (III) is a structural unit produced from ethylene glycol, and a structural unit (IV) is terephthalic acid, isophthalic acid, 4,
4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,
Each of the structural units formed from an aromatic dicarboxylic acid selected from 4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and diphenyl ether dicarboxylic acid is shown. Of these, in the case of a copolymer composed of the structural units (I), (II), (III) and (IV), R 1 is
【化7】 であるものが構造単位(II)の70モル%以上を、R2 が[Chemical 7] Is 70% by mole or more of the structural unit (II), and R 2 is
【化8】 であるものが構造単位(IV)の70モル%以上を占めるも
のが特に好ましい。[Chemical 8] Particularly preferably those having 70 mol% or more of the structural unit (IV).
【0018】また、上記構造単位(I) 、(III) 、(IV)か
らなる共重合体の場合R2 が、Further, in the case of a copolymer comprising the above structural units (I), (III) and (IV), R 2 is
【化9】 であるものが特に好ましい。[Chemical 9] Are particularly preferred.
【0019】上記構造単位(I) 、(II)、(IV)からなる共
重合体の場合R1 が、In the case of a copolymer comprising the above structural units (I), (II) and (IV), R 1 is
【化10】 および/または[Chemical 10] And / or
【化11】 R2 が[Chemical 11] R 2 is
【化12】 および/または[Chemical 12] And / or
【化13】 であるものが特に好ましい。[Chemical 13] Are particularly preferred.
【0020】上記構造単位(I) 、(II)、(III) および(I
V)の共重合量は任意である。しかし、流動性の点から次
の共重合量であることが好ましい。The above structural units (I), (II), (III) and (I
The copolymerization amount of V) is arbitrary. However, from the viewpoint of fluidity, the following copolymerization amount is preferable.
【0021】すなわち、上記構造単位(I) 、(III) 、(I
V)からなる共重合体の場合は、上記構造単位(I) は
[(I) +(III) ]の30〜95モル%が好ましく、40
〜95モル%がより好ましい。また、構造単位(IV)は構
造単位(III) と実質的に等モルである。That is, the above structural units (I), (III) and (I
In the case of a copolymer comprising V), the structural unit (I) is preferably 30 to 95 mol% of [(I) + (III)],
˜95 mol% is more preferred. Further, the structural unit (IV) is substantially equimolar to the structural unit (III).
【0022】上記構造単位(I) 、(II)、(III) 、(IV)か
らなる共重合体の場合は、上記構造単位[(I) +(II)]
は[(I) +(II)+(III) ]の60〜95モル%が好まし
く、82〜92モル%がより好ましい。また、構造単位
(III) は[(I) +(II)+(III) ]の40〜5モル%が好
ましく、18〜8モル%がより好ましい。また、構造単
位(I) /(II)のモル比は耐熱性と流動性のバランスの点
から好ましくは75/25〜95/5であり、より好ま
しくは78/22〜93/7である。また、構造単位(I
V)は構造単位[(II)+(III) ]と実質的に等モルであ
る。In the case of a copolymer comprising the above structural units (I), (II), (III) and (IV), the above structural units [(I) + (II)]
Is preferably 60 to 95 mol% of [(I) + (II) + (III)], and more preferably 82 to 92 mol%. Also, the structural unit
(III) is preferably 40 to 5 mol% of [(I) + (II) + (III)], and more preferably 18 to 8 mol%. The molar ratio of structural unit (I) / (II) is preferably 75/25 to 95/5, more preferably 78/22 to 93/7 from the viewpoint of the balance between heat resistance and fluidity. Also, the structural unit (I
V) is substantially equimolar to the structural unit [(II) + (III)].
【0023】上記構造単位(I) 、(II)、(IV)からなる共
重合体の場合は流動性の点から上記構造単位(I) は
[(I) +(II)]の40〜90モル%であることが好まし
く、60〜88モル%であることが特に好ましく、構造
単位(IV)は構造単位(II)と実質的に等モルである。In the case of a copolymer comprising the above structural units (I), (II) and (IV), the structural unit (I) is 40 to 90 of [(I) + (II)] from the viewpoint of fluidity. It is preferably mol%, particularly preferably 60 to 88 mol%, and the structural unit (IV) is substantially equimolar to the structural unit (II).
【0024】なお、本発明で好ましく使用できる上記液
晶性ポリエステルを重縮合する際には上記構造単位(I)
〜(IV)を構成する成分以外に3,3´−ジフェニルジカ
ルボン酸、2,2´−ジフェニルジカルボン酸などの芳
香族ジカルボン酸、アジピン酸、アゼライン酸、セバシ
ン酸、ドデカンジオン酸などの脂肪族ジカルボン酸、ヘ
キサヒドロテレフタル酸などの脂環式ジカルボン酸、ク
ロルハイドロキノン、メチルハイドロキノン、4,4´
−ジヒドロキシジフェニルスルホン、4,4´−ジヒド
ロキシジフェニルスルフィド、4,4´−ジヒドロキシ
ベンゾフェノン等の芳香族ジオール、1,4−ブタンジ
オール、1,6−ヘキサンジオール、ネオペンチルグリ
コール、1,4−シクロヘキサンジオール、1,4−シ
クロヘキサンジメタノール等の脂肪族、脂環式ジオール
およびm−ヒドロキシ安息香酸、2,6−ヒドロキシナ
フトエ酸などの芳香族ヒドロキシカルボン酸およびp−
アミノフェノール、p−アミノ安息香酸などを本発明の
目的を損なわない程度の少割合の範囲でさらに共重合せ
しめることができる。When the above-mentioned liquid crystalline polyester which can be preferably used in the present invention is polycondensed, the above structural unit (I) is used.
To an aromatic dicarboxylic acid such as 3,3′-diphenyldicarboxylic acid or 2,2′-diphenyldicarboxylic acid, or an aliphatic compound such as adipic acid, azelaic acid, sebacic acid or dodecanedioic acid Alicyclic dicarboxylic acids such as dicarboxylic acid and hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4,4 '
-Aromatic diols such as dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxybenzophenone, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexane Aliphatic and alicyclic diols such as diols and 1,4-cyclohexanedimethanol and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-
Aminophenol, p-aminobenzoic acid and the like can be further copolymerized in a small proportion within a range not impairing the object of the present invention.
【0025】本発明における液晶性ポリエステルの反応
機構的製造方法は、特に制限がなく、公知の液晶性ポリ
エステルの重縮合法に準じて製造できる。There is no particular limitation on the reaction mechanistic production method of the liquid crystalline polyester in the present invention, and it can be produced according to the known polycondensation method of the liquid crystalline polyester.
【0026】例えば、上記好ましく用いられる液晶性ポ
リエステルの製造において、上記構造単位(III) を含ま
ない場合は(1)および(2)、構造単位(III) を含む
場合は(3)の製造方法が好ましく挙げられる。For example, in the production of the above-mentioned preferably used liquid crystalline polyester, the production method of (1) and (2) when the structural unit (III) is not contained, and (3) when the structural unit (III) is contained. Are preferred.
【0027】(1)p−アセトキシ安息香酸、4,4´
−ジアセトキシビフェニル、ジアセトキシベンゼンなど
の芳香族ジヒドロキシ化合物のジアシル化物とテレフタ
ル酸などの芳香族ジカルボン酸から脱酢酸重縮合反応に
よって製造する方法。(1) p-acetoxybenzoic acid, 4,4 '
A method for producing a diacylated aromatic dihydroxy compound such as diacetoxybiphenyl or diacetoxybenzene and an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction.
【0028】(2)p−ヒドロキシ安息香酸、4,4´
−ジヒドロキシビフェニル、ハイドロキノンなどの芳香
族ジヒドロキシ化合物、テレフタル酸などの芳香族ジカ
ルボン酸に無水酢酸を反応させて、フェノール性水酸基
をアシル化した後、脱酢酸重縮合反応によって製造する
方法。(2) p-hydroxybenzoic acid, 4,4 '
A method in which an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone or an aromatic dicarboxylic acid such as terephthalic acid is reacted with acetic anhydride to acylate a phenolic hydroxyl group, and then a deacetic acid polycondensation reaction is used for production.
【0029】(3)ポリエチレンテレフタレ―トなどの
ポリエステルのポリマ、オリゴマまたはビス(β−ヒド
ロキシエチル)テレフタレートなど芳香族ジカルボン酸
のビス(β−ヒドロキシエチル)エステルの存在下で
(1)または(2)の方法により製造する方法。(3) In the presence of a polyester polymer such as polyethylene terephthalate, an oligomer, or a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate, (1) or ( The method of manufacturing by the method of 2).
【0030】これらの重縮合反応は無触媒でも進行する
が、酢酸第一錫、テトラブチルチタネート、酢酸カリウ
ムおよび酢酸ナトリウム、三酸化アンチモン、金属マグ
ネシウムなどの金属化合物を添加した方が好ましいとき
もある。Although these polycondensation reactions proceed without a catalyst, it is sometimes preferable to add a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, or metal magnesium. .
【0031】本発明においてはかくして得られた液晶性
ポリエステルを缶残ポリマが重合缶の内容積1m3 当り
30kg以下、好ましくは25kg以下となるよう吐出
することが重要である。吐出する内容物のなかで温度が
低く、十分な溶融状態になっていない部分があるとその
部分が吐出せずに缶残ポリマとなってしまうため、内容
物全体が十分な溶融状態となっている必要がある。この
ためには重合缶内温度を後述の[融点(Tm)−5℃]
以上で1.5時間以上、好ましくは2時間以上および/
またはTm以上で0.3時間以上、好ましくは0.5時
間以上の重合条件下で重合することが好ましい。In the present invention, it is important to discharge the liquid crystalline polyester thus obtained so that the residual polymer is 30 kg or less, preferably 25 kg or less per 1 m 3 of the inner volume of the polymerization can. If there is a part of the contents to be discharged that has a low temperature and is not in a sufficiently molten state, that part will not be discharged and will become a residual polymer, so the entire contents will be in a sufficiently molten state. Need to be For this purpose, the temperature inside the polymerization vessel is set to [melting point (Tm) -5 ° C] described later.
1.5 hours or more, preferably 2 hours or more and /
Alternatively, it is preferable to carry out the polymerization under a polymerization condition of Tm or more for 0.3 hour or more, preferably 0.5 hour or more.
【0032】缶残ポリマが重合缶内容積1m3 あたり3
0kgより多いと缶残ポリマが冷却時、あるいは次の重
合時に高融点化し、その高融点物が次のバッチの重合ポ
リマ中に異物として混入し、吐出口の口金を詰まらせた
り、成形品の物性が不良となる。Polymer remaining in the can is 3 per 1 m 3 of the inner volume of the polymerization can.
If the amount is more than 0 kg, the bottom polymer has a high melting point at the time of cooling or during the next polymerization, and the high melting point substance is mixed as foreign matter in the next batch of polymerized polymer, clogging the mouthpiece of the discharge port, The physical properties become poor.
【0033】本発明に好ましく使用できる上記液晶性ポ
リエステルの溶融粘度はペンタフルオロフェノール中で
対数粘度を測定することが可能なものもあり、その際に
は0.1g/dlの濃度で60℃で測定した値で0.3
以上が好ましく、特に上記構造単位(III) を含む場合は
0.5〜3.0dl/gが好ましく、上記構造単位(II
I) を含まない場合は2.0〜10.0dl/gが好ま
しい。The melt viscosity of the above-mentioned liquid crystalline polyester which can be preferably used in the present invention can be measured in logarithmic viscosity in pentafluorophenol, and in that case, at a concentration of 0.1 g / dl at 60 ° C. 0.3 in measured value
The above is preferable, and particularly when the above structural unit (III) is included, 0.5 to 3.0 dl / g is preferable, and the above structural unit (II
When I) is not included, 2.0 to 10.0 dl / g is preferable.
【0034】また、本発明における液晶性ポリエステル
は10〜20,000ポイズが好ましく、特に20〜1
0,000ポイズがより好ましい。The liquid crystalline polyester in the present invention is preferably 10 to 20,000 poise, and more preferably 20 to 1 poise.
More preferably 10,000 poise.
【0035】なお、この溶融粘度は融点(Tm)+10
℃の条件で、ずり速度1,000(1/秒)の条件下で
高化式フローテスターによって測定した値である。The melt viscosity is the melting point (Tm) +10.
It is a value measured by a Koka type flow tester under conditions of a shear rate of 1,000 (1 / sec) under conditions of ° C.
【0036】ここで、融点(Tm)とは示差熱量測定に
おいて、重合を完了したポリマを室温から20℃/分の
昇温条件で測定した際に観測される吸熱ピーク温度(T
m1)の観測後、Tm1 +20℃の温度で5分間保持し
た後、20℃/分の降温条件で室温まで一旦冷却した
後、再度20℃/分の昇温条件で測定した際に観測され
る吸熱ピーク温度(Tm2 )を指す。Here, the melting point (Tm) is the endothermic peak temperature (T) observed in the differential calorimetric measurement when the polymerized polymer is measured at a temperature rising condition from room temperature to 20 ° C./min.
After observing m 1 ), the temperature was maintained at Tm 1 + 20 ° C. for 5 minutes, then cooled once to room temperature under the temperature lowering condition of 20 ° C./min, and then measured again under the temperature rising condition of 20 ° C./min. is the point to the endothermic peak temperature (Tm 2).
【0037】[0037]
【実施例】以下、実施例により本発明をさらに詳述す
る。EXAMPLES The present invention will be described in more detail below with reference to examples.
【0038】実施例1 縦と横の比が2.5の内容積0.1m3 の重合装置に掻
き下げ方向のヘリカルリボン翼を0.035m3 の高さ
まで取り付けた撹拌翼を設けた反応缶と重縮合用の重合
缶を使い、次のように重合した。[0038] Example 1 vertical and horizontal reactor which ratio the scraping-down direction of the helical ribbon blade into the polymerization apparatus having an inner volume of 0.1 m 3 of 2.5 is provided with a stirrer fitted to a height of 0.035 m 3 Was polymerized as follows using a polymerization can for polycondensation.
【0039】反応缶にp−ヒドロキシ安息香酸22.1
kg、4,4’−ジヒドロキシビフェニル2.8kg、
ポリエチレンテレフタレート4.8kg、テレフタル酸
2.5kgおよび無水酢酸21.7kgを仕込み、13
0〜250℃で5時間反応を行い、その後反応物を重合
缶に移液して、2時間かけて缶内温度を250〜315
℃にし、重合缶を1.0Torrまで減圧し、315℃
で2時間撹拌を続け重縮合を完了した。その後重合缶内
を4kg/cm2 に加圧後、口金を経由してポリマをス
トランド状に吐出した。このときの缶残ポリマは1.8
kg(重合缶内容積1m3 当り18kg)ペレット化収
率93%であった。22.1 p-hydroxybenzoic acid was added to the reaction can.
kg, 4,4'-dihydroxybiphenyl 2.8 kg,
Charge 4.8 kg of polyethylene terephthalate, 2.5 kg of terephthalic acid and 21.7 kg of acetic anhydride, and
The reaction is carried out at 0 to 250 ° C. for 5 hours, then the reaction product is transferred to a polymerization vessel, and the temperature inside the vessel is 250 to 315 over 2 hours.
℃, depressurize the polymerization can to 1.0 Torr, 315 ℃
The stirring was continued for 2 hours to complete polycondensation. Thereafter, the inside of the polymerization vessel was pressurized to 4 kg / cm 2 , and then the polymer was discharged in a strand shape through the die. The remaining polymer at this time is 1.8.
kg (18 kg per 1 m 3 of the inner volume of the polymerization vessel) The pelletization yield was 93%.
【0040】得られた液晶性ポリエステルの理論構造式
は次のとおりである。The theoretical structural formula of the obtained liquid crystalline polyester is as follows.
【0041】[0041]
【化14】 k/l/m/n=80/7.5/12.5/20 この液晶性ポリエステルをパーキンエルマー社製のDS
C−7型を用いて、室温から20℃/分のスピードで昇
温して融点(Tm1 )を測定した結果316℃であっ
た。[Chemical 14] k / l / m / n = 80 / 7.5 / 12.5 / 20 This liquid crystalline polyester is manufactured by DS manufactured by Perkin Elmer.
The melting point (Tm 1 ) of the C-7 type was measured at a temperature of 20 ° C./minute from room temperature and the melting point (Tm 1 ) was 316 ° C.
【0042】ポリマの吐出が完了した後、重合缶のジャ
ケットに水を流し、缶内温度を250℃に冷却し、直ち
に反応缶で前記と同条件で反応させた次のバッチの反応
物を重合缶に移液し、同条件で重合した。重合後吐出し
てペレット化収率93%で液晶性ポリエステルを得た。After the discharge of the polymer was completed, water was poured into the jacket of the polymerization vessel to cool the temperature inside the vessel to 250 ° C., and immediately the reaction product of the next batch reacted in the reaction vessel under the same conditions as above was polymerized. The solution was transferred to a can and polymerized under the same conditions. After the polymerization, the mixture was discharged to obtain liquid crystalline polyester with a pelletization yield of 93%.
【0043】実施例2、比較例1 実施例1と重合温度以外は同様に反応缶と重合缶を用い
て反応を行い、重合温度を実施例2は315℃以上で
1.5時間、比較例1は315℃以上で0.1時間にし
て、実施例1と同じ組成の液晶性ポリエステルを吐出し
た。その時の缶残ポリマ量は表1に示した通りである。
その後、実施例1と同様に第2バッチを重合し吐出、ペ
レット化し液晶性ポリエステルを得た。これら液晶性ポ
リエステルの第1バッチの缶残ポリマ量と第2バッチの
ペレット化収率を表1に示す。Example 2 and Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except for the polymerization temperature, using a reaction vessel and a polymerization vessel. The polymerization temperature in Example 2 was 315 ° C. or higher for 1.5 hours. In No. 1, liquid crystalline polyester having the same composition as in Example 1 was discharged at 315 ° C. or higher for 0.1 hour. The amount of residual polymer at that time is as shown in Table 1.
Then, the second batch was polymerized, discharged and pelletized in the same manner as in Example 1 to obtain a liquid crystalline polyester. Table 1 shows the amount of bottom polymer in the first batch of these liquid crystalline polyesters and the pelletization yield of the second batch.
【0044】比較例2 実施例1と同様に重合したポリマを重合缶内圧力を1k
g/cm2 に加圧して、実施例1と同じ組成の液晶性ポ
リエステルを吐出した。その時の缶残ポリマ量は表1に
示した通りである。その後、実施例1と同様に第2バッ
チを重合し吐出、ペレット化し液晶性ポリエステルを得
た。ペレット化収率を表1に示す。Comparative Example 2 A polymer polymerized in the same manner as in Example 1 was polymerized at a pressure of 1 k.
After pressurizing to g / cm 2 , liquid crystalline polyester having the same composition as in Example 1 was discharged. The amount of residual polymer at that time is as shown in Table 1. Then, the second batch was polymerized, discharged and pelletized in the same manner as in Example 1 to obtain a liquid crystalline polyester. The pelletizing yield is shown in Table 1.
【0045】[0045]
【表1】 第1バッチの缶残ポリマ量が重合缶の内容積1m3 あた
り30kgより多いと第2バッチの液晶性ポリエステル
の吐出時に高融点ポリマが口金詰まりを起こし、ペレッ
ト化収率が低下することがわかる。[Table 1] It can be seen that when the residual polymer amount in the first batch is more than 30 kg per 1 m 3 of the inner volume of the polymerization can, the high melting point polymer causes clogging of the die at the time of discharging the liquid crystalline polyester in the second batch, and the pelletization yield decreases. .
【0046】[0046]
【発明の効果】本発明は重合した溶融ポリマを缶残ポリ
マ量が重合缶の内容積1m3 あたり30kg以下となる
よう吐出し、その後、次回の原料を投入するので、缶残
ポリマの高融点化に基づく異物の混入がなく、ペレット
化収率が向上する。Industrial Applicability According to the present invention, the polymerized molten polymer is discharged so that the residual polymer amount is 30 kg or less per 1 m 3 of the internal volume of the polymerization container, and then the next raw material is charged. As a result, the pelletization yield is improved because no foreign matter is mixed in due to the formation.
Claims (3)
口、撹拌装置およびジャケットを有する重合缶内で液晶
性ポリエステルを溶融重合し、溶融ポリマを吐出した
後、次回の原料を同じ重合缶に投入して重合を繰り返す
バッチ式連続重合法において、ポリマを吐出する際、缶
残ポリマを重合缶の内容積1m3 当り30kg以下に
し、その後、次回の原料を投入することを特徴とする液
晶性ポリエステルのバッチ式連続重合法。1. A liquid crystal polyester is melt-polymerized in a polymerization container having a raw material charging port or liquid transfer port, a polymer discharging port, a stirrer and a jacket, and a molten polymer is discharged, and then the next raw material is the same polymerization container. In a batch-type continuous polymerization method in which the polymer is discharged into the reactor, the residual polymer is reduced to 30 kg or less per 1 m 3 of the inner volume of the polymerization container when the polymer is discharged, and then the next raw material is charged. Batch continuous polymerization of water-soluble polyester.
が下記(I) 、(II)、(IV)または(I) 、(III) 、(IV)ある
いは(I) 、(II)、(III) 、(IV)の構造単位からなるもの
である請求項1記載の液晶性ポリエステルのバッチ式連
続重合法。 【化1】 (ただし式中のR1 は 【化2】 から選ばれた一種以上の基を示し、R2 は 【化3】 から選ばれた一種以上の基を示す。また式中Xは水素原
子または塩素原子を示し、構造単位[(II)+(III) ]と
構造単位(IV)は実質的に等モルである)。2. The liquid crystalline polyester according to claim 1, wherein the liquid crystalline polyester is (I), (II), (IV) or (I), (III), (IV) or (I), (II), (III) below. The batch-type continuous polymerization method for a liquid crystalline polyester according to claim 1, which comprises the structural unit of (IV). [Chemical 1] (However, R 1 in the formula is R 1 represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (III)] and the structural unit (IV) are substantially equimolar).
が上記(I) 、(II)、(IV)または(I) 、(II)、(III) 、(I
V)の構造単位からなるものである請求項1記載の液晶性
ポリエステルのバッチ式連続重合法。3. The liquid crystalline polyester according to claim 1, wherein the liquid crystalline polyester is (I), (II), (IV) or (I), (II), (III), (I).
The batch type continuous polymerization method of a liquid crystalline polyester according to claim 1, which comprises a structural unit of V).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34462492A JP3265662B2 (en) | 1992-12-24 | 1992-12-24 | Repeated batch polymerization of liquid crystalline polyester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34462492A JP3265662B2 (en) | 1992-12-24 | 1992-12-24 | Repeated batch polymerization of liquid crystalline polyester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06192403A true JPH06192403A (en) | 1994-07-12 |
JP3265662B2 JP3265662B2 (en) | 2002-03-11 |
Family
ID=18370706
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP34462492A Expired - Lifetime JP3265662B2 (en) | 1992-12-24 | 1992-12-24 | Repeated batch polymerization of liquid crystalline polyester |
Country Status (1)
Country | Link |
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JP (1) | JP3265662B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6642349B1 (en) | 1999-09-13 | 2003-11-04 | Polyplastics Co., Ltd. | Batch type apparatus for production of liquid crystalline polymer, and method for continuous production of liquid crystalline polymer using the apparatus |
JP2008201995A (en) * | 2007-02-22 | 2008-09-04 | Mitsubishi Chemicals Corp | Batchwise production method of polyester-based resin |
US8501897B2 (en) | 2011-07-28 | 2013-08-06 | Sumitomo Chemical Co., Ltd. | Method for producing liquid-crystalline polyester |
-
1992
- 1992-12-24 JP JP34462492A patent/JP3265662B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6642349B1 (en) | 1999-09-13 | 2003-11-04 | Polyplastics Co., Ltd. | Batch type apparatus for production of liquid crystalline polymer, and method for continuous production of liquid crystalline polymer using the apparatus |
JP2008201995A (en) * | 2007-02-22 | 2008-09-04 | Mitsubishi Chemicals Corp | Batchwise production method of polyester-based resin |
US8501897B2 (en) | 2011-07-28 | 2013-08-06 | Sumitomo Chemical Co., Ltd. | Method for producing liquid-crystalline polyester |
Also Published As
Publication number | Publication date |
---|---|
JP3265662B2 (en) | 2002-03-11 |
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