JP3116512B2 - Batch continuous polymerization of liquid crystalline polyester - Google Patents
Batch continuous polymerization of liquid crystalline polyesterInfo
- Publication number
- JP3116512B2 JP3116512B2 JP04021374A JP2137492A JP3116512B2 JP 3116512 B2 JP3116512 B2 JP 3116512B2 JP 04021374 A JP04021374 A JP 04021374A JP 2137492 A JP2137492 A JP 2137492A JP 3116512 B2 JP3116512 B2 JP 3116512B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- liquid crystalline
- crystalline polyester
- 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.)
- Expired - Lifetime
Links
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- Polyesters Or Polycarbonates (AREA)
Description
【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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a batch type continuous polymerization method for obtaining a 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、種々の新規性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性質を有する点で注目され
ている。2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, optics characterized by a parallel arrangement of molecular chains. Attention has been paid to anisotropic liquid crystalline polyesters for having 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。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
した反応を行ない、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回目の液晶ポリエステルは重合缶の吐出口から吐出さ
せる。重合缶からの吐出が終了したなら、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、バッチ重合を押出し式に
連続して行なうものである。As a method for producing a large amount of liquid crystalline polyester, a batch continuous polymerization method is known. In this method, for example, in the case of a deacetic acid polycondensation reaction, for example, two reaction vessels, a reaction vessel and a polymerization vessel, are allowed to communicate with each other, and the first liquid crystal polyester raw material is mainly acetylated in the reaction vessel. After the reaction, the reaction product is transferred to a polymerization vessel to initiate polymerization. Then, the second liquid crystal polyester raw material is charged into the empty reaction vessel, and a reaction mainly involving acetylation is performed. Next, the first liquid crystal polyester which has been polymerized in the polymerization can is discharged from the discharge port of the polymerization can. When the discharge from the polymerization vessel is completed, the second reaction product in which the reaction mainly including acetylation is completed is transferred from the reaction vessel to the polymerization vessel. Thus, the batch polymerization is continuously performed in an extrusion manner.
【0004】[0004]
【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。従来、この冷
却は自然冷却させていたが、従来のバッチ式連続重合法
で得られる液晶ポリエステルには異物が混入しているこ
とが多かった。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。However, the polymerization in the batch 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. It is necessary to cool the temperature in the can to start the polymerization of the batch. Conventionally, this cooling was naturally cooled, but in many cases, foreign substances were mixed in the liquid crystal polyester obtained by the conventional batch-type continuous polymerization method. An object of the present invention is to provide a batch-type continuous polymerization method for obtaining a high-quality liquid crystalline polyester free of such foreign substances.
【0005】[0005]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意検討した結果、次のような本発明に到達
した。即ち本発明は、原料投入口または移液口、重合体
吐出口、攪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返す
バッチ式連続重合法において、溶融ポリマを吐出した
後、1.5時間以内に重合缶の缶内温度をポリマの降温
結晶化温度(Tc)−5℃以下の温度まで冷却し、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。Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention as follows. That is, the present invention melt-polymerizes a liquid crystalline polyester in a polymerization vessel having a material input port or a liquid transfer port, a polymer discharge port, a stirrer, and a jacket, and discharges the molten polymer. It was charged into the <br/> batch continuous polymerization method repeating the polymerization, after discharging the molten polymer, cooling crystallization temperature of the polymer to the temperature in the reactor of the polymerization reactor within 1.5 hours (Tc) -5 ° C. It is intended to provide a batch-type continuous polymerization method for a liquid crystalline polyester, which is cooled to the following temperature, and then the next raw material is charged.
【0006】本発明における降温結晶化温度 (Tc) とは
示差走査熱量測定 (DSC) において、吐出したポリマ
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 (Tm) よりも20℃高い温度 (Tm+20
℃) で5分間保持した後、20℃/分の降温条件で測定し
た際に観測される発熱ピーク温度である。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
行ない、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返えし行なう重合
法のことを言う。[0006] In the present invention, the falling temperature crystallization temperature (Tc) refers to an endothermic peak temperature (Dc) observed when a discharged polymer is measured from room temperature under a heating condition of 20 ° C / min in a differential scanning calorimetry (DSC). 20 ° C higher than (Tm) (Tm + 20
(° C.) for 5 minutes, and the exothermic peak temperature observed when measured under a temperature-lowering condition of 20 ° C./min. The batch continuous polymerization in the present invention refers to a polymerization in which polymerization is carried out for a predetermined time in a reaction vessel, a polymer is discharged, the next raw material is transferred to the reaction vessel, and polymerization is started. Say legal.
【0007】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、攪拌装置およびジャケット
を備えたものである。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
を行ない、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。The number of reaction vessels may be one or more, but at least one vessel (polymerization can) is provided with a raw material inlet or a liquid transfer port, a polymer discharge port, a stirrer, and a jacket. is there. As a process for producing the liquid crystalline polyester, for example, a reaction and polymerization mainly involving acetylation may be carried out in a single vessel in the case of deacetic acid polycondensation reaction, or acetylation may be carried out in a first vessel. The reaction is mainly performed, and the reaction product is transferred to a polymerization vessel through a liquid transfer port,
A method in which polymerization is performed in a polymerization vessel may be used.
【0008】なお、攪拌機の回転方向は攪拌翼により内
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攪拌翼の上部や缶壁の上部に付着
し高融点化するので好ましくない。重合缶および攪拌翼
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
んでもよいがヘリカル翼が好ましい。It is preferable that the rotating direction of the stirrer is a direction in which the contents are scraped down by the stirring blade. In the scraping direction, the polymer adheres to the upper portion of the stirring blade or the upper portion of the can wall and becomes high in melting point, which is not preferable. The shape of the polymerization vessel and the stirring blade may be any shape as long as it is used for ordinary polyester polymerization, but a helical blade is preferable.
【0009】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、特に好ましくは、下記構
造単位 (I)、 (II)、 (IV) または (I)、 (II)、 (III)、
(IV)の構造単位からなる液晶性ポリエステルである。The liquid crystalline polyester obtained by the present invention is a polyester having a melt anisotropy among polyesters comprising units selected from aromatic oxycarboxylate units, aromatic dioxy units, aromatic dicarbonyl units, ethylenedioxy units and the like. And particularly preferably the following structural units (I), (II), (IV) or (I), (II), (III),
It is a liquid crystalline polyester comprising the structural unit of (IV).
【0010】 [0010]
【0011】(ただし式中R1 は (Where R 1 is
【0012】から選ばれた一種以上の基を示し、R2 は And R 2 represents one or more groups selected from
【0013】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(I
I)および(III)の合計と構造単位(IV)は実質
的に等モルである。)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(III)を含む場合は
R1が[0013] One or more groups selected from Also,
In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit (I
The sum of I) and (III) and the structural unit (IV) are substantially equimolar. ) The structural unit (I) is a structural unit of a polyester formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl- 4,4'-
Selected from dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, and 4,4'-dihydroxydiphenyl ether A structural unit generated from an aromatic dihydroxy compound, a structural unit (III) a structural unit generated from ethylene glycol, a structural unit (IV) a terephthalic acid,
Isophthalic acid, 4,4′-diphenylcarboxylic acid, 2,
Selected from 6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and diphenyletherdicarboxylic acid The structural units produced from the aromatic dicarboxylic acids obtained are shown below. When the above structural unit (III) is contained, R 1 is
【0014】 [0014]
【0015】であるものが構造単位 (II) の70モル%以
上を、R2 が 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。一方、上記構造単位 (III)を含まな
い場合R1 がIs at least 70 mol% of the structural unit (II), and R 2 is Those which occupy at least 70 mol% of the structural unit (IV) are particularly preferred. On the other hand, when the above structural unit (III) is not contained, R 1 is
【0016】 [0016]
【0017】R2 は R 2 is
【0018】が特に好ましい。上記構造単位 (I) 〜
(IV) 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。Is particularly preferred. The above structural unit (I)
The copolymerization amount of (IV) is optional. However, the following copolymerization amount is preferred from the viewpoint of fluidity.
【0019】すなわち、上記構造単位(III)を含む
場合は、耐熱性、難燃性および機械的特性の点から上記
構造単位(I)および(II)の合計は構造単位
(I)、(II)および(III)の合計に対して60
〜95モル%が好ましく、82〜93モル%がより好ま
しい。また、構造単位(III)は構造単位(I)、
(II)および(III)の合計に対して40〜5モル
%が好ましく、18〜7モル%がより好ましい。また、
構造単位(I)と(II)のモル比〔(I)/(I
I)〕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78/2
2〜93/7である。また、構造単位(IV)は構造単
位(II)および(III)の合計と実質的に等モルで
ある。That is, when the above-mentioned structural unit (III) is contained, the total of the above-mentioned structural units (I) and (II) is calculated from the viewpoint of heat resistance, flame retardancy and mechanical properties.
60 based on the sum of (I), (II) and (III)
-95 mol% is preferable, and 82-93 mol% is more preferable. Further, the structural unit (III) is the structural unit (I),
It is preferably from 40 to 5 mol%, more preferably from 18 to 7 mol% , based on the total of (II) and (III) . Also,
The molar ratio of the structural units (I) and (II) [(I) / (I
I)] is preferably 75/25 to 95/5, more preferably 78/2, from the viewpoint of the balance between heat resistance and fluidity.
2 to 93/7. Further, the structural unit (IV) is structural units
It is substantially equimolar to the sum of positions (II) and (III) .
【0020】一方、上記構造単位(III)を含まない
場合は流動性の点から上記構造単位(I)は構造単位
(I)および(II)の合計に対して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。なお、本発明の液晶性ポリエス
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。On the other hand, when the structural unit (III) is not contained, the structural unit (I) is a structural unit from the viewpoint of fluidity.
40 to 90 mol% based on the sum of (I) and (II)
The structural unit (IV) is preferably substantially equimolar to the structural unit (II). When the liquid crystalline polyester of the present invention is polycondensed, the above structural units (I) to (IV)
3,3'-diphenyldicarboxylic acid, aromatic dicarboxylic acids such as 2,2'-diphenyldicarboxylic acid, adipic acid, azelaic acid, sebacic acid,
Aliphatic dicarboxylic acids such as dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4 ' Aromatic diols such as dihydroxybenzophenone, 1,4-butanediol, 1,6-hexanediol neopentyl glycol, 1,4-cyclohexanediol, aliphatic and alicyclic diols such as 1,4-cyclohexanedimethanol; Aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid and p-aminophenol, p-aminobenzoic acid and the like are further copolymerized in a small proportion that does not impair the object of the present invention. I can do it.
【0021】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
エステルの溶融重縮合法に準じて製造できるが上記構造
単位(III)を含まない場合は下記 (1), (2) 、構造単
位 (III)を含む場合は下記 (3) の製造方法が好ましく
挙げられる。 (1) p−アセトキシ安息香酸および4, 4'−ジアセト
キシビフェニル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。The method of producing the liquid crystalline polyester in the present invention is not particularly limited, and can be produced according to a known melt polycondensation method of the liquid crystalline polyester. However, when the above structural unit (III) is not contained, the following method is used. When (1), (2) or structural unit (III) is included, the following production method (3) is preferably mentioned. (1) A method of producing from a diacylated product of an aromatic dihydroxy compound such as p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl and an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction.
【0022】(2) p−ヒドロキシ安息香酸および4,
4'−ジヒドロキシビフェニル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。 (3) エチレングリコールとテレフタル酸などの芳香族
ジカルボン酸からのポリエステルポリマ、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。(2) p-hydroxybenzoic acid and 4,
A method of reacting an aromatic dihydroxy compound such as 4'-dihydroxybiphenyl or an aromatic dicarboxylic acid such as terephthalic acid with acetic anhydride to acylate a phenolic hydroxyl group, followed by a deacetic acid polycondensation reaction. (3) In the presence of a polyester polymer, oligomer or bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate from ethylene glycol and an aromatic dicarboxylic acid such as terephthalic acid (1) or A method of manufacturing according to the method of (2).
【0023】かくして得られた液晶性ポリエステルを吐
出せしめた後、重合缶ジャケット温度をポリマの降温結
晶化温度 (Tc) −5℃以下の温度まで1.5時間以内、好
ましくは1時間以内で冷却することが重要であり (Tc−
10℃) 以下が好ましく、 (Tc−15℃) 以下が更に好まし
い。(Tc−5℃) よりも高温であったり、 (Tc−5℃)
以下であっても1.5時間よりも長く放置すると缶内の残
存ポリマが高融点化するため、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。After discharging the thus obtained liquid crystalline polyester, the temperature of the jacket of the polymerization vessel is cooled to a temperature lower than the crystallization temperature (Tc) -5 ° C. of the polymer within 1.5 hours, preferably within 1 hour. Is important (Tc−
10 ° C.) or lower, more preferably (Tc−15 ° C.) or lower. Higher than (Tc-5 ℃) or (Tc-5 ℃)
Even if it is below, if left for more than 1.5 hours, the remaining polymer in the can will have a high melting point, and the high-melting substance will be mixed as foreign matter into the polymerized polymer of the next batch and clog the nozzle of the discharge port. Or the physical properties of the molded article become poor.
【0024】なお本発明に使用する液晶性ポリエステル
(A) は、多くのものが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であり、その際には0.1
g/dlの濃度で60℃で測定した値で0.5以上が好まし
く、特に上記構造単位 (III)を含む場合は1.0〜3.0dl
/g が好ましく、上記構造単位 (III)を含まない場合は
2.0〜10.0dl/g が好ましい。The liquid crystalline polyester used in the present invention
(A) indicates that many of them can measure the logarithmic viscosity in pentafluorophenol, in which case 0.1
It is preferably 0.5 or more when measured at 60 ° C. at a concentration of g / dl, particularly 1.0 to 3.0 dl when the above structural unit (III) is contained.
/ G is preferable, and when the above structural unit (III) is not contained,
2.0 to 10.0 dl / g is preferred.
【0025】また、本発明に使用する液晶性ポリエステ
ル (A) の溶融粘度は10〜20,000ポイズが好ましく、特
に20〜10,000ポイズがより好ましい。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 of the liquid crystalline polyester (A) used in the present invention is preferably from 10 to 20,000 poise, more preferably from 20 to 10,000 poise. The melt viscosity was determined at a melting point (Tm) of + 10 ° C. and a shear rate of 1,000 (1/1).
(Seconds) under the condition of a Koka flow tester.
【0026】[0026]
【実施例】以下、実施例により本発明をさらに説明す
る。 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
付けた攪拌軸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。The present invention will be further described with reference to the following examples. Example 1 vertical and horizontal ratio for the reaction can and polycondensation in which a stirring shaft fitted with a scraping-down direction of the helical ribbon blade into the polymerization apparatus having an inner volume of 0.1 m 3 of 2.5 to a height of 0.035 m 3 The polymerization was carried out as follows using a polymerization can.
【0027】反応缶にp−ヒドロキシ安息香酸22.1kg、
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、 130〜250℃で5時間反応を行
い、その後反応物を重合缶に移液して 250〜330℃で2
時間反応後、2時間かけて重合缶を1.0Torrまで減圧
し、1時間攪拌を続け重縮合反応を完了した。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。得られた液晶性ポリエステル
(A) の理論構造式は次のとおりである。In a reaction vessel, 22.1 kg of p-hydroxybenzoic acid,
2.8 kg of 4,4'-dihydroxybiphenyl, 4.8 kg of polyethylene terephthalate, 2.5 kg of terephthalic acid and 21.7 kg of acetic anhydride were charged, and reacted at 130 to 250 ° C. for 5 hours. Thereafter, the reaction product was transferred to a polymerization vessel. And at 250-330 ℃ 2
After the reaction for 2 hours, the pressure in the polymerization vessel was reduced to 1.0 Torr over 2 hours, and stirring was continued for 1 hour to complete the polycondensation reaction. Then, after pressurizing the inside of the polymerization can to 4 kg / cm 2 , the polymer was discharged in the form of a strand via a die. The obtained liquid crystalline polyester
The theoretical structural formula of (A) is as follows.
【0028】 [0028]
【0029】この液晶性ポリエステル (A) をパーキン
エルマー社製のDSC−7型を用いて、室温から20℃/
分のスピードで昇温して融点 (Tm) を測定した結果 316
℃であった。This liquid crystalline polyester (A) was converted from room temperature to 20 ° C./200° C. using a DSC-7 model manufactured by PerkinElmer.
The melting point (Tm) was measured at a speed of
° C.
【0030】次にこのポリマをTm+20℃、即ち 336℃で
5分間保持した後、20℃/分の速度で降温し、降温結晶
化温度 (Tc) を測定したところ 269℃であった。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、
50分かけて缶内温度を 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、吐出して液晶性
ポリエステル (B) を得た。これらの液晶性ポリエステ
ルのペレット化収率と熱特性を表1に示す。Next, this polymer was kept at Tm + 20 ° C., that is, 336 ° C. for 5 minutes, and then cooled at a rate of 20 ° C./min, and the crystallization temperature (Tc) was measured to be 269 ° C. After the polymer discharge is completed, pour water into the jacket of the polymerization can,
The temperature in the vessel was cooled to 250 ° C. over 50 minutes, and the reaction product of the next batch immediately reacted under the same conditions in the reaction vessel was transferred to a polymerization vessel and polymerized under the same conditions. After the polymerization, the mixture was discharged to obtain a liquid crystalline polyester (B). Table 1 shows the pelletizing yield and thermal characteristics of these liquid crystalline polyesters.
【0031】 [0031]
【0032】実施例2〜5、比較例1〜3 実施例1と同条件で反応缶と重合缶を用いて反応を行な
い、表1の特性の液晶性ポリエステル (A) を吐出終了
後、表2に示す温度 (T) まで所定の時間 (t 1 ) で冷
却した後、その温度で所定の時間 (t2 ) 保持した後、
反応缶で反応させた第2のバッチの反応物を重合缶に移
液し、T〜330℃で実施例1記載のように重合し吐出、
ペレット化し液晶性ポリエステル (C) を得た。これら
液晶性ポリエステル (C) のペレット化収率と熱特性を
表2に示す。Examples 2 to 5 and Comparative Examples 1 to 3 The reaction was carried out under the same conditions as in Example 1 using a reaction vessel and a polymerization vessel.
Discharging of liquid crystalline polyester (A) with the characteristics shown in Table 1
Then, a predetermined time (t) until the temperature (T) shown in Table 2 1) Cold
After the cooling, at that temperature for a predetermined time (tTwo) After holding,
The reactants of the second batch reacted in the reaction vessel are transferred to the polymerization vessel.
Liquor, polymerize and discharge at T-330 ° C. as described in Example 1,
Pellets were obtained to obtain a liquid crystalline polyester (C). these
Pelletization yield and thermal properties of liquid crystalline polyester (C)
It is shown in Table 2.
【0033】 [0033]
【0034】t1 が1時間より長かったり (比較例1、
2) 、Tが (Tc−5℃) より高い時(比較例3) には融
点が表2のように上昇し、液晶性ポリエステル (C) の
吐出時にこの高融点ポリマが口金詰りを起こし、ペレッ
ト化収率が低下することがわかる。When t 1 is longer than 1 hour (Comparative Example 1,
2) When T is higher than (Tc-5 ° C.) (Comparative Example 3), the melting point rises as shown in Table 2, and when the liquid crystalline polyester (C) is discharged, the high melting point polymer causes clogging, It can be seen that the pelletization yield decreases.
【0035】[0035]
【発明の効果】本発明は重合した溶融ポリマを吐出した
後、1.5時間以内に重合缶の缶内温度を、ポリマの降温
結晶化温度 (Tc) −5℃以下の温度まで冷却し、その
後、次回の原料を投入するので、残存ポリマの高融点化
が防止され、その結果、異物の混入がなく、ペレット化
収率が向上する。According to the present invention, after the polymerized molten polymer is discharged, the temperature in the polymerization can is cooled within 1.5 hours to a temperature lower than the crystallization temperature (Tc) of the polymer −5 ° C. After that, since the next raw material is added, the melting point of the remaining polymer is prevented from being increased, and as a result, there is no contamination of foreign matters, and the pelletization yield is improved.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−104932(JP,A) (58)調査した分野(Int.Cl.7,DB名) C08G 63/78 - 63/87 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-56-104932 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 63/78-63/87
Claims (1)
口、攪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返すバ
ッチ式連続重合法において、溶融ポリマを吐出した後、
1.5時間以内に重合缶の缶内温度をポリマの降温結晶
化温度(Tc)−5℃以下の温度まで冷却し、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 vessel having a material input port or a liquid transfer port, a polymer discharge port, a stirrer, and a jacket, and a molten polymer is discharged. In a batch-type continuous polymerization method in which the polymerization is repeated by charging the molten polymer, the molten polymer is discharged,
Within 1.5 hours, the inside temperature of the polymerization can is cooled to a temperature lower than the temperature drop crystallization temperature (Tc) -5 ° C. of the polymer,
A batch type continuous polymerization method for liquid crystalline polyester characterized by charging the next raw material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04021374A JP3116512B2 (en) | 1992-02-06 | 1992-02-06 | Batch continuous polymerization of liquid crystalline polyester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04021374A JP3116512B2 (en) | 1992-02-06 | 1992-02-06 | Batch continuous polymerization of liquid crystalline polyester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05255495A JPH05255495A (en) | 1993-10-05 |
JP3116512B2 true JP3116512B2 (en) | 2000-12-11 |
Family
ID=12053324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP04021374A Expired - Lifetime JP3116512B2 (en) | 1992-02-06 | 1992-02-06 | Batch continuous polymerization of liquid crystalline polyester |
Country Status (1)
Country | Link |
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JP (1) | JP3116512B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5616680A (en) * | 1994-10-04 | 1997-04-01 | Hoechst Celanese Corporation | Process for producing liquid crystal polymer |
-
1992
- 1992-02-06 JP JP04021374A patent/JP3116512B2/en not_active Expired - Lifetime
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JPH05255495A (en) | 1993-10-05 |
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