JP2004099683A - Wholly aromatic polyester and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-stable amorphous wholly aromatic polyester and its manufacturing process. <P>SOLUTION: The wholly aromatic polyester substantially comprises a repeating unit expressed by general formula (I) (wherein R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB>and R<SB>4</SB>are the same or different and each represents a hydrogen atom or a methyl group; A is a 6-20C divalent aromatic group; and X is selected from (a) and (b) in a ratio of 100-0 mol%) and an intrinsic viscosity of ≥ 0.3 dL/g (measured at a concentration of 1.2 g/dL in a mixed solvent (wt.ratio of 60/40) of phenol and 1,1,2,2-tetrachloroehtane at 35°C). <P>COPYRIGHT: (C)2004,JPO

Description

【００１３】
（上記式（Ｉ）中のＲ_１、Ｒ_２、Ｒ_３、Ｒ_４は、同一または異なり、水素原子またはメチル基を示す。Ａは炭素数６〜２０の２価の芳香族基を表わし、Ｘは、
【００１４】
【化６】

【００１５】
とから、１００〜０モル％の割合で選択される）
で表される繰り返し単位から実質的になり、固有粘度（フェノール／１，１，２，２−テトラクロロエタン混合溶液（重量比６０／４０）を溶媒として１．２ｇ／ｄｌ濃度、３５℃で測定）が０．３ｄｌ／ｇ以上であることを特徴とする全芳香族ポリエステルによって達成される。
【００１６】
本発明の全芳香族ポリエステルは、本発明の下記の製造方法によって工業的に有利に製造できる。本発明の方法において用いられる芳香族ジオール成分は下記式（ＩＩ）及び／あるいは（ＩＩＩ）
【００１７】
【化７】

【００１８】
（Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は、同一または異なり、水素原子またはメチル基を示す。）
で表されるものである。
【００１９】
本芳香族ジオール成分は環状テルペン１分子にフェノール類２分子を付加反応させて得られる化合物である。このような化合物としては、１，３−ビス（４−ヒドロキシフェニル）−ｐ−メンタン、２，８−ビス（４−ヒドロキシフェニル）−ｐ−メンタン、１，３−ビス（３−メチル−４−ヒドロキシフェニル）−ｐ−メンタン、２，８−ビス（３−メチル−４−ヒドロキシフェニル）−ｐ−メンタン、１，３−ビス（３，５−ジメチル−４−ヒドロキシフェニル）−ｐ−メンタン、２，８−ビス（３，５−ジメチル−４−ヒドロキシフェニル）−ｐ−メンタン等が挙げられ、これらのうち、１，３−ビス（４−ヒドロキシフェニル）−ｐ−メンタン、２，８−ビス（４−ヒドロキシフェニル）−ｐ−メンタンが好ましい。これらの芳香族ジオール成分は必要に応じて、１種あるいは２種以上含有させることができる。
【００２０】
一方、本発明の方法で用いられる芳香族ジカルボン酸ジアリールエステル成分（ｂ）は下記式（ＩＶ）
【００２１】
【化８】

【００２２】
（Ａは炭素数６〜２０の２価の芳香族基である。２個のＲ_５は、それぞれ、互いに同一または相異なり、水素原子、ハロゲン原子、水酸基、カルボキシル基、エステル基、炭素数１〜６のアルコキシル基、あるいは炭素数１〜６のアルキル基から選ばれる。）
で表されるものである。
【００２３】
上記式（ＩＶ）中のＡは芳香核の水素の一部または全部が塩素、臭素等のハロゲン原子あるいは炭素数１〜３の低級アルキル基等で置換されていてもよい。具体的にはフェニレン基、ナフチレン基、ジフェニル基、ジフェニルエーテル基、ジフェニルスルホン基、ジフェニルインダン基等の炭素数６〜２０の二価の芳香族基である。
【００２４】
このような芳香族ジカルボン酸ジアリールエステルとしては、例えば、テレフタル酸ジフェニル、イソフタル酸ジフェニル、メチルテレフタル酸ジフェニル、メチルイソフタル酸ジフェニル、ナフタレン−２，６−ジカルボン酸ジフェニル、ナフタレン−２，７−ジカルボン酸ジフェニル、ジフェニルジカルボン酸ジフェニル、ジフェニルエーテルジカルボン酸ジフェニル、ジフェニルスルホンジカルボン酸ジフェニル、テレフタル酸ジ（ｐ−トリル）、イソフタル酸ジ（ｐ−トリル）、メチルテレフタル酸ジ（ｐ−トリル）、メチルイソフタル酸ジ（ｐ−トリル）、ナフタレン−２，６−ジカルボン酸ジ（ｐ−トリル）、ナフタレン−２，７−ジカルボン酸ジ（ｐ−トリル）、ジフェニルジカルボン酸ジ（ｐ−トリル）、ジフェニルエーテルジカルボン酸ジ（ｐ−トリル）、ジフェニルスルホンジカルボン酸ジ（ｐ−トリル）、テレフタル酸ジ（ｐ−クロロフェニル）、イソフタル酸ジ（ｐ−クロロフェニル）、メチルテレフタル酸ジ（ｐ−クロロフェニル）、メチルイソフタル酸ジ（ｐ−クロロフェニル）、ナフタレン−２，６−ジカルボン酸ジ（ｐ−クロロフェニル）、ナフタレン−２，７−ジカルボン酸ジ（ｐ−クロロフェニル）、ジフェニルジカルボン酸ジ（ｐ−クロロフェニル）、ジフェニルエーテルジカルボン酸ジ（ｐ−クロロフェニル）、ジフェニルスルホンジカルボン酸ジ（ｐ−クロロフェニル）、テレフタル酸ジ（２−メトキシカルボニルフェニル）、イソフタル酸ジ（２−メトキシカルボニルフェニル）、メチルテレフタル酸ジ（２−メトキシカルボニルフェニル）、メチルイソフタル酸ジ（２−メトキシカルボニルフェニル）、ナフタレン−２，６−ジカルボン酸ジ（２−メトキシカルボニルフェニル）、ナフタレン−２，７−ジカルボン酸ジ（２−メトキシカルボニルフェニル）、ジフェニルジカルボン酸ジ（２−メトキシカルボニルフェニル）、ジフェニルエーテルジカルボン酸ジ（２−メトキシカルボニルフェニル）、ジフェニルスルホンジカルボン酸ジ（２−メトキシカルボニルフェニル）、テレフタル酸ジナフチル、イソフタル酸ジナフチル、メチルテレフタル酸ジナフチル、メチルイソフタル酸ジナフチル、ナフタレン−２，６−ジカルボン酸ジナフチル、ナフタレン−２，７−ジカルボン酸ジナフチル、ジフェニルジカルボン酸ジナフチル、ジフェニルエーテルジカルボン酸ジナフチル、ジフェニルスルホンジカルボン酸ジナフチル等を挙げることができる。これらの芳香族ジカルボン酸ジアリールエステルは必要に応じて、１種あるいは２種以上含有させることができる。これらのジアリールエステル基は芳香核を構成する水素原子の一部または全部が塩素、臭素等のハロゲン原子あるいは炭素数１〜３の低級アルキル基等で置換されていてもよい。また、これらのアリールエステル基は１種類のアリールエステル基で使用してもよく、２種以上を併用してもよい。
【００２５】
これらの化合物の溶融縮重合は好ましくは触媒の存在下に実施される。かかる触媒としては、通常エステル化反応、エステル交換反応に使用される触媒を用いることができる。このような化合物としては、アルカリ金属化合物、アルカリ土類金属化合物、亜鉛化合物類、ホウ素化合物類、アルミニウム化合物類、ケイ素化合物類、ゲルマニウム化合物類、有機スズ化合物類、鉛化合物類、チタン化合物類、オスミウム化合物類、アンチモン化合物類およびジルコニウム化合物類，含窒素塩基性化合物などが挙げられる。この中でもアルカリ金属化合物、アルカリ土類金属化合物が好ましく用いられる。
【００２６】
アルカリ金属化合物およびアルカリ土類金属化合物としては、例えばこれらの金属の水酸化物、炭酸水素塩、炭酸塩、酢酸塩、水素化ホウ素塩、ステアリン酸塩、安息香酸およびビスフェノールとの塩等を挙げることができる。
【００２７】
アルカリ金属化合物の具体的な例としては水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素ルビジウム、炭酸水素セシウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウム、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸ルビジウム、酢酸セシウム、ステアリン酸リチウム、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸ルビジウム、ステアリン酸セシウム、安息香酸リチウム、安息香酸ナトリウム、安息香酸カリウム、安息香酸ルビジウム、安息香酸セシウム、リン酸水素二リチウム、リン酸水素二ナトリウム、リン酸水素二カリウム、リン酸水素二ルビジウム、リン酸水素二セシウム、ビスフェノールＡの二リチウム塩、二ナトリウム塩、二カリウム塩、二ルビジウム塩、二セシウム塩、フェノールの二リチウム塩、二ナトリウム塩、二カリウム塩、二ルビジウム塩、および二セシウム塩等が挙げられる。
【００２８】
また、アルカリ土類金属化合物の具体的な例としては、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、炭酸水素マグネシウム、炭酸水素カルシウム、炭酸水素ストロンチウム、炭酸水素バリウム、炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウム、酢酸マグネシウム、酢酸カルシウム、酢酸ストロンチウム、酢酸バリウム、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸ストロンチウムおよびステアリン酸バリウム等を挙げることができる。
【００２９】
これらの触媒の使用量は特に制限はないが、アルカリ金属化合物および／あるいはアルカリ土類金属化合物の場合は芳香族ジオール成分１モルに対して０．００１モル％〜０．１モル％とすることが好ましい。０．００１モル％より少ないと該アルカリ（土類）金属化合物の触媒としての効果が不十分となる。また、０．１モル％より多いと得られるポリマーの物性が低下することがあり好ましくない。より好ましくは０．００５モル％〜０．８モル％である。
【００３０】
本発明の製造方法で製造される全芳香族ポリエステルを含めポリアリレートは一般に高粘度、高融点のため溶融重合が困難とされている。これらの問題を改善する方法の１つとして、特開昭５８−２７７１７号公報にあるようなポリエステルを製造する方法おいて生成するポリエステルと非反応性でかつ分子内にハロゲンを含有しない芳香族イミド化合物の存在下で重合反応を行う技術を適用することも可能である。例えば、イソホロンビスフタルイミドやＮ，Ｎ’−ヘキサメチレンビスフタルイミドなどのような芳香族イミド化合物を可塑剤として使うことができる。
【００３１】
加熱縮重合する際の重合温度は、２００〜４００℃とすることが好ましい。ここで重合温度とは、重合後期あるいはその終了時における反応系の温度を意味する。重合温度が２００℃より低いと、ポリマーの溶融粘度が高くなるため高重合度のポリマーを得ることが困難な場合があり、また４００℃よりも高いと、ポリマー劣化等が生じやすくなることがある。
【００３２】
本発明の製造方法では、重合反応温度の初期は比較的低温とし、これを徐々に昇温して最終的に上記重合温度にすることが好ましい。この際の初期重合反応の重合温度は、好ましくは１８０〜３００℃である。
【００３３】
この重合反応は常圧下もしくは減圧下で実施されるが、初期重合反応時は常圧下とし、徐々に減圧とすることが好ましい。また、常圧時には反応系は窒素、アルゴン等の不活性ガス雰囲気下とすることが好ましい。重合反応時間は特に制限はないが、およそ０．２〜１０時間程度である。
【００３４】
上記の如き方法によれば、本発明の前記新規重合体が得られる。用途や必要に応じて酸化防止剤、紫外線吸収剤、離型剤などの添加剤を配合することができる。
【００３５】
【発明の効果】
本発明によれば、従来の全芳香族ポリエステルの機械特性を保持したまま、耐熱性に優れた非晶性の全芳香族ポリエステルを得ることができる。本発明の全芳香族ポリエステルは耐熱性、透明性等を有し、自動車用ライトカバー、電子部材等の成形品に好適に用いることができる。
【００３６】
【実施例】
以下、実施例および比較例を挙げて本発明を詳述するが、本発明はこれらによって何ら限定されるものではない。なお、本発明において物性評価に用いた方法は以下の通りである。
（１）固有粘度測定
測定は、フェノール／１，１，２，２−テトラクロロエタン混合溶媒（重量比６０／４０）中、１．２ｇ／ｄｌの濃度で、温度３５℃で測定した。
（２）ガラス転移温度
測定は、ＤＳＣ（ＴＡ　Ｉｎｓｔｒｕｍｅｎｔｓ製２９２０型）を用い、１０℃／ｍｉｎの昇温速度にて測定した。
（３）ジクロロメタン溶解性
得られた全芳香族ポリエステルを１８重量％の濃度でジクロロメタンに溶解し、溶液の状態を目視で観察した。
（４）引張強度
（３）で得られた溶液を用い、厚み約５０μｍの溶液キャストフィルムを作成した。このフィルムについてＪＩＳ　Ｋ７１２７に基づいて引張強度を測定した。
【００３７】
［実施例１］
１，３−ビス（４−ヒドロキシフェニル）−ｐ−メンタン（ＹＰ−９０：ヤスハラケミカル（株））９７．２ｇ、テレフタル酸ジフェニルエステル２８．９ｇ、ナフタレン−２，６−ジカルボン酸ジフェニルエステル７８．１ｇ、４−ジメチルアミノピリジン０．０７３ｇ、炭酸セシウム０．１９５ｇ、イソホロンビスフタルイミド１３５ｇを撹拌装置および窒素導入口を備えた真空留出系を有する反応容器に入れ、反応容器中を窒素雰囲気とした後、常圧下２００℃で反応を開始した。３０分後常圧のまま２４０℃に昇温し、同温度にてフェノールの留出を確認した後、系内を徐々に減圧した。反応開始から１時間後、原料が均一に溶解していることを確認した。
【００３８】
その後さらに、昇温、減圧し、反応開始から３時間後、系内の最終到達温度を２８０℃、真空度を約０．５ｍｍＨｇとした。同条件下にて３時間重合を行い、非晶性の全芳香族ポリエステルを得た。このとき昇華物はほとんど生じなかった。得られたポリマーは淡黄色透明であった。
【００３９】
冷却後、得られたポリマーを粉砕し、ジクロロメタン２７００ｇに溶解した後、激しく攪拌している大量のアセトン中にそのジクロロメタン溶液を投入し、ポリマーを沈殿させた。沈殿したポリマーを濾別・乾燥し、耐熱性全芳香族ポリエステルが得られた。
【００４０】
得られたポリマーについてそれぞれ前述した評価を行った。ポリマーの還元粘度は、０．６２、ガラス転移温度は２８７℃であった。また、ジクロロメタンに対する溶解性は完全溶解であり、キャストフィルムによる引張強度は８１ＭＰａであった。
【００４１】
［実施例２、３］
表１に示した原料を用い、実施例１と同様にして全芳香族ポリエステルを得た。得られた全芳香族ポリエステルの物性を表１に示した。
【００４２】
【表１】

【００４３】
［実施例４］
１，３−ビス（４−ヒドロキシフェニル）−ｐ−メンタン６８．０ｇ、２，８−ビス（４−ヒドロキシフェニル）−ｐ−メンタン２９．２ｇ、テレフタル酸ジフェニルエステル９６．４ｇ、４−ジメチルアミノピリジン０．０７３ｇ、炭酸セシウム０．１９５ｇ、イソホロンビスフタルイミド１３５ｇを撹拌装置および窒素導入口を備えた真空留出系を有する反応容器に入れ、反応容器中を窒素雰囲気とした後、常圧下２００℃で反応を開始した。３０分後常圧のまま２４０℃に昇温し、同温度にてフェノールの留出を確認した後、系内を徐々に減圧した。反応開始から１時間後、原料が均一に溶解していることを確認した。
【００４４】
その後さらに、昇温、減圧し、反応開始から３時間後、系内の最終到達温度を２８０℃、真空度を約０．５ｍｍＨｇとした。同条件下にて３時間重合を行い、非晶性の全芳香族ポリエステルを得た。このとき昇華物はほとんど生じなかった。得られたポリマーは淡黄色透明であった。
【００４５】
冷却後、得られたポリマーを粉砕し、ジクロロメタン２７００ｇに溶解した後、激しく攪拌している大量のアセトン中にそのジクロロメタン溶液を投入し、ポリマーを沈殿させた。沈殿したポリマーを濾別・乾燥し、耐熱性全芳香族ポリエステルが得られた。得られたポリマーについてそれぞれ前述した評価を行った。ポリマーの還元粘度は、０．６０、ガラス転移温度は２３０℃であった。また、ジクロロメタンに対する溶解性は完全溶解であり、キャストフィルムによる引張強度は５８ＭＰａであった。
【００４６】
［実施例５，６］
表２に示した原料を用い、実施例４と同様にして同様にして全芳香族ポリエステルを得た。得られた全芳香族ポリエステルの物性を表２に示した。
【００４７】
【表２】

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the production of wholly aromatic polyesters. More specifically, the present invention relates to a wholly aromatic polyester that is amorphous and has excellent heat stability, and a method for producing the same.
[0002]
[Prior art]
In recent years, performance requirements for engineering plastics having high heat resistance and excellent mechanical strength have been increasing. As one of the heat-resistant amorphous engineering plastics, an amorphous wholly aromatic polyester (hereinafter sometimes referred to as “polyarylate”), which is a polyester derived from an aromatic dicarboxylic acid and an aromatic diol, is well known. ing.
[0003]
For example, amorphous polyarylate synthesized using bisphenols such as 2,2-bis (4-hydroxyphenyl) propane as an aromatic diol and terephthalic acid and isophthalic acid as an aromatic dicarboxylic acid is relatively balanced. It has excellent characteristics and is used for various purposes.
[0004]
Such polyarylate has high heat resistance, excellent mechanical strength and dimensional stability represented by impact strength, and because it is transparent, its molded products can be widely applied to fields such as electric / electronics, automobiles and machinery. It is well known that it is being done. However, in recent years, in such application fields, further reduction in thickness of parts has been demanded in accordance with the demand for weight reduction, and residues of 2,2-bis (4-hydroxyphenyl) propane and terephthalic acid as well as acrylic resins and polycarbonates have been demanded. And / or polyarylate comprising a residue of isophthalic acid also did not have sufficient heat resistance. Under such circumstances, a polymer having high heat resistance has been demanded.
[0005]
As an attempt to improve the heat resistance of polyarylate, various bisphenols are used instead of 2,2-bis (4-hydroxyphenyl) propane, or there is a copolymerized polyarylate (for example, Patent Document 1). , Patent Document 2, Patent Document 3, and Patent Document 4).
[0006]
In addition, there is a method in which the acid component is changed from terephthalic acid and isophthalic acid to various naphthalenedicarboxylic acids to improve heat resistance (for example, refer to Patent Document 5, Patent Document 6, Patent Document 7).
[0007]
Various studies have hitherto been made on methods for producing these amorphous wholly aromatic polyesters, and among them, an interfacial polycondensation method between an acid halide of an aromatic dicarboxylic acid and an aromatic diol has been industrialized. However, methylene chloride, which is usually used as a reaction solvent in this interfacial polycondensation method, is a chemical substance having environmental and sanitary problems, and its handling requires great care. However, since its boiling point is as low as 40 ° C., it is difficult to make a closed system in which methylene chloride used in the production of polyarylate can be completely recycled in terms of equipment, and it is very costly. There is also a problem that methylene adversely affects the environment and hygiene.
[0008]
Therefore, a method of producing these polyarylates by a melt polymerization method has been studied (for example, see Patent Document 8).
[0009]
[Patent Document 1]
Japanese Patent Publication No. 4-50324 (page 2-3)
[Patent Document 2]
JP-A-57-192432 (pages 4-6)
[Patent Document 3]
JP-A-2-233720 (pages 1-5, page 8, Table 1)
[Patent Document 4]
JP-A-6-329969 (page 2-5, Table 1)
[Patent Document 5]
JP-A-6-122775 (page 2-3, Table 1)
[Patent Document 6]
JP-A-2-255719 (page 2-5, Table 1)
[Patent Document 7]
JP-A-9-124781 (pages 2-6, Table 1)
[Patent Document 8]
JP-A-7-133345 (pages 3-6)
[0010]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a wholly aromatic polyester having excellent heat stability and a method for producing the same.
[0011]
[Means for Solving the Problems]
According to the present invention, the above object of the present invention is achieved by the following formula (I)
[0012]
Embedded image

[0013]
(R ₁ , R ₂ , R ₃ , and R ₄ in the above formula (I) are the same or different and represent a hydrogen atom or a methyl group. A represents a divalent aromatic group having 6 to 20 carbon atoms; X is
[0014]
Embedded image

[0015]
Is selected at a ratio of 100 to 0 mol%)
Consisting essentially of a repeating unit represented by the following formula, and measured at 35 ° C. at a concentration of 1.2 g / dl using an intrinsic viscosity (phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40) as a solvent). ) Is at least 0.3 dl / g.
[0016]
The wholly aromatic polyester of the present invention can be industrially advantageously produced by the following production method of the present invention. The aromatic diol component used in the method of the present invention has the following formula (II) and / or (III)
[0017]
Embedded image

[0018]
(R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and represent a hydrogen atom or a methyl group.)
It is represented by
[0019]
The aromatic diol component is a compound obtained by subjecting one molecule of cyclic terpene to an addition reaction of two molecules of phenols. Such compounds include 1,3-bis (4-hydroxyphenyl) -p-menthane, 2,8-bis (4-hydroxyphenyl) -p-menthane, 1,3-bis (3-methyl-4 -Hydroxyphenyl) -p-menthane, 2,8-bis (3-methyl-4-hydroxyphenyl) -p-menthane, 1,3-bis (3,5-dimethyl-4-hydroxyphenyl) -p-menthane , 2,8-bis (3,5-dimethyl-4-hydroxyphenyl) -p-menthane and the like, among which 1,3-bis (4-hydroxyphenyl) -p-menthane and 2,8 -Bis (4-hydroxyphenyl) -p-menthane is preferred. One or more of these aromatic diol components can be contained as necessary.
[0020]
On the other hand, the aromatic dicarboxylic acid diaryl ester component (b) used in the method of the present invention has the following formula (IV)
[0021]
Embedded image

[0022]
(A is a divalent aromatic group having 6 to 20 carbon atoms. Two R _{5 s} are the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, an ester group, Selected from an alkoxy group of 1 to 6 or an alkyl group of 1 to 6 carbon atoms.)
It is represented by
[0023]
In A in the above formula (IV), part or all of the hydrogen of the aromatic nucleus may be substituted with a halogen atom such as chlorine or bromine, or a lower alkyl group having 1 to 3 carbon atoms. Specifically, it is a divalent aromatic group having 6 to 20 carbon atoms such as a phenylene group, a naphthylene group, a diphenyl group, a diphenyl ether group, a diphenylsulfone group, and a diphenylindane group.
[0024]
Examples of such an aromatic dicarboxylic acid diaryl ester include diphenyl terephthalate, diphenyl isophthalate, diphenyl methyl terephthalate, diphenyl methyl isophthalate, diphenyl naphthalene-2,6-dicarboxylate, and naphthalene-2,7-dicarboxylic acid. Diphenyl, diphenyl diphenyl dicarboxylate, diphenyl diphenyl ether dicarboxylate, diphenyl diphenyl sulfone dicarboxylate, di (p-tolyl) terephthalate, di (p-tolyl) isophthalate, di (p-tolyl) methyl terephthalate, di-methyl isophthalate (P-tolyl), naphthalene-2,6-dicarboxylic acid di (p-tolyl), naphthalene-2,7-dicarboxylic acid di (p-tolyl), diphenyldicarboxylic acid di (p-tolyl), diphenyl ether Dicarboxylic acid di (p-tolyl), diphenylsulfone dicarboxylic acid di (p-tolyl), terephthalic acid di (p-chlorophenyl), isophthalic acid di (p-chlorophenyl), methyl terephthalic acid di (p-chlorophenyl), methyl isophthalate Acid di (p-chlorophenyl), naphthalene-2,6-dicarboxylic acid di (p-chlorophenyl), naphthalene-2,7-dicarboxylic acid di (p-chlorophenyl), diphenyldicarboxylic acid di (p-chlorophenyl), diphenyl ether dicarboxylic acid Acid di (p-chlorophenyl), diphenylsulfonodicarboxylic acid di (p-chlorophenyl), terephthalic acid di (2-methoxycarbonylphenyl), isophthalic acid di (2-methoxycarbonylphenyl), methyl terephthalic acid di (2-methoxycarbonyl) H Nyl), di (2-methoxycarbonylphenyl) methylisophthalate, di (2-methoxycarbonylphenyl) naphthalene-2,6-dicarboxylate, di (2-methoxycarbonylphenyl) naphthalene-2,7-dicarboxylate, diphenyl Di (2-methoxycarbonylphenyl) dicarboxylate, di (2-methoxycarbonylphenyl) diphenyl ether dicarboxylate, di (2-methoxycarbonylphenyl) diphenylsulfonate, dinaphthyl terephthalate, dinaphthyl isophthalate, dinaphthyl methyl terephthalate, methyl Dinaphthyl isophthalate, dinaphthyl naphthalene-2,6-dicarboxylate, dinaphthyl naphthalene-2,7-dicarboxylate, dinaphthyl diphenyldicarboxylate, dinaphthyl diphenylether dicarboxylate Tyl and dinaphthyl diphenylsulfonedicarboxylate. One or two or more of these aromatic dicarboxylic acid diaryl esters can be contained as necessary. In these diaryl ester groups, some or all of the hydrogen atoms constituting the aromatic nucleus may be substituted by halogen atoms such as chlorine and bromine, or lower alkyl groups having 1 to 3 carbon atoms. Further, these aryl ester groups may be used as one kind of aryl ester group, or two or more kinds thereof may be used in combination.
[0025]
The melt condensation polymerization of these compounds is preferably carried out in the presence of a catalyst. As such a catalyst, a catalyst usually used for an esterification reaction or a transesterification reaction can be used. Such compounds include alkali metal compounds, alkaline earth metal compounds, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, titanium compounds, Examples include osmium compounds, antimony compounds, zirconium compounds, and nitrogen-containing basic compounds. Among them, alkali metal compounds and alkaline earth metal compounds are preferably used.
[0026]
Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides, hydrogen carbonates, carbonates, acetates, borohydrides, stearates, salts with benzoic acid and bisphenol of these metals. be able to.
[0027]
Specific examples of the alkali metal compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, Lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, lithium stearate, sodium stearate, potassium stearate, rubidium stearate, cesium stearate, Lithium benzoate, sodium benzoate, potassium benzoate, rubidium benzoate, cesium benzoate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dirubidium hydrogen phosphate, Dicesium hydrogen oxy, bislithium dilithium salt, disodium salt, dipotassium salt, dirubidium salt, dicesium salt, phenol dilithium salt, disodium salt, dipotassium salt, dirubidium salt, and dicesium salt And the like.
[0028]
Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, Examples include calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, strontium stearate, and barium stearate.
[0029]
The use amount of these catalysts is not particularly limited, but in the case of an alkali metal compound and / or an alkaline earth metal compound, the amount is 0.001 mol% to 0.1 mol% based on 1 mol of an aromatic diol component. Is preferred. When the amount is less than 0.001 mol%, the effect of the alkali (earth) metal compound as a catalyst becomes insufficient. On the other hand, if it is more than 0.1 mol%, the physical properties of the obtained polymer may be undesirably reduced. More preferably, it is 0.005 mol% to 0.8 mol%.
[0030]
Polyarylates, including wholly aromatic polyesters produced by the production method of the present invention, are generally considered to be difficult to melt-polymerize due to their high viscosity and high melting point. One of the methods for solving these problems is an aromatic imide which is non-reactive with a polyester produced in a method for producing a polyester as disclosed in JP-A-58-27717 and which does not contain a halogen in the molecule. It is also possible to apply a technique of performing a polymerization reaction in the presence of a compound. For example, an aromatic imide compound such as isophorone bisphthalimide or N, N'-hexamethylenebisphthalimide can be used as a plasticizer.
[0031]
The polymerization temperature during the heat condensation polymerization is preferably from 200 to 400 ° C. Here, the polymerization temperature means the temperature of the reaction system at the end of the polymerization or at the end of the polymerization. If the polymerization temperature is lower than 200 ° C., it may be difficult to obtain a polymer having a high degree of polymerization because the melt viscosity of the polymer becomes high, and if it is higher than 400 ° C., the polymer may be easily deteriorated. .
[0032]
In the production method of the present invention, it is preferable that the initial temperature of the polymerization reaction is relatively low, and the temperature is gradually increased to finally reach the polymerization temperature. The polymerization temperature of the initial polymerization reaction at this time is preferably 180 to 300 ° C.
[0033]
This polymerization reaction is carried out under normal pressure or under reduced pressure, but it is preferable to reduce the pressure to normal pressure during the initial polymerization reaction and gradually reduce the pressure. Further, at normal pressure, the reaction system is preferably placed under an atmosphere of an inert gas such as nitrogen or argon. The polymerization reaction time is not particularly limited, but is about 0.2 to 10 hours.
[0034]
According to the above method, the novel polymer of the present invention is obtained. Additives such as an antioxidant, an ultraviolet absorber, and a release agent can be blended according to the use and need.
[0035]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the amorphous wholly aromatic polyester excellent in heat resistance can be obtained, maintaining the mechanical characteristics of the conventional wholly aromatic polyester. The wholly aromatic polyester of the present invention has heat resistance, transparency and the like, and can be suitably used for molded articles such as automobile light covers and electronic members.
[0036]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the method used for the physical property evaluation in the present invention is as follows.
(1) Intrinsic Viscosity Measurement The measurement was carried out in a phenol / 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 60/40) at a concentration of 1.2 g / dl at a temperature of 35 ° C.
(2) The glass transition temperature was measured at a heating rate of 10 ° C./min using DSC (model 2920 manufactured by TA Instruments).
(3) Solubility in dichloromethane The obtained wholly aromatic polyester was dissolved in dichloromethane at a concentration of 18% by weight, and the state of the solution was visually observed.
(4) Using the solution obtained in tensile strength (3), a solution cast film having a thickness of about 50 μm was prepared. The tensile strength of this film was measured based on JIS K7127.
[0037]
[Example 1]
97.2 g of 1,3-bis (4-hydroxyphenyl) -p-menthane (YP-90: Yasuhara Chemical Co., Ltd.), 28.9 g of terephthalic acid diphenyl ester, 78.1 g of naphthalene-2,6-dicarboxylic acid diphenyl ester , 4-dimethylaminopyridine 0.073 g, cesium carbonate 0.195 g, and isophorone bisphthalimide 135 g were placed in a reaction vessel having a vacuum distillation system equipped with a stirrer and a nitrogen inlet, and the inside of the reaction vessel was set to a nitrogen atmosphere. The reaction was started at 200 ° C. under normal pressure. After 30 minutes, the temperature was raised to 240 ° C. at normal pressure, and at the same temperature, the distillation of phenol was confirmed. One hour after the start of the reaction, it was confirmed that the raw materials were uniformly dissolved.
[0038]
Thereafter, the temperature was further increased and the pressure was reduced. After 3 hours from the start of the reaction, the final temperature in the system was set to 280 ° C., and the degree of vacuum was set to about 0.5 mmHg. Polymerization was carried out under the same conditions for 3 hours to obtain an amorphous wholly aromatic polyester. At this time, almost no sublimate was generated. The obtained polymer was pale yellow and transparent.
[0039]
After cooling, the obtained polymer was pulverized, dissolved in 2700 g of dichloromethane, and then poured into a large amount of vigorously stirred acetone to precipitate the polymer. The precipitated polymer was separated by filtration and dried to obtain a heat-resistant wholly aromatic polyester.
[0040]
Each of the obtained polymers was evaluated as described above. The reduced viscosity of the polymer was 0.62, and the glass transition temperature was 287 ° C. The solubility in dichloromethane was complete dissolution, and the tensile strength of the cast film was 81 MPa.
[0041]
[Examples 2 and 3]
Using the raw materials shown in Table 1, a wholly aromatic polyester was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the obtained wholly aromatic polyester.
[0042]
[Table 1]

[0043]
[Example 4]
68.0 g of 1,3-bis (4-hydroxyphenyl) -p-menthane, 29.2 g of 2,8-bis (4-hydroxyphenyl) -p-menthane, 96.4 g of terephthalic acid diphenyl ester, 4-dimethylamino Pyridine (0.073 g), cesium carbonate (0.195 g), and isophorone bisphthalimide (135 g) were placed in a reaction vessel having a vacuum distillation system equipped with a stirrer and a nitrogen inlet. The reaction was started. After 30 minutes, the temperature was raised to 240 ° C. at normal pressure, and at the same temperature, the distillation of phenol was confirmed. One hour after the start of the reaction, it was confirmed that the raw materials were uniformly dissolved.
[0044]
Thereafter, the temperature was further increased and the pressure was reduced. After 3 hours from the start of the reaction, the final temperature in the system was set to 280 ° C., and the degree of vacuum was set to about 0.5 mmHg. Polymerization was carried out under the same conditions for 3 hours to obtain an amorphous wholly aromatic polyester. At this time, almost no sublimate was generated. The obtained polymer was pale yellow and transparent.
[0045]
After cooling, the obtained polymer was pulverized, dissolved in 2700 g of dichloromethane, and then poured into a large amount of vigorously stirred acetone to precipitate the polymer. The precipitated polymer was separated by filtration and dried to obtain a heat-resistant wholly aromatic polyester. Each of the obtained polymers was evaluated as described above. The reduced viscosity of the polymer was 0.60, and the glass transition temperature was 230 ° C. The solubility in dichloromethane was complete dissolution, and the tensile strength of the cast film was 58 MPa.
[0046]
[Examples 5 and 6]
Using the raw materials shown in Table 2, a wholly aromatic polyester was obtained in the same manner as in Example 4. Table 2 shows the physical properties of the obtained wholly aromatic polyester.
[0047]
[Table 2]

Claims (2)

The following formula (I)

(R ₁ , R ₂ , R ₃ and R ₄ in the above formula (I) are the same or different and represent a hydrogen atom or a methyl group. A represents a divalent aromatic group having 6 to 20 carbon atoms; X is

Is selected at a ratio of 100 to 0 mol%)
Consisting essentially of a repeating unit represented by the following formula, and measured at 35 ° C. at a concentration of 1.2 g / dl using an intrinsic viscosity (phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40) as a solvent). ) Is 0.3 dl / g or more. Formula (II) or (III) below

(R ₁ , R ₂ , R ₃ , and R ₄ in the above formulas (II) and (III) are the same or different and represent a hydrogen atom or a methyl group.)
An aromatic diol component represented by the following formula (IV):

(A in the above formula (IV) is a divalent aromatic group having 6 to 20 carbon atoms. The two R _{5 s} are the same or different from each other and are a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group. , An ester group, an alkoxyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.)
Is reacted with a melt of the aromatic dicarboxylic acid diaryl ester component represented by the formula (1), and the intrinsic viscosity (phenol / 1,1,2,2-tetrachloroethane mixed solution (weight ratio 60/40) as a solvent, a concentration of 1.2 g / dl). , Measured at 35 ° C.) of at least 0.3 dl / g.