JPH059274A - Manufacture of aromatic polyester - Google Patents
Manufacture of aromatic polyesterInfo
- Publication number
- JPH059274A JPH059274A JP18702591A JP18702591A JPH059274A JP H059274 A JPH059274 A JP H059274A JP 18702591 A JP18702591 A JP 18702591A JP 18702591 A JP18702591 A JP 18702591A JP H059274 A JPH059274 A JP H059274A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- ester
- component
- acid
- present
- 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
【０００１】[0001]
【産業上の利用分野】本発明は２，６−ナフタレンジカ
ルボン酸と２，２−ビス（Ｐ−ヒドロキシフェニル）プ
ロパン（以下、ビスフェノールＡと称することがある）
とから主としてなるポリエステルの製造方法に関する。
更に詳しくは熱変型温度が高く、透明性、耐熱性、機械
的特性、耐薬品性に優れたポリエステルの製造方法に関
する。The present invention relates to 2,6-naphthalenedicarboxylic acid and 2,2-bis (P-hydroxyphenyl) propane (hereinafter sometimes referred to as bisphenol A).
It relates to a method for producing a polyester mainly consisting of
More specifically, the present invention relates to a method for producing a polyester having a high heat deformation temperature, excellent transparency, heat resistance, mechanical properties, and chemical resistance.
【０００２】[0002]
【従来の技術】従来、２，６−ナフタレンジカルボン酸
とビスフェノールＡのポリエステルについては、“ＰＯ
ＬＹＭＥＲ ＬＥＴＴＥＲＳ”３巻 Ｐ９４１（１９６
５年）に界面重縮合により重合した例が述べられてい
る。しかしながら、この方法を用いて得られたポリマー
は融点が３７５℃と非常に高く、成形性が悪いという欠
点がある。また、特公昭５６−３２３２９号公報には、
２６０℃で固相重合を行った例が掲げられている。しか
しこの方法においても固相重合に要する時間が長いとい
う問題点がある。2. Description of the Related Art Conventionally, polyesters of 2,6-naphthalenedicarboxylic acid and bisphenol A are "PO
LYMER LETTERS "Volume 3 P941 (196
5 years), an example of polymerization by interfacial polycondensation is described. However, the polymer obtained by this method has a drawback that it has a very high melting point of 375 ° C. and poor moldability. In addition, Japanese Patent Publication No. 56-32329 discloses that
An example in which solid-phase polymerization is performed at 260 ° C. is listed. However, this method also has a problem that the time required for solid phase polymerization is long.
【０００３】[0003]
【発明の目的】そこで、本発明者らは、２，６−ナフタ
レンジカルボン酸とビスフェノールＡとからなる芳香族
ポリエステルの融点より低い温度で安定した溶融状態を
保持することができ、成形性の優れたポリマーを容易な
方法で得ることを目的に鋭意研究を行った。SUMMARY OF THE INVENTION Therefore, the present inventors can maintain a stable molten state at a temperature lower than the melting point of an aromatic polyester composed of 2,6-naphthalenedicarboxylic acid and bisphenol A, and have excellent moldability. Earnestly researched for the purpose of obtaining the above polymer by an easy method.
【０００４】[0004]
【発明の構成】すなわち本発明は、（Ａ）２，６−ナフ
タレンジカルボン酸及び／またはそのエステルを６０〜
９７モル％と（Ｂ）２，６−ナフタレンジカルボン酸以
外の芳香族ジカルボン酸及び／またはそのエステルを４
０〜３モル％と（Ｃ）２，２−ビス（Ｐ−ヒドロキシフ
ェニル）プロパン及び／またはそのエステルをＡ成分と
Ｂ成分との合計に対して９５〜１２０モル％の割合で、
触媒存在下加熱反応せしめる方法において、該ポリエス
テルの固有粘度が０．１以上の段階で重合温度を３３０
℃以上として、該ポリエステルを溶融下反応せしめるこ
とを特徴とする芳香族ポリエステルの製造方法である。That is, the present invention provides (A) 2,6-naphthalenedicarboxylic acid and / or its ester in an amount of 60 to 60%.
97 mol% of (B) an aromatic dicarboxylic acid other than 2,6-naphthalenedicarboxylic acid and / or its ester 4
0 to 3 mol% and (C) 2,2-bis (P-hydroxyphenyl) propane and / or its ester in a proportion of 95 to 120 mol% with respect to the total of A component and B component,
In the method of reacting by heating in the presence of a catalyst, the polymerization temperature is set to 330 when the intrinsic viscosity of the polyester is 0.1 or more.
A method for producing an aromatic polyester, which comprises reacting the polyester under melting at a temperature of not lower than 0 ° C.
【０００５】以下本発明について詳細に説明する。The present invention will be described in detail below.
【０００６】本発明ではＡ成分として２，６−ナフタレ
ンジカルボン酸及び／またはそのエステルを用いるが、
そのエステルとしては炭素数１から６までのアルキルエ
ステル、炭素数６から１２までのアリールエステル等で
あり、特にアリールエステルが好ましい。アリールエス
テルとしてはフェニルエステル、トリルエステル等が例
示され、特にフェニルエステルが好ましい。In the present invention, 2,6-naphthalenedicarboxylic acid and / or its ester is used as the component A,
Examples of the ester include an alkyl ester having 1 to 6 carbon atoms and an aryl ester having 6 to 12 carbon atoms, and the aryl ester is particularly preferable. Examples of the aryl ester include phenyl ester and tolyl ester, and phenyl ester is particularly preferable.
【０００７】本発明の（Ｂ）成分としては２，６−ナフ
タレンジカルボン酸以外の芳香族ジカルボン酸及び／ま
たはそのエステルを用いるが、かかる芳香族ジカルボン
酸としてはテレフタル酸、イソフタル酸、２−メチルテ
レフタル酸、４−メチルイソフタル酸、３，４′−ジフ
ェニルエーテルジカルボン酸、４，４′−ジフェニルエ
ーテルジカルボン酸、２，７−ナフタレンジカルボン酸
等が例示され、特にイソフタル酸、テレフタル酸が好ま
しい。As the component (B) of the present invention, an aromatic dicarboxylic acid other than 2,6-naphthalenedicarboxylic acid and / or an ester thereof is used. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid and 2-methyl Examples thereof include terephthalic acid, 4-methylisophthalic acid, 3,4'-diphenyletherdicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid and 2,7-naphthalenedicarboxylic acid, with isophthalic acid and terephthalic acid being particularly preferred.
【０００８】本発明方法ではＡ成分とＢ成分の割合を９
７／３〜６０／４０の割合で用いる。より好ましくは９
５／５〜７０／３０、特に好ましくは９０／１０〜８０
／２０である。In the method of the present invention, the ratio of the A component and the B component is 9
It is used at a ratio of 7/3 to 60/40. More preferably 9
5/5 to 70/30, particularly preferably 90/10 to 80
/ 20.
【０００９】Ｃ成分としては２，２−ビス（Ｐ−ヒドロ
キシフェニル）プロパンを用い、その割合はＡ成分とＢ
成分の合計量に対して９５〜１２０モル％である。より
好ましくは１００〜１１０モル％ある。これ以外の範囲
では重合反応が遅くなり、好ましくない。又本発明に於
てはＣ成分の一部（例えば３０モル％以下）を他の芳香
族ジヒドロキシ化合物に置きかえても良い。かかる化合
物としては１，１−ビス（Ｐ−ヒドロキシフェニル）シ
クロヘキサン（ビスフェノールＺ）、レゾルシン、フェ
ノールフタレイン等が例示される。2,2-bis (P-hydroxyphenyl) propane is used as the C component, and the ratio thereof is the A component and the B component.
It is 95 to 120 mol% with respect to the total amount of the components. More preferably, it is 100 to 110 mol%. If the content is outside this range, the polymerization reaction becomes slow, which is not preferable. In the present invention, part of the C component (for example, 30 mol% or less) may be replaced with another aromatic dihydroxy compound. Examples of such compounds include 1,1-bis (P-hydroxyphenyl) cyclohexane (bisphenol Z), resorcin, and phenolphthalein.
【００１０】本発明は上記したＡ，Ｂ，Ｃ成分を触媒の
存在下で溶融重合せしめる。この際特に好ましい各成分
の態様は以下のとおりである。In the present invention, the above-mentioned components A, B and C are melt-polymerized in the presence of a catalyst. At this time, particularly preferable embodiments of each component are as follows.
【００１１】（１）Ａ及びＢ成分として主としてアリー
ルエステルを用い、Ｃ成分として主にビスフェノールＡ
を用いる方法 （２）Ａ及びＢ成分として芳香族ジカルボン酸を用い、
Ｃ成分として主にビスフェノールＡの脂肪族エステルを
用いる方法 本発明に於ては上記したＡ，Ｂ，Ｃ成分を触媒の存在下
溶融状態で加熱反応せしめる。一般に本発明の（Ｂ）成
分を含まない２，６−ナフタレンジカルボン酸ジフェニ
ルエステルとビスフェノールＡとからなるポリエステル
は融点が高く、比較例１に示す如く、低い重合温度条件
では反応中に結晶固化してしまう。本発明は溶融状態で
重合する方法でありその目的のためには重合温度を
（Ｂ）成分を含有させたポリエステルの固有粘度が０．
１以上の段階で３３０℃以上、好ましくは、３４０℃以
上とすることが必要である。しかるに本発明の方法によ
れば実施例に示す如く、（Ｂ）成分を含有させることに
より、（Ｂ）成分を含有せず、（Ａ）成分と（Ｃ）成分
とからなるポリエステルの融点より低い３４０℃で重合
しても安定に溶融状態で重合でき、高重合度のポリマー
を得ることができるのである。(1) Aryl ester is mainly used as the A and B components, and bisphenol A is mainly used as the C component.
(2) Using an aromatic dicarboxylic acid as the A and B components,
Method in which aliphatic ester of bisphenol A is mainly used as C component In the present invention, the above A, B and C components are heated and reacted in a molten state in the presence of a catalyst. Generally, the polyester composed of 2,6-naphthalenedicarboxylic acid diphenyl ester not containing the component (B) of the present invention has a high melting point, and as shown in Comparative Example 1, it crystallizes and solidifies during the reaction at low polymerization temperature conditions. Will end up. The present invention is a method of polymerizing in a molten state, and for that purpose, the intrinsic viscosity of the polyester containing the component (B) at a polymerization temperature of 0.
It is necessary to raise the temperature to 330 ° C or higher, preferably 340 ° C or higher in one or more stages. However, according to the method of the present invention, as shown in the examples, by containing the component (B), it is lower than the melting point of the polyester containing the component (A) and the component (C) without containing the component (B). Even if it is polymerized at 340 ° C., it can be stably polymerized in a molten state, and a polymer having a high degree of polymerization can be obtained.
【００１２】本発明では触媒を用いることが必要であ
り、かかる触媒としては従来公知のエステル交換触媒が
使用できる。例えば、アンチモン化合物、スズ化合物、
チタニウム化合物が好ましく、特に三酸化アンチモン、
酢酸錫、チタニウムテトラブトキシドが好ましい。In the present invention, it is necessary to use a catalyst, and a conventionally known transesterification catalyst can be used as such a catalyst. For example, antimony compound, tin compound,
Titanium compounds are preferred, especially antimony trioxide,
Tin acetate and titanium tetrabutoxide are preferred.
【００１３】なお本発明に際しては各種の重合安定剤を
添加することが好ましく、かかる安定剤としては特にリ
ン酸、亜リン酸又はこれらのエステル等が好ましく例示
される。In the present invention, it is preferable to add various polymerization stabilizers. As such stabilizers, phosphoric acid, phosphorous acid or their esters are preferably exemplified.
【００１４】[0014]
【発明の効果】本発明の製造方法によれば、成形性に優
れた芳香族ポリエステルを溶融重合によって、容易に得
ることが可能となる。According to the production method of the present invention, an aromatic polyester having excellent moldability can be easily obtained by melt polymerization.
【００１５】[0015]
【実施例】以下実施例をあげて本発明について説明す
る。なおポリエステルの固有粘度はＰ−クロロフェノー
ル：テトラクロロエチレン混合溶媒（容積比１：１）中
３５℃にて測定した値であり、ガラス転移温度はＤＳＣ
測定より求めた。EXAMPLES The present invention will be described below with reference to examples. The intrinsic viscosity of the polyester is a value measured at 35 ° C. in a P-chlorophenol: tetrachloroethylene mixed solvent (volume ratio 1: 1), and the glass transition temperature is DSC.
Obtained from measurement.
【００１６】[0016]
【実施例１〜６、比較例１〜２】表１に示すごとく２，
６−ナフタレンジカルボン酸ジフェニルエステル、他の
芳香族ジカルボン酸ジフェニルエステル、ビスフェノー
ルＡ、触媒および安定剤を所定量撹拌装置を備えた重合
フラスコに入れ、２６０℃から２時間かけて所定の重合
温度まで昇温加熱した。その重合温度で３０分間保持し
た後、約３０分間かけて絶対圧力を０．５mmHg以下にし
て重合反応を進めポリエステルを得た。仕込量と重合温
度および重合結果を下記の表１に示す。Examples 1-6, Comparative Examples 1-2 As shown in Table 1, 2,
6-Naphthalenedicarboxylic acid diphenyl ester, other aromatic dicarboxylic acid diphenyl ester, bisphenol A, catalyst and stabilizer were placed in a polymerization flask equipped with a predetermined amount of stirrer and heated from 260 ° C to a predetermined polymerization temperature over 2 hours. Heated. After maintaining at the polymerization temperature for 30 minutes, the absolute pressure was adjusted to 0.5 mmHg or less over about 30 minutes to proceed the polymerization reaction to obtain a polyester. The charged amount, the polymerization temperature and the polymerization result are shown in Table 1 below.
【００１７】[0017]
【表１】 [Table 1]
Claims (1)
び／またはそのエステルを６０〜９７モル％と（Ｂ）
２，６−ナフタレンジカルボン酸以外の芳香族ジカルボ
ン酸及び／またはそのエステルを４０〜３モル％と
（Ｃ）２，２−ビス（Ｐ−ヒドロキシフェニル）プロパ
ン及び／またはそのエステルをＡ成分とＢ成分との合計
に対して９５〜１２０モル％の割合で、触媒存在下加熱
反応せしめる方法において、該ポリエステルの固有粘度
が０．１以上の段階で重合温度を３３０℃以上として、
該ポリエステルを溶融下反応せしめることを特徴とする
芳香族ポリエステルの製造方法。Claims: (A) 2,6-naphthalenedicarboxylic acid and / or its ester in an amount of 60 to 97 mol% and (B).
Aromatic dicarboxylic acid other than 2,6-naphthalenedicarboxylic acid and / or its ester 40 to 3 mol% and (C) 2,2-bis (P-hydroxyphenyl) propane and / or its ester A component and B In a method of reacting by heating in the presence of a catalyst in a proportion of 95 to 120 mol% with respect to the total of the components, the polymerization temperature is set to 330 ° C. or higher when the intrinsic viscosity of the polyester is 0.1 or higher,
A process for producing an aromatic polyester, which comprises reacting the polyester under melting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03187025A JP3121865B2 (en) | 1991-07-02 | 1991-07-02 | Method for producing aromatic polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03187025A JP3121865B2 (en) | 1991-07-02 | 1991-07-02 | Method for producing aromatic polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH059274A true JPH059274A (en) | 1993-01-19 |
| JP3121865B2 JP3121865B2 (en) | 2001-01-09 |
Family
ID=16198879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03187025A Expired - Fee Related JP3121865B2 (en) | 1991-07-02 | 1991-07-02 | Method for producing aromatic polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3121865B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2018110091A1 (en) * | 2016-12-15 | 2019-10-24 | 京セラドキュメントソリューションズ株式会社 | Polyarylate resin and electrophotographic photosensitive member |
-
1991
- 1991-07-02 JP JP03187025A patent/JP3121865B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2018110091A1 (en) * | 2016-12-15 | 2019-10-24 | 京セラドキュメントソリューションズ株式会社 | Polyarylate resin and electrophotographic photosensitive member |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3121865B2 (en) | 2001-01-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |