JPH0570583A - Production of modified polycarbonate - Google Patents
Production of modified polycarbonateInfo
- Publication number
- JPH0570583A JPH0570583A JP26259491A JP26259491A JPH0570583A JP H0570583 A JPH0570583 A JP H0570583A JP 26259491 A JP26259491 A JP 26259491A JP 26259491 A JP26259491 A JP 26259491A JP H0570583 A JPH0570583 A JP H0570583A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- biphenol
- bischloroformate
- bisphenol
- added
- 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、透明性および耐熱性の
優れた変性ポリカーボネートの製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a modified polycarbonate having excellent transparency and heat resistance.
【０００２】[0002]
【従来の技術】プラスチックを光ファイバーに使用する
必要性が益々大きくなっているが、そのためには透明性
の良いことと同時に耐熱性の良いものを用いることが要
求される。2. Description of the Related Art The necessity of using plastics for optical fibers is increasing more and more, and for that purpose, it is required to use one having good transparency and heat resistance.
【０００３】従来、光ファイバー用のプラスチックに
は、主に透明性の良いアクリル系の重合体が用いられて
いたが、最近ではポリカーボネートが用いられるように
なってきた。しかしながら、ポリカーボネートも透明性
および耐熱性の点で、実用上問題がある。Conventionally, an acrylic polymer having good transparency has been mainly used as a plastic for an optical fiber, but recently, a polycarbonate has been used. However, polycarbonate also has a problem in practical use in terms of transparency and heat resistance.
【０００４】本発明に類似のビフェノールとビスフェノ
ールとの共重合体が特開昭６２−１５３２２号に開示さ
れている。しかしながらこの共重合体はビスフェノール
のオリゴマーとビフェノールとの反応で製造されてお
り、本発明により製造される交互共重合体は知られてい
なかった。A copolymer of biphenol and bisphenol similar to the present invention is disclosed in JP-A-62-15322. However, this copolymer is produced by reacting an oligomer of bisphenol and biphenol, and the alternating copolymer produced by the present invention has not been known.
【０００５】[0005]
【発明が解決しょうとする課題】本発明は、透明性およ
び耐熱性の優れたポリカーボネートを得ることを目的と
する。DISCLOSURE OF THE INVENTION An object of the present invention is to obtain a polycarbonate having excellent transparency and heat resistance.
【０００６】[0006]
【課題を解決するための手段】本発明は化７SUMMARY OF THE INVENTION
【化７】 （式中Ｒ1 及びＲ2 はそれぞれ水素原子、低級アルキル
基またはトリフルオロメチル基を示す。さらにＲ1 、Ｒ
2 が一緒になって環を形成してもよい。）で表わされる
平均分子量２０，０００〜１００，０００の変性ポリカ
ーボネートの製造方法である。[Chemical 7] (Each of R 1 and R 2 wherein hydrogen atom, a lower alkyl group or a trifluoromethyl group. Further R 1, R
Two may together form a ring. ) Is a method for producing a modified polycarbonate having an average molecular weight of 20,000 to 100,000.
【０００７】本発明変性ポリカーボネートは以下の通り
に製造できる。 （１）The modified polycarbonate of the present invention can be manufactured as follows. (1)
【化８】 反応は式〔II〕で表わされるビフェノールビスクロロ蟻
酸エステルを塩化メチレン等の有機溶媒あるいは有機溶
媒と水との混合溶媒に溶解し、式〔III 〕で表わされる
ビスフェノール及び苛性ソーダ等の水酸化アルカリの水
溶液を０〜５０℃で滴下あるいは数回に分けて添加し、
その後、目的の分子量になるまで通常は２時間から１０
数時間攪拌することにより行なわれる。反応のモル比は
式〔II〕で表わされるビフェノールビスクロロ蟻酸エス
テル１モルに対し、式〔III 〕で表わされるビスフェノ
ール０．９〜１．１モル、好しくは等モル、水酸化アル
カリは１．８〜２．２モル、好しくは２モル付近であ
り、さらに速度調整用として０〜２．０モル追加するこ
ともできる。目的の分子量になったら攪拌を止め、慣用
の後処理を行なうことにより共重合体を得ることができ
る。[Chemical 8] The reaction is carried out by dissolving the biphenol bischloroformate ester represented by the formula [II] in an organic solvent such as methylene chloride or a mixed solvent of an organic solvent and water to prepare a bisphenol represented by the formula [III] and an alkali hydroxide such as caustic soda. Aqueous solution is added dropwise at 0 to 50 ° C or added in several times,
Then, usually 2 hours to 10 until the desired molecular weight is reached.
It is carried out by stirring for several hours. The molar ratio of the reaction is 0.9 to 1.1 moles of the bisphenol represented by the formula [III], preferably 1 mole thereof, and 1 mole of the alkali hydroxide based on 1 mole of the biphenol bischloroformate ester represented by the formula [II]. It is about 0.8 to 2.2 mol, preferably about 2 mol, and 0 to 2.0 mol can be added for speed adjustment. When the desired molecular weight is reached, stirring is stopped and a conventional post-treatment is carried out to obtain a copolymer.
【０００８】（２）(2)
【化９】 反応、後処理等は（１）の場合と同様に行なうことがで
きる。[Chemical 9] The reaction, post-treatment and the like can be carried out in the same manner as in (1).
【０００９】式〔II〕あるいは式〔IV〕で表わされるビ
スクロロ蟻酸エステルはそれぞれ式〔Ｖ〕あるいは式
〔III 〕で表わされる化合物をホスゲン化することによ
って得られる。The bischloroformate represented by the formula [II] or the formula [IV] can be obtained by phosgenating the compound represented by the formula [V] or the formula [III], respectively.
【００１０】[0010]
【実施例】次に実施例、及び製造例を挙げ本発明を更に
詳細に説明する。 製造例１．ビフェノールビスクロロ蟻酸エステルの製
造：EXAMPLES The present invention will be described in more detail with reference to Examples and Production Examples. Production Example 1. Production of biphenol bischloroformate:
【化１０】 攪拌機、温度計、ガス導入管を備えた、１リットルフラ
スコに、テトラヒドロフラン４００mlを加えた後、ホス
ゲン１４０ｇを−１０〜−５℃で吹込み、溶解した。次
いで、これに攪拌しながら、ビフェノール７４．４ｇを
加え、溶解した後、Ｎ，Ｎ−ジメチルアニリン９６．８
ｇを−５〜−０℃で１時間で滴下した。滴下後、同温で
３０分間攪拌した後、徐々に昇温し、２０〜２５℃で３
時間攪拌を続け、反応完結と脱ガスを行った。反応液は
氷水中に注入し、析出する結晶を濾取し、水洗、乾燥後
アセトンで再結晶した。 収量 ７３．０ｇ（収率５９％）、ｍｐ １３０〜１３
１℃[Chemical 10] After adding 400 ml of tetrahydrofuran to a 1 liter flask equipped with a stirrer, a thermometer, and a gas introduction tube, 140 g of phosgene was blown thereinto at -10 to -5 ° C to dissolve it. Then, while stirring, 74.4 g of biphenol was added and dissolved, and then N, N-dimethylaniline 96.8 was added.
g was added dropwise at −5 to −0 ° C. for 1 hour. After dropping, the mixture was stirred at the same temperature for 30 minutes and then gradually heated to 3 at 20 to 25 ° C.
The stirring was continued for an hour to complete the reaction and degas. The reaction solution was poured into ice water, and the precipitated crystals were collected by filtration, washed with water, dried and recrystallized with acetone. Yield 73.0 g (59% yield), mp 130-13
1 ° C
【００１１】実施例１． ビスフェノール−Ａ−ビフェ
ノール型ポリカーボネートの合成：Embodiment 1. Synthesis of bisphenol-A-biphenol type polycarbonate:
【化１１】 攪拌機、温度計を備えた１リットルフラスコに塩化メチ
レン６２５mlを加え、攪拌しながら、ビフェノールビス
クロロ蟻酸エステル３１．１ｇを加え、溶解した。更に
これにイオン交換水１２５mlを加えた後、十分攪拌しな
がら３．５％水酸化ナトリウム水溶液２２８．６ｇにビ
スフェノール−Ａ２２．８ｇを溶解した液を２０〜２５
℃で１時間で滴下した。滴下後、同温で攪拌を続け、８
時間後に分子量が３０，０００（ＧＰＣ，ポリスチレン
換算）となり、攪拌を停止し、静置した。水層を分液
し、塩化メチレン層はイオン交換水、１％塩酸、イオン
交換水の順で洗浄し、共沸脱水した後、０．１μｍのフ
ィルターを通した。次いで、これをメタノール１．２リ
ットル中に注入し、析出した結晶を濾過、乾燥した。 収量 ３９．５ｇ（収率８５％） 得られたポリカーボネートは 1Ｈ−ＮＭＲより交互共重
合体であった。 δ（ｐｐｍ）：１．７０（ｓ，６Ｈ），７．２０（ｄ，
４Ｈ），７．２７（ｄ，４Ｈ），７．３５（ｄ，４
Ｈ），７．５９（ｄ，４Ｈ）[Chemical 11] To a 1 liter flask equipped with a stirrer and a thermometer, 625 ml of methylene chloride was added, and 31.1 g of biphenol bischloroformate ester was added and dissolved while stirring. Further, 125 ml of ion-exchanged water was added to this, and a solution prepared by dissolving 22.8 g of bisphenol-A in 228.6 g of a 3.5% aqueous sodium hydroxide solution was stirred for 20 to 25
It was added dropwise at 1 ° C for 1 hour. After dropping, continue stirring at the same temperature for 8
After a lapse of time, the molecular weight became 30,000 (GPC, converted to polystyrene), stirring was stopped, and the mixture was allowed to stand. The aqueous layer was separated, and the methylene chloride layer was washed with ion-exchanged water, 1% hydrochloric acid and ion-exchanged water in this order, azeotropically dehydrated, and then passed through a 0.1 μm filter. Next, this was poured into 1.2 liters of methanol, and the precipitated crystals were filtered and dried. Yield 39.5 g (yield 85%) The obtained polycarbonate was an alternating copolymer by 1 H-NMR. δ (ppm): 1.70 (s, 6H), 7.20 (d,
4H), 7.27 (d, 4H), 7.35 (d, 4)
H), 7.59 (d, 4H)
【００１２】実施例２． ビスフェノール−Ａ−ビフェ
ノール型ポリカーボネートの合成：Example 2. Synthesis of bisphenol-A-biphenol type polycarbonate:
【化１２】 攪拌機、温度計を備えた１リットルフラスコに塩化メチ
レン６２５mlを加え、攪拌しながら、ビスフェノールＡ
ビスクロロ蟻酸エステル３５．３ｇを加え、溶解した。
更にこれにイオン交換水１２５mlを加えた後、十分攪拌
しながら３．５％水酸化ナトリウム水溶液２２８．６ｇ
にビフェノール１８．６ｇを溶解した液を２０〜２５℃
で１時間で滴下した。滴下後、同温で攪拌を続け、４時
間後に２８％水酸化ナトリウム水溶液１４．３ｇを加
え、更に５時間攪拌を続け、分子量が６０，０００（Ｇ
ＰＣ，ポリスチレン換算）となり攪拌を停止し、静置し
た。後処理は実施例１と同様に行った。 収量 ３６．７ｇ（収率７９％） 得られたポリカーボネートは実施例１と同様交互共重合
体であった。[Chemical formula 12] To a 1 liter flask equipped with a stirrer and a thermometer, 625 ml of methylene chloride was added, and bisphenol A was added while stirring.
35.3 g of bischloroformate ester was added and dissolved.
Further, 125 ml of ion-exchanged water was added to this, and 228.6 g of 3.5% aqueous sodium hydroxide solution was added while sufficiently stirring.
A solution of 18.6 g of biphenol dissolved in 20 to 25 ° C
At 1 hour. After the dropwise addition, stirring was continued at the same temperature, and 4 hours later, 14.3 g of 28% sodium hydroxide aqueous solution was added, and the mixture was further stirred for 5 hours to give a molecular weight of 60,000 (G
Then, the stirring was stopped and the mixture was allowed to stand. The post-treatment was performed in the same manner as in Example 1. Yield 36.7 g (yield 79%) The obtained polycarbonate was an alternating copolymer as in Example 1.
【００１３】[0013]
【化１３】 実施例３． ビスフェノール−ＡＦ−ビフェノール型ポ
リカーボネートの合成： 攪拌機、温度計を備えた１リットルフラスコに塩化メチ
レン６２５mlを加え、攪拌しながら、ビフェノールビス
クロロ蟻酸エステル３１．１ｇを加え、溶解した。更に
これにイオン交換水１２５mlを加えた後、十分攪拌しな
がら３．５％水酸化ナトリウム水溶液２２８．６ｇにビ
スフェノール−ＡＦ３３．６ｇを溶解した液を２０〜２
５℃で１時間で滴下した。滴下後、同温で攪拌を続け、
７時間後に分子量が３０，０００（ＧＰＣ，ポリスチレ
ン換算）となり攪拌を停止し、静置した。後処理は実施
例１と同様に行った。 収量 ４２．５ｇ（収率７４％） 得られたポリカーボネートは 1Ｈ−ＮＭＲより交互共重
合体であった。 δ（ｐｐｍ）：７．３５（ｄ，４Ｈ），７．３７（ｄ，
４Ｈ），７．４７（ｄ，４Ｈ），７．６１（ｄ，４
Ｈ），[Chemical 13] Example 3. Synthesis of bisphenol-AF-biphenol type polycarbonate: 625 ml of methylene chloride was added to a 1 liter flask equipped with a stirrer and a thermometer, and 31.1 g of biphenol bischloroformate ester was added and dissolved while stirring. Further, 125 ml of ion-exchanged water was added thereto, and then a solution prepared by dissolving 33.6 g of bisphenol-AF33.6 in 228.6 g of a 3.5% sodium hydroxide aqueous solution while sufficiently stirring was added to 20-2.
It was added dropwise at 5 ° C. for 1 hour. After dropping, continue stirring at the same temperature,
After 7 hours, the molecular weight became 30,000 (GPC, converted to polystyrene), stirring was stopped, and the mixture was allowed to stand. The post-treatment was performed in the same manner as in Example 1. Yield 42.5 g (yield 74%) The obtained polycarbonate was an alternating copolymer by 1 H-NMR. δ (ppm): 7.35 (d, 4H), 7.37 (d,
4H), 7.47 (d, 4H), 7.61 (d, 4)
H),
【００１４】[0014]
【発明の効果】本発明のポリカーボネートは透明度が高
いと同時に熱処理後も透明度が維持されるのでプラスチ
ック光ファイバーの材料等に用いられる。INDUSTRIAL APPLICABILITY The polycarbonate of the present invention has a high transparency and at the same time maintains the transparency even after a heat treatment, and is therefore used as a material for a plastic optical fiber.
Claims (2)
２ 【化２】 （式中Ｒ1 及びＲ2 はそれぞれ水素原子、低級アルキル
基またはトリフルオロメチル基を示す。さらにＲ1 、Ｒ
2 が一緒になって環を形成してもよい。）で表わされる
化合物とを反応させることを特徴とする化３ 【化３】 で表わされる平均分子量２０，０００〜１００，０００
の変性ポリカーボネートの製造方法。1. Chemical formula 1 A biphenol bischloroformate ester represented by (Each of R 1 and R 2 wherein hydrogen atom, a lower alkyl group or a trifluoromethyl group. Further R 1, R
Two may together form a ring. ) A compound represented by the formula: Average molecular weight represented by 20,000-100,000
Of the modified polycarbonate of 1.
わされるビスフェノールビスクロロ蟻酸エステルと化５ 【化５】 で表わされるビフェノールとを反応させることを特徴と
する化６ 【化６】 で表わされる平均分子量２０，０００〜１００，０００
の変性ポリカーボネートの製造方法。2. Chemical formula 4 (In the formula, R 1 and R 2 have the same meanings as described above.) And a bisphenol bischloroformate ester Which is characterized by reacting with a biphenol represented by: Average molecular weight represented by 20,000-100,000
Of the modified polycarbonate of 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03262594A JP3136696B2 (en) | 1991-09-17 | 1991-09-17 | Method for producing modified polycarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03262594A JP3136696B2 (en) | 1991-09-17 | 1991-09-17 | Method for producing modified polycarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570583A true JPH0570583A (en) | 1993-03-23 |
| JP3136696B2 JP3136696B2 (en) | 2001-02-19 |
Family
ID=17377972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03262594A Expired - Fee Related JP3136696B2 (en) | 1991-09-17 | 1991-09-17 | Method for producing modified polycarbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3136696B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008050669A1 (en) * | 2006-10-18 | 2008-05-02 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
| US8344092B2 (en) | 2009-06-26 | 2013-01-01 | Idemitsu Kosan Co., Ltd. | Method for producing bischloroformate compound, polycarbonate oligomer having small number of monomers and solution containing bischloroformate compound |
-
1991
- 1991-09-17 JP JP03262594A patent/JP3136696B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008050669A1 (en) * | 2006-10-18 | 2008-05-02 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
| US7888455B2 (en) | 2006-10-18 | 2011-02-15 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
| US7893185B2 (en) | 2006-10-18 | 2011-02-22 | Idemitsu Kosan Co., Ltd. | Polycarbonate copolymer, method for producing the same, molded body, optical material, and electrophotographic photosensitive body |
| US8344092B2 (en) | 2009-06-26 | 2013-01-01 | Idemitsu Kosan Co., Ltd. | Method for producing bischloroformate compound, polycarbonate oligomer having small number of monomers and solution containing bischloroformate compound |
| US8470957B2 (en) | 2009-06-26 | 2013-06-25 | Idemitsu Kosan Co., Ltd. | Method for producing bischloroformate compound, polycarbonate oligomer having small number of monomers and solution containing bischloroformate compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3136696B2 (en) | 2001-02-19 |
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