JP4149602B2 - Aromatic polycarbonate copolymer and method for producing the same - Google Patents

Description

（Ｒ ^１ およびＲ ^２ はそれぞれ独立に炭素数１〜２０のアルキレン基を表し、Ｒ ^３ は炭素数１〜２０のアルキル基を表し、ｐは１から４の整数を表す。）
で表される化合物、
（Ｂ）成分）：下記式（２）
【００１０】
【化６】

（式中、Ｒ ^４ およびＲ ^５ はそれぞれ独立に、水素原子、または炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数６〜２０のシクロアルコキシ基、または炭素数６〜２０のアリールオキシ基を表し、ｍおよびｎはそれぞれ独立に１〜４の整数である。Ｘは単結合または酸素原子、カルボニル基、炭素数１〜２０のアルキレン基、炭素数６〜２０のシクロアルキレン基、または炭素数６〜２０のアリーレン基を表す。）
で表される化合物、
（Ｃ）成分）：下記式（３）
ＨＯ−Ｒ ^６ −ＯＨ ・・・（３）
（式中、Ｒ ^６ は炭素数１〜４０のアルキル基を表す。）
で表される化合物
すなわち本発明は、下記式（５）、（６）、および（７）で表される繰り返し単位を含むポリカーボネート、およびその製造法に関する。下記にその繰り返し単位（５）〜（７）を示す。
【００１１】
【化７】

（上記式（５）〜（７）において、Ｒ^１〜Ｒ^９、ｍ、ｎ、ｐ、Ｘの定義は上記式（１）〜（３）に同じである。）
【００１２】
上記式（１）であらわされる上記（Ａ）成分のジヒドロキシ化合物としては、上記式（１）におけるＲ^１およびＲ^２の炭素数がそれぞれ３〜１２であることが好ましく、加えてコスト面から炭素数がそれぞれ６〜９であることがより好ましい。具体的には以下のような化合物が挙げられる。
【００１３】
【化８】

【００１４】
【化９】

【００１５】
本発明において上記（２）で表されるジヒドロキシ化合物としては例えば２，２−ビス（４−ヒドロキシフェニル）プロパン（以下ビスフェノールＡという）、ビス（２−ヒドロキシフェニル）メタン、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、１，１−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（２−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、２，２−ビス（４−ヒドロキシフェニル）ペンタン、３，３−ビス（４−ヒドロキシフェニル）ペンタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、ビス（４−ヒドロキシフェニル）サルファイド、ビス（４−ヒドロキシフェニル）スルホン等及びその芳香環に例えばアルキル基、アリール基等が置換されたものがあげられ、これらは単独で用いてもまたは二種以上併用してもよい。なかでもビスフェノールＡが特に好ましい。
【００１６】
上記式（３）であらわされる上記（Ｃ）成分のジヒドロキシ化合物としては、９−ノニル−１０−オクチル−１，１８−オクタデシルジオール、８−ノニル−９−オクチル−１，１７−ヘプタデシルジオール、８−オクチル−９−ノニル−１、１７−ヘプタデシルジオール、８−ノニル−９−オクチル−１，１８−オクタデシルジオール、８−オクチル−９−ノニル−１，１８−オクタデシルジオール、９−ノニル−１０−オクチル−１，１８−オクタデシルジオール、９−デシル−１０−ヘプチル−１，１８−オクタデシルジオール、７−ノニル−８−オクチル−１，１８−オクタデシルジオール、７−オクチル−８−ノニル−１，１８−オクタデシルジオール、９−ノニル−１０−オクチル−１，１８−オクタデシルジオール、９，１０−ジオクチル−１，１８−オクタデシルジオールが挙げられる。
【００１７】
ジヒドロキシ化合物について、（Ａ）成分、（Ｂ）成分、（Ｃ）成分としたとき、その成分モル比は、（Ａ）成分；０．６〜０．０１、（Ｂ）成分；０．４〜０．９９、（Ｃ）成分；０．２〜０．０１であることが好ましい。
【００１８】
さらに溶融流動性に加え、優れた熱的安定性をもつ芳香族ポリカーボネートを得るためにはその成分モル比は、（Ａ）成分；０．１〜０．０１、（Ｂ）成分；０．９〜０．９９、（Ｃ）成分；０．１〜０．０１であることが好ましく、さらには（Ａ）成分と（Ｃ）成分の合計モル比が；０．１〜０．０１、（Ｂ）成分；０．９〜０．９９であることが好ましい。
【００１９】
本発明において式（１）、（２）、および（３）で表されるジヒドロキシ化合物の純度は９５％以上であることが好ましい。ポリマー原料である式（１）、（２）、および（３）で表されるジヒドロキシ化合物中には、不純物として対応するモノマーアルコールとトリマーアルコールがそれぞれ１％以下含まれる。この原料の純度が９５％未満の場合、所望の重合度と流動性をもつポリマーが得られず好ましくない。
【００２０】
炭酸エステル形成性化合物としては、ホスゲン、炭酸ジエステルが挙げられる。炭酸ジエステルとしては例えばジフェニルカーボネート、ジナフチルカーボネート、ビス（ジフェニル）カーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート等があげられ、なかでもコスト面からジフェニルカーボネートが好ましい。
【００２１】
また本発明のポリカーボネート共重合体は、塩化メチレンを溶媒とする０．５ｇ／ｄｌ濃度の溶液の２０℃における固有粘度（[η]）が少なくとも０．３ｇ／ｄｌであり、ガラス転移温度が少なくとも１００℃であることを特徴とする。[η]が０．３ｇ／ｄｌ未満の場合は耐衝撃性に劣るため、成形材料として好ましくない。またガラス転移温度によって成形品の耐熱性や、溶融成形時の熱安定性の程度が評価されるが、ここで、成形加工に十分な熱安定性を得るために、ガラス転移温度は１００℃以上が好ましく、１２０℃以上がより好ましい。塩化メチレンを溶媒とする０．５ｇ／ｄｌ濃度の溶液の２０℃における固有粘度（[η]）が０．３ｇ／ｄｌを超えていても、ガラス転移温度が１００℃未満であれば熱安定性の点で好ましくない。
【００２２】
本発明で開示しているポリカーボネート樹脂は、いかなる製造法で合成してもよく、例えば炭酸エステル形成性化合物として、ホスゲンを用いる界面重合法や、炭酸ジエステルを用いる溶融法（エステル交換反応）や固相重合法でもよい。このなかで、有害なハロゲン化物を使わずにすむ理由から炭酸ジアリールエステルを用いる溶融法や、固相重合法が好ましく、さらにコスト面やプロセスが簡単であるなどの面から炭酸ジエステルを用いる溶融法がより好ましい。
【００２３】
溶融法は常圧およびまたは減圧窒素雰囲気下で二価フェノールと炭酸ジエステルとを加熱しながら攪拌して、生成するアルコールまたはフェノールを留出させることで行われる。
【００２４】
溶融法の場合、その反応温度は生成物の沸点等により異なるが、反応により生成するアルコールまたはフェノールを除去するため通常１２０〜３５０℃の範囲であり、好ましくは良好な色相や熱安定性が得られる理由で１８０〜２８０℃の範囲である。
【００２５】
反応後期には系を減圧にして生成するアルコールまたはフェノールの留出を容易にさせる。反応後期の系の内圧は好ましくは１ｍｍＨｇ以下であり、より好ましくは０．５ｍｍＨｇ以下である。
【００２６】
重合速度を速めるために重合触媒を使用することができ、重合触媒としては例えば水酸化ナトリウムや水酸化カリウム等のアルカリ金属やアルカリ土類金属の水酸化物、ホウ素やアルミニウムの水酸化物、アルカリ金属塩、アルカリ土類金属塩、第４級アンモニウム塩、アルカリ金属やアルカリ土類金属のアルコキシド、アルカリ金属やアルカリ土類金属の有機酸塩、亜鉛化合物、ホウ素化合物、ケイ素化合物、ゲルマニウム化合物、有機スズ化合物、鉛化合物、アンチモン化合物、マンガン化合物、チタン化合物、ジルコニウム化合物等の通常エステル化反応やエステル交換反応に使用される触媒があげられる。触媒は単独で用いてもまたは二種以上併用してもよい。なかでも色相や熱安定性または重合速度が大きい点から、（ｉ）含窒素塩基性化合物および（ｉｉ）アルカリ金属およびまたはアルカリ土類金属化合物を組み合わせた触媒が好ましい。
【００２７】
本発明におけるこれらの重合触媒の使用量は、アルカリ金属化合物およびアルカリ土類金属化合物の場合は、全ジヒドロキシ化合物１モルに対し１＊１０^−７〜１＊１０^−４当量、好ましくは１＊１０^−７〜５＊１０^−６当量の範囲で選ばれる。また含窒素塩基性化合物を使用する場合は、全ジヒドロキシ化合物１モルに対し１＊１０^−５〜１＊１０^−３当量、好ましくは１＊１０^−５〜１＊１０^−４当量の範囲で選ばれる。
【００２８】
本発明においては、特に重合終了後に触媒失活剤を適用することが好ましい。本発明における触媒失活剤とは、ポリカーボネート製造時に使用する重合触媒の活性の一部または全部を失活させるものである。
【００２９】
触媒失活剤を添加する方法としては、例えば、反応生成物であるポリカーボネートが溶融状態にある間に添加してもよいし、一旦ポリカーボネートをペレタイズした後、再溶解し添加しても良い。前者においては、反応槽内または押し出し機内の反応生成物であるポリカーボネートが溶融状態にある間に添加してもよいし、また重合後得られたポリカーボネートが反応槽から押し出し機を通ってペレタイズされる間に、中和剤を添加して混練することもできる。
【００３０】
触媒失活剤としては、得られるポリマーの色相や耐熱性、耐沸水性などの物性の向上に対する効果が大きい点から、スルホン酸のホスホニウム塩および／またはスルホン酸のアンモニウム塩を使用することが好ましい。そのなかでも特に、ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩やパラトルエンスルホン酸テトラブチルアンモニウム塩などが好ましい例として挙げられる。
【００３１】
上記の方法により本発明の新規共重合体が得られるが、これを用いて各種成形品を成形する場合に用途に応じて従来公知の酸化防止剤、紫外線吸収剤、離型剤を加えてもよい。
【００３２】
本発明の共重合体は、前記の各成分を任意の方法、例えばタンブラー、ブレンダー、ナウターミキサー、バンバリーミキサー、混練ロール、押し出し機等により混合して製造することができる。
【００３３】
【発明の効果】
特定のジヒドロキシ化合物成分を共重合させることにより、特に射出成形用材料として、従来のポリカーボネートでは得られなかった優れた流動性を持つ流動性改善されたポリカーボネートを得ることができる。
【００３４】
【実施例】
以下に実施例をあげて更に説明するが、本発明はこれらの実施例により限定されるものではない。各項目の測定は下記の方法によった。
（１）Ｔｇ：デュポン社製２０００型ＤＳＣにより窒素気流下で毎分１０℃の昇温速度で測定した。
（２）溶融流動性：ペレットを０．５ｍｍＨｇ圧下１３０℃で６時間乾燥した後、東洋精機製作所社製メルトインデクサーを用いて熱可塑性プラスチックの流れ試験法（ＪＩＳ−Ｋ７２１０）に従い、試験荷重２１６０ｇ、２８０℃で測定した。
（３）固有粘度［η］：塩化メチレン中２０℃でウベローデ粘度計で測定した。
【００３５】
［実施例１］
攪拌装置、精留塔および減圧装置を備えた反応槽に、原料としてビスフェノールＡ１３６．９７ｇ（０．６０モル）、ジフェニルカーボネート１３４．９５ｇ（０．６３モル）、および下記式（９）
【００３６】
【化１０】

で示されるジオール化合物と下記式（１０）
【００３７】
【化１１】

【００３８】
で示されるジオール化合物とを３：１のモル比で含む混合物（共重合成分（ア））１．５４ｇ（２．８７ミリモル）、重合触媒としてビスフェノール２ナトリウム塩５．４５＊１０^−４ｇ（２マイクロモル）、テトラメチルアンモニウムヒドロキシド９．１２＊１０^−３ｇ（１００マイクロモル）を仕込んで窒素雰囲気下１８０℃で溶融した。攪拌下、反応槽内を１００ｍｍＨｇに減圧し、生成するフェノールを溜去しながら２０分間反応させた。次に２００℃に昇温した後、徐々に減圧し、フェノールを溜去しながら３０ｍｍＨｇで２０分間反応させた。さらに徐々に昇温し２２０℃で２０分間、２４０℃で２０分間、２８０℃で２０分間反応させ、その後、２８０℃で徐々に減圧し２０ｍｍＨｇで１０分間、１０ｍｍＨｇで５分間反応を続行し、最終的に２８０℃／０．５ｍｍＨｇで２時間反応せしめた。得られた共重合ポリカーボネート樹脂の物性を上記の方法で評価し、結果を下記表１に示した。
【００３９】
［実施例２］
ビスフェノールＡを１３６．９５ｇ、実施例１で示した上式（９）で示されるジオール化合物と上式（１０）で示されるジオール化合物との混合物（共重合成分（ア））を４．７２ｇ（８．７９ミリモル）用いた以外は、実施例１と同様の操作を行い、共重合ポリカーボネート樹脂を得た。このポリマーの物性を上記の方法で評価し、結果を下記表１に示した。
【００４０】
［実施例３］
ビスフェノールＡを１３２．６３ｇ（０．５８モル）、実施例１で示した上記式（９）で示されるジオール化合物と上記式（１０）で示されるジオール化合物との混合物（共重合成分（ア））を１０．８ｇ（２０．１ミリモル）用いた以外は、実施例１と同様の操作を行い、共重合ポリカーボネート樹脂を得た。このポリマーの物性を上記の方法で評価し、結果を下記表１に示した。
【００４１】
［比較例１］
ジヒドロキシ化合物として２，２−ビスフェノールＡ１３６．９７ｇ、（０．６０モル）のみを用いた他は、実施例１と同様の操作を行い、、ポリカーボネート樹脂を得た。このポリマーの物性を上記の方法で評価し、結果を下記表１に示した。
【００４２】
［比較例２］
ホスゲン吹き込み管、温度計及び攪拌機を設けた容量５０リットルの反応槽に、ビスフェノールA５０２８ｇ、７．２％水酸化水溶液２２．１リットル及びハイドロサルファイトナトリウム９．８ｇを仕込んで溶解し攪拌下、下式で示す化合物（ａ）（共重合成分（ウ））
【００４３】
【化１２】

【００４４】
を６ｇ、塩化メチレン１２．７リットルおよび４８．５％水酸化ナトリウム水溶液８０７ｇを加えた後、ホスゲン２５０８ｇを２５℃で９０分かけて加えホスゲン化反応させた。ホスゲン化終了後、ｐ−ｔｅｒｔ−ブチルフェノール１７５．１ｇ、４８．５％水酸化ナトリウム水溶液８０４ｇ及び触媒としてトリエチルアミン１８．１ｍｌを加え、３３℃に保持して２時間攪拌して反応を終了させた。反応混合液から塩化メチレン層を分離し、水洗により精製して粘度平均分子量１５３００の共重合ポリカーボネート樹脂を得た。このポリマーの物性を上記の方法で評価し、結果を下記表１に示した。
【００４５】
［比較例３］
共重合成分（ウ）の使用量を３０ｇに変更する以外は比較例２と同様にして粘度平均分子量１５３００の共重合ポリカーボネート樹脂を得た。このポリマーの物性を上記の方法で評価し、結果を下記表１に示した。
【００４６】
［比較例４］
共重合成分（ウ）の使用量を３ｇに変更する以外は比較例２と同様にして粘度平均分子量１５３００の共重合ポリカーボネート樹脂を得た。このポリマーの物性を上記の方法で評価し、結果を下記表１に示した。
【００４７】
【表１】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel copolymer polycarbonate. More specifically, the present invention relates to a copolymer polycarbonate resin having excellent fluidity that has not been obtained with conventional polycarbonates and excellent in thermal stability, and a method for producing the same.
[0002]
[Prior art]
Polycarbonate is a molding material excellent in mechanical properties such as impact resistance, toughness, dimensional stability, transparency, and heat resistance. However, since polycarbonate generally has a high melt viscosity, it has a drawback of poor melt fluidity at the time of molding, and it has been difficult to injection mold precision parts and thin materials. In order to improve the melt fluidity, it is necessary to raise the molding temperature and the mold temperature. For this reason, there are problems that the molding cycle becomes long, the cost of molding becomes high, and deterioration such as coloring and a decrease in polymerization degree occurs during molding.
[0003]
In order to improve the fluidity, as exemplified in JP-A-5-186676 and JP-A-6-25523, there is a method of mixing a low molecular weight polycarbonate to lower the weight average molecular weight. However, the polycarbonate obtained by this method has the disadvantage that the impact resistance and thermal stability are significantly reduced.
[0004]
In addition, attempts have been made to improve fluidity and moldability by adding plasticizers and lubricants such as fatty acid esters to polycarbonate. However, as pointed out in JP-A-9-227773, the effects of improving the flowability and moldability of polycarbonate are recognized in these methods, but they are not necessarily satisfactory in terms of the compatibility and miscibility of the additives. In addition, there are disadvantages such as greatly reducing the above-mentioned properties of polycarbonate.
[0005]
As another method for improving fluidity, a copolymer polycarbonate containing a component having a high aliphatic content has been studied, and its effect is exemplified in JP-A-9-208683. In general, however, in this method, although the fluidity of the polycarbonate is improved by the copolymerization component, there is a problem that the thermal stability is greatly reduced. For this reason, there is a strong demand for the development of an effective copolymer component that can improve fluidity while maintaining good thermal stability.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to obtain a polycarbonate having excellent fluidity that cannot be obtained by a conventional polycarbonate, particularly as an injection molding material.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, the present inventors have studied the fluidity and thermal stability of various copolymer polycarbonates. As a result, by copolymerizing a specific dihydroxy compound component, the fluidity and thermal stability are improved. The inventors have found that an excellent polycarbonate can be obtained and have reached the present invention.
[0008]
That is, the present invention comprises a polycondensation of a dihydroxy compound comprising the following components (A) and (B), or the following components (A), (B), and (C) with a carbonate-forming compound. An excellent melt flow of a manufactured polycarbonate having a 0.5 g / dl concentration solution using methylene chloride as a solvent and an intrinsic viscosity at 20 ° C. of at least 0.3 g / dl and a glass transition temperature of at least 100 ° C. It is the aromatic polycarbonate which has property, and its manufacturing method.
[0009]
(A) component): following formula (1)
[Chemical formula 5]

(R ¹ and R ² each independently represent an alkylene group having 1 to 20 carbon atoms , R ³ represents an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 1 to 4)
A compound represented by
(B) component): following formula (2)
[0010]
[Chemical 6]

(In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 represents an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and m and n are each independently an integer of 1 to 4. X is a single bond or an oxygen atom. Represents a carbonyl group, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.)
A compound represented by
(C) component): following formula (3)
HO—R ⁶ —OH (3)
(In the formula, R ⁶ represents an alkyl group having 1 to 40 carbon atoms.)
The present invention relates to a polycarbonate containing repeating units represented by the following formulas (5), (6) and (7), and a method for producing the same . Shows the repeating units under Symbol (5) to (7).
[0011]
[Chemical 7]

(In the above formulas (5) to (7) , the definitions of R ^{1 to} R ⁹ , m, n, p, and X are the same as those in the above formulas (1) to (3) .)
[0012]
The dihydroxy compound of the component (A) represented by the above formula (1) preferably has 3 to 12 carbon atoms for R ¹ and R ² in the above formula (1). It is more preferable that the number is 6 to 9, respectively. Specific examples include the following compounds.
[0013]
[Chemical 8 ]

[0014]
[Chemical 9]

[0015]
Examples of the dihydroxy compound represented by the above (2) in the present invention include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), bis (2-hydroxyphenyl) methane, and bis (4-hydroxyphenyl). ) Methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (2-hydroxyphenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2 -Bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4 Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like, and those having an aromatic group substituted with an alkyl group, aryl group, etc., are used, and these are used alone. Or two or more of them may be used in combination. Of these, bisphenol A is particularly preferred.
[0016]
Examples of the dihydroxy compound of the component (C) represented by the above formula (3) include 9-nonyl-10-octyl-1,18-octadecyldiol, 8-nonyl-9-octyl-1,17-heptadecyldiol, 8-octyl-9-nonyl-1, 17-heptadecyldiol, 8-nonyl-9-octyl-1,18-octadecyldiol, 8-octyl-9-nonyl-1,18-octadecyldiol, 9-nonyl- 10-octyl-1,18-octadecyldiol, 9-decyl-10-heptyl-1,18-octadecyldiol, 7-nonyl-8-octyl-1,18-octadecyldiol, 7-octyl-8-nonyl-1 , 18-octadecyldiol, 9-nonyl-10-octyl-1,18-octadecyldiol, 9,10 Dioctyl-1,18-octadecyl-diol, and the like.
[0017]
About a dihydroxy compound, when it is set as (A) component, (B) component, and (C) component, the component molar ratio is (A) component; 0.6-0.01, (B) component; 0.4- 0.99, component (C); preferably 0.2 to 0.01.
[0018]
Furthermore, in order to obtain an aromatic polycarbonate having excellent thermal stability in addition to melt fluidity, the component molar ratio is (A) component: 0.1-0.01, (B) component: 0.9 ~ 0.99, (C) component; preferably 0.1 to 0.01, and further the total molar ratio of (A) component and (C) component; 0.1 to 0.01, (B ) Component; preferably 0.9 to 0.99.
[0019]
In the present invention, the purity of the dihydroxy compound represented by the formulas (1), (2), and (3) is preferably 95% or more. The dihydroxy compound represented by the formulas (1), (2), and (3) , which are polymer raw materials, each contain 1% or less of the corresponding monomer alcohol and trimer alcohol as impurities. When the purity of this raw material is less than 95%, a polymer having a desired degree of polymerization and fluidity cannot be obtained.
[0020]
Examples of the carbonate ester-forming compound include phosgene and carbonic acid diester. Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable from the viewpoint of cost.
[0021]
The polycarbonate copolymer of the present invention has an intrinsic viscosity ([η]) at 20 ° C. of a 0.5 g / dl concentration solution using methylene chloride as a solvent at least 0.3 g / dl, and a glass transition temperature of at least It is 100 degreeC. When [η] is less than 0.3 g / dl, it is inferior in impact resistance and is not preferable as a molding material. The glass transition temperature is used to evaluate the heat resistance of the molded product and the degree of thermal stability during melt molding. Here, in order to obtain sufficient thermal stability for the molding process, the glass transition temperature is 100 ° C. or higher. Is preferable, and 120 degreeC or more is more preferable. Even if the intrinsic viscosity ([η]) at 20 ° C. of a 0.5 g / dl concentration solution using methylene chloride as a solvent exceeds 0.3 g / dl, the glass plate has a glass transition temperature of less than 100 ° C. This is not preferable.
[0022]
The polycarbonate resin disclosed in the present invention may be synthesized by any production method. For example, as a carbonate ester-forming compound, an interfacial polymerization method using phosgene, a melting method (ester exchange reaction) using a carbonate diester, or a solid A phase polymerization method may be used. Among these, a melting method using a diaryl carbonate ester or a solid phase polymerization method is preferred because it eliminates the use of harmful halides, and a melting method using a carbonate diester from the viewpoint of cost and process being simple. Is more preferable.
[0023]
The melting method is carried out by distilling the produced alcohol or phenol by stirring the dihydric phenol and carbonic acid diester under heating under normal pressure and / or reduced pressure nitrogen atmosphere.
[0024]
In the case of the melting method, the reaction temperature varies depending on the boiling point of the product, etc., but is usually in the range of 120 to 350 ° C. in order to remove alcohol or phenol produced by the reaction, and preferably good hue and thermal stability are obtained. The reason is that it is in the range of 180 to 280 ° C.
[0025]
In the latter stage of the reaction, the system is reduced in pressure to facilitate the distillation of the alcohol or phenol produced. The internal pressure of the system in the late reaction phase is preferably 1 mmHg or less, more preferably 0.5 mmHg or less.
[0026]
A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, boron and aluminum hydroxides, and alkalis. Metal salts, alkaline earth metal salts, quaternary ammonium salts, alkoxides of alkali metals and alkaline earth metals, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, silicon compounds, germanium compounds, organic Examples thereof include catalysts usually used for esterification and transesterification of tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. A catalyst may be used independently or may be used together 2 or more types. Among them, a catalyst combining (i) a nitrogen-containing basic compound and (ii) an alkali metal and / or an alkaline earth metal compound is preferable from the viewpoint of hue, thermal stability, or polymerization rate.
[0027]
In the present invention, these polymerization catalysts are used in an amount of 1 * 10 ⁻⁷ to 1 * 10 ⁻⁴ equivalents, preferably 1 * 10 to 1 mol of all dihydroxy compounds in the case of alkali metal compounds and alkaline earth metal compounds. It is selected in the range of ^{−7 to} 5 * 10 ⁻⁶ equivalents. When a nitrogen-containing basic compound is used, it is selected in the range of 1 * 10 ⁻⁵ to 1 * 10 ⁻³ equivalent, preferably 1 * 10 ⁻⁵ to 1 * 10 ⁻⁴ equivalent, relative to 1 mol of all dihydroxy compounds. It is.
[0028]
In the present invention, it is particularly preferable to apply a catalyst deactivator after completion of polymerization. The catalyst deactivator in the present invention deactivates part or all of the activity of the polymerization catalyst used in the production of polycarbonate.
[0029]
As a method for adding the catalyst deactivator, for example, it may be added while the polycarbonate which is a reaction product is in a molten state, or it may be pelletized once and then dissolved again and added. In the former, the polycarbonate which is a reaction product in the reaction vessel or the extruder may be added while it is in a molten state, and the polycarbonate obtained after polymerization is pelletized from the reaction vessel through the extruder. In between, a neutralizing agent can be added and kneaded.
[0030]
As the catalyst deactivator, it is preferable to use a phosphonium salt of sulfonic acid and / or an ammonium salt of sulfonic acid from the viewpoint of a large effect on improvement of physical properties such as hue and heat resistance and boiling water resistance of the obtained polymer. . Among them, particularly preferred examples include dodecylbenzenesulfonic acid tetrabutylphosphonium salt and paratoluenesulfonic acid tetrabutylammonium salt.
[0031]
Although the novel copolymer of the present invention can be obtained by the above-described method, a conventionally known antioxidant, ultraviolet absorber, or release agent may be added depending on the application when molding various molded articles using the copolymer. Good.
[0032]
The copolymer of the present invention can be produced by mixing the above-described components by an arbitrary method such as a tumbler, blender, nauter mixer, Banbury mixer, kneading roll, extruder.
[0033]
【The invention's effect】
By copolymerizing a specific dihydroxy compound component, it is possible to obtain a fluidity-improved polycarbonate having excellent fluidity that cannot be obtained by a conventional polycarbonate, particularly as an injection molding material.
[0034]
【Example】
The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Each item was measured by the following method.
(1) Tg: Measured with a temperature increase rate of 10 ° C. per minute under a nitrogen stream by a DuPont 2000 type DSC.
(2) Melt fluidity: The pellets were dried at 130 ° C. under 0.5 mmHg pressure for 6 hours and then subjected to a test load of 2160 g according to a thermoplastic flow test method (JIS-K7210) using a melt indexer manufactured by Toyo Seiki Seisakusho. Measured at 280 ° C.
(3) Intrinsic viscosity [η]: Measured with an Ubbelohde viscometer at 20 ° C. in methylene chloride.
[0035]
[Example 1]
Bisphenol A 136.97 g (0.60 mol), diphenyl carbonate 134.95 g (0.63 mol), and the following formula (9) as a raw material in a reaction vessel equipped with a stirrer, a rectifying column and a decompression device
[0036]
[Chemical Formula 10]

And a diol compound represented by the following formula (10):
[0037]
Embedded image

[0038]
The mixture (copolymerization component (a)) 1.54 g (2.87 mmol) containing a diol compound represented by formula (5), and bisphenol disodium salt 5.45 * 10 ⁻⁴ g as a polymerization catalyst ( 2 micromoles) and tetramethylammonium hydroxide 9.12 * 10 ⁻³ g (100 micromoles) were charged and melted at 180 ° C. in a nitrogen atmosphere. Under stirring, the pressure in the reaction vessel was reduced to 100 mmHg, and the reaction was carried out for 20 minutes while distilling off the produced phenol. Next, after raising the temperature to 200 ° C., the pressure was gradually reduced and the reaction was carried out at 30 mmHg for 20 minutes while distilling off the phenol. Furthermore, the temperature was gradually raised and reacted at 220 ° C. for 20 minutes, 240 ° C. for 20 minutes, 280 ° C. for 20 minutes, and then gradually reduced in pressure at 280 ° C., and the reaction was continued for 10 minutes at 20 mmHg and 5 minutes at 10 mmHg. The reaction was performed at 280 ° C./0.5 mmHg for 2 hours. The physical properties of the obtained copolymer polycarbonate resin were evaluated by the above methods, and the results are shown in Table 1 below.
[0039]
[Example 2]
136.95 g of bisphenol A, 4.72 g of a mixture of the diol compound represented by the above formula (9) shown in Example 1 and the diol compound represented by the above formula (10) (copolymerization component (A)) ( Except for using 8.79 mmol), the same operation as in Example 1 was performed to obtain a copolymer polycarbonate resin. The physical properties of this polymer were evaluated by the above methods, and the results are shown in Table 1 below.
[0040]
[Example 3]
132.63 g (0.58 mol) of bisphenol A, a mixture of the diol compound represented by the above formula (9) shown in Example 1 and the diol compound represented by the above formula (10) (copolymerization component (a)) ) Was used in the same manner as in Example 1 except that 10.8 g (20.1 mmol) was used to obtain a copolymer polycarbonate resin. The physical properties of this polymer were evaluated by the above methods, and the results are shown in Table 1 below.
[0041]
[Comparative Example 1]
A polycarbonate resin was obtained in the same manner as in Example 1, except that only 2,2-bisphenol A 136.97 g (0.60 mol) was used as the dihydroxy compound. The physical properties of this polymer were evaluated by the above methods, and the results are shown in Table 1 below.
[0042]
[Comparative Example 2]
In a 50 liter reactor equipped with a phosgene blowing tube, a thermometer and a stirrer, 5028 g of bisphenol A, 22.1 liters of a 7.2% aqueous solution of hydroxide and 9.8 g of hydrosulfite sodium were charged and dissolved. Compound (a) represented by formula (copolymerization component (c))
[0043]
Embedded image

[0044]
6 g, 12.7 liters of methylene chloride and 807 g of 48.5% aqueous sodium hydroxide solution were added, and then 2508 g of phosgene was added at 25 ° C. over 90 minutes to carry out a phosgenation reaction. After the completion of phosgenation, 175.1 g of p-tert-butylphenol, 804 g of 48.5% aqueous sodium hydroxide solution and 18.1 ml of triethylamine as a catalyst were added, and the reaction was terminated by stirring for 2 hours while maintaining at 33 ° C. The methylene chloride layer was separated from the reaction mixture and purified by washing with water to obtain a copolymer polycarbonate resin having a viscosity average molecular weight of 15300. The physical properties of this polymer were evaluated by the above methods, and the results are shown in Table 1 below.
[0045]
[Comparative Example 3]
A copolymer polycarbonate resin having a viscosity average molecular weight of 15300 was obtained in the same manner as in Comparative Example 2 except that the amount of the copolymer component (c) used was changed to 30 g. The physical properties of this polymer were evaluated by the above methods, and the results are shown in Table 1 below.
[0046]
[Comparative Example 4]
A copolymer polycarbonate resin having a viscosity average molecular weight of 15300 was obtained in the same manner as in Comparative Example 2 except that the amount of the copolymer component (c) used was changed to 3 g. The physical properties of this polymer were evaluated by the above methods, and the results are shown in Table 1 below.
[0047]
[Table 1]

Claims (5)

A polycarbonate produced by polycondensation of the following (A) component and (B) component, or a dihydroxy compound comprising the following (A), (B) component, and (C) component and a carbonate-forming compound. An aromatic polycarbonate having an excellent melt fluidity in which a 0.5 g / dl concentration solution using methylene chloride as a solvent has an intrinsic viscosity at 20 ° C. of at least 0.3 g / dl and a glass transition temperature of at least 100 ° C. .
(A) component): following formula (1)

(R ¹ And R ² Each independently represents an alkylene group having 1 to 20 carbon atoms; ³ Represents an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 1 to 4. )
A compound represented by
(B) component): following formula (2)

(Wherein R ⁴ And R ⁵ Are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 represents a cycloalkoxy group or an aryloxy group having 6 to 20 carbon atoms, and m and n are each independently an integer of 1 to 4. X represents a single bond or an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. )
A compound represented by
(C) component): following formula (3)
    HO-R ⁶ -OH (3)
(Wherein R ⁶ Represents an alkyl group having 1 to 40 carbon atoms. )
Compound represented by The following (A) component and (B) component, or the following (A), (B) component, and the dihydroxy compound consisting of (C) component, and a carbonate ester-forming compound,
A method for producing polycarbonate by melt polycondensation.
(A) component): following formula (1)

(R ¹ And R ² Each independently represents an alkylene group having 1 to 20 carbon atoms; ³ Represents an alkyl group having 1 to 20 carbon atoms, and p represents an integer of 1 to 4. )
A compound represented by
(B) component): following formula (2)

(Wherein R ⁴ And R ⁵ Are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 represents a cycloalkoxy group or an aryloxy group having 6 to 20 carbon atoms, and m and n are each independently an integer of 1 to 4. X represents a single bond or an oxygen atom, a carbonyl group, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. )
A compound represented by
(C) component): following formula (3)
    HO-R ⁶ -OH (3)
(Wherein R ⁶ Represents an alkyl group having 1 to 40 carbon atoms. )
Compound represented by The production method according to claim 2, wherein the purity of the dihydroxy compound is 95% or more. The presence of a polymerization catalyst, a dihydroxy compound, and a carbonic acid diester Le melt polycondensation method according to any one of claims 2-3, characterized in that the addition of a catalyst deactivator after the completion of polymerization. The production method according to claim 4, wherein the polymerization catalyst is (i) a nitrogen-containing basic compound, and / or (ii) an alkali metal or alkaline earth metal compound.