JP2005097541A5

JP2005097541A5 -

Info

Publication number: JP2005097541A5
Application number: JP2004199846A
Authority: JP
Filing date: 2004-07-06
Publication date: 2007-08-16

Description

本発明者等は、成形特性を維持しながら、色調の良い芳香族ポリカーボネートを提供すべく鋭意検討したところ、加水分解物が主鎖中の分岐構造と目される特定の構造単位に由来すると考えられる化合物を特定量含有し、且つ溶融樹脂を押出したときのオリフィス断面積とストランド断面積の比であるスウェル比が特定の範囲である芳香族ポリカーボネートは、成形特性が改良され、さらに優れた色相を有するものとなることを見出し、本発明を完成するに至った。
The present inventors have, while maintaining the forming characteristics, were intensely studied to provide an aromatic polycarbonate has good color tone, if derived from a particular structural unit hydrolyzate is branched structures and eyes in the main chain An aromatic polycarbonate containing a specific amount of a possible compound and having a swell ratio, which is the ratio of the cross-sectional area of the orifice and the cross-sectional area of the strand when extruding the molten resin, is improved in molding characteristics and further excellent The present inventors have found that it has a hue and have completed the present invention.

すなわち、本発明の要旨は、エステル交換法により得られる粘度平均分子量１６，０００以上の芳香族ポリカーボネートであって、２８０℃でのメルトインデックス測定において、溶融樹脂に対して１１ｋｇの荷重を加えた場合に押出されたストランドの断面積をオリフィス断面積で除した値であるスウェル比が１．２以上４．０以下の範囲であり、且つこのポリカーボネートを加水分解したものが、下記式（９）で表される化合物に対し下記式（１０）〜（１３）で表される化合物を合計で０．３ｍｏｌ％を越え０．８ｍｏｌ％以下の範囲で含有していることを特徴とする芳香族ポリカーボネートに存する。
That is, the gist of the present invention is a viscosity-average molecular weight of 16,000 or more aromatic polycarbonate obtained by the transesterification method, the melt index measured at 2 80 ° C., was added a load of 11kg to the molten resin the cross-sectional area of the extruded strand is divided by the orifice cross-sectional area swell ratio Ri der range of 1.2 to 4.0 in the case, and that the polycarbonate was hydrolyzed is a compound represented by the following formula (9 The compound represented by the following formulas (10) to (13) with respect to the compound represented by the formula (10) is contained in a total amount exceeding 0.3 mol% and 0.8 mol% or less. Located in polycarbonate.

（式（９）〜（１３）中、Ｘは、単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基又は、−Ｏ−，−Ｓ−，−ＣＯ−，−ＳＯ−，−ＳＯ₂−で示される２価の基か
らなる群から選ばれるものである。）
(In the formulas (9) to (13), X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, or 5 to 15 carbon atoms. Or a divalent group represented by —O—, —S—, —CO—, —SO—, —SO ₂ —.

本発明の芳香族ポリカーボネートは、エステル交換法により得られる粘度平均分子量１６，０００以上の芳香族ポリカーボネートであるが、その加水分解物が式（９）で表される化合物に対して式（１０）〜（１３）で表される化合物を合計で０．３ｍｏｌ％を越え０．８ｍｏｌ％以下の範囲で含有していることが必要である。このことは構造単位でみれば、後記する式（１）で表される構造単位に対し後記する式（２）〜（５）で表される分岐構造単位の合計モル数が０．３ｍｏｌ％を越え０．８ｍｏｌ％の範囲内であることが必要であることを意味している。

（上記式（１）から（５）とも、Ｘは、単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基又は、−Ｏ−，−Ｓ−，−ＣＯ−，−ＳＯ−，−ＳＯ ₂ −で示される２価
の基からなる群から選ばれるものである。）
上記式（２）、（３）の構造単位は、式（１）を用いたポリカーボネートのエステル交換法（溶融法）の製造方法において、重合反応系中で転位反応を併発することにより生成することが従来より知られている（例えばＥｎｃｙｃｌｏｐｅｄｉａｏｆＰｏｌｙｍ
ｅｒＳｃｉｅｎｃｅａｎｄＴｅｃｈｎｏｌｏｇｙ，ｖｏｌ，１０．ｐ．７２３（１９６９））。一方、さらに特定の反応条件で溶融法によりポリカーボネートを製造した場合に式（４）及び／又は式（５）の構造単位が生ずることが見出された。式（４）、（５）の構造単位の生成過程は必ずしも明確ではないが、以下のような経路を経て生成しているものと推定している。
Aromatic polycarbonate of the present invention is Ru viscosity average molecular weight of 16,000 or more aromatic polycarbonates der obtained by an ester exchange method, the formula (10 with respect to the compound hydrolyzate thereof is represented by the formula (9) ) To (13) in a total amount exceeding 0.3 mol% and 0.8 mol% or less. In terms of the structural unit, this means that the total number of moles of the branched structural units represented by the formulas (2) to (5) described later is 0.3 mol % with respect to the structural unit represented by the formula (1) described later. This means that it is necessary to be within the range of more than 0.8 mol%.

(In the above formulas (1) to (5), X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, or 5 to 5 carbon atoms. 15 cycloalkylidene group or a, -O -, - S -, - CO -, - SO -, - SO 2 - 2 divalent represented by
Selected from the group consisting of )
The structural units of the above formulas (2) and (3) are generated by simultaneously performing a rearrangement reaction in the polymerization reaction system in the production method of the transesterification method (melting method) of polycarbonate using the formula (1). Is conventionally known (for example, Encyclopedia of Polym
er Science and Technology, vol. p. 723 (1969)). On the other hand, it has been found that structural units of the formula (4) and / or the formula (5) are produced when a polycarbonate is produced by a melting method under more specific reaction conditions. Although the generation process of the structural units of the formulas (4) and (5) is not necessarily clear, it is assumed that they are generated through the following route.

さらに本発明の芳香族ポリカーボネートは、２８０℃でのメルトインデックス測定において、溶融樹脂に対して１１ｋｇの荷重を加えた場合に押出されたストランド断面積をオリフィス断面積で除した値であるスウェル比が１．２以上４．０以下の範囲であることが必要である。
Furthermore, the aromatic polycarbonate of the present invention has a swell ratio that is a value obtained by dividing the cross-sectional area of the extruded strand by the orifice cross-sectional area when a load of 11 kg is applied to the molten resin in the melt index measurement at 280 ° C. It is necessary to be in the range of 1.2 or more and 4.0 or less.

また、上記式（１）で表される構造単位１モルに対する上記式（２）〜（５）で表される分岐構造単位の合計モル数の比は、製造された芳香族ポリカーボネートをアルカリ加水分解後、高速液体クロマトグラフィー（ＨＰＬＣ）、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）等により、各々の構造単位に対応する化合物の量を測定することにより、容易に求められる。例えばアルカリ加水分解物を高速液体クロマトグラフィー（ＨＰＬＣ）等で分析した場合には、式（１）〜（５）で表される構造単位は、それぞれ下記式（９）〜（１３）の化合物として検知される。
The ratio of the total number of moles of the branched structural units represented by the above formulas (2) to (5) to 1 mol of the structural unit represented by the above formula (1) is determined by alkaline hydrolysis of the produced aromatic polycarbonate. Thereafter, it can be easily determined by measuring the amount of the compound corresponding to each structural unit by high performance liquid chromatography (HPLC), gel permeation chromatography (GPC) or the like. For example, when an alkaline hydrolyzate is analyzed by high performance liquid chromatography (HPLC) or the like, the structural units represented by the formulas (1) to (5) are as compounds of the following formulas (9) to (13) , respectively. Detected.

前記式（１）〜（５）で表される構造単位は、下記式（１４）〜（１８）の化合物として検知されるので、Ａｇｉｌｅｎｔ（株）製ＬＣ−ＭＳ（Ａｇｉｌｅｎｔ−１１００）及び日本電子製ＮＭＲ（ＡＬ−４００）を用いて同定した。また、各構造単位の含有量は、各化合物の標準物質を用いて濃度とピーク面積の検量線を作成し、各々の含有量を定量した。 Structural unit represented by the formula (1) to (5), since it is detected as a compound of the following formula (14) - (18), Agilent (KK) LC-MS (Agilent-1100) and Japan It identified using electronic NMR (AL-400). The content of each structural unit was determined by preparing a calibration curve of concentration and peak area using the standard substance of each compound, and quantifying each content.

Claims

A viscosity average molecular weight of 16,000 or more aromatic polycarbonate obtained by the transesterification method, the melt index measured at 2 80 ° C., strand cross-sectional area which is extruded when a load is applied in the 11kg to the molten resin following to the Ri swell ratio of 1.2 to 4.0 in the range der is a value obtained by dividing the orifice cross-sectional area, and that the polycarbonate was hydrolyzed, the compound represented by the following formula (9) An aromatic polycarbonate comprising the compounds represented by the formulas (10) to (13) in a total amount exceeding 0.3 mol% and not more than 0.8 mol% .

(In the formulas (9) to (13), X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, or 5 to 15 carbon atoms. Or a divalent group represented by —O—, —S—, —CO—, —SO—, —SO ₂ —
Is selected from the group consisting of )

Aromatic polycarbonate according to claim 1, scan swell ratio is equal to or in the range of 1.4 to 3.0.

Aromatic polycarbonate according to claim 1 or 2 viscosity average molecular weight and wherein the at 21,000 or more.

The aromatic polycarbonate according to claim 1 or 2, wherein the viscosity average molecular weight is 22,300 or more and 28,200 or less.

It hydrolyzate claims 1, wherein the content ratio of the compound represented by the formula (12) to the compound of formula (9) is 0.0001 or more 0.15mol less any 4 The aromatic polycarbonate according to any one of the above.

It hydrolyzate claims 1, wherein the content ratio of the compound represented by the formula (13) to the compound of formula (9) is 0.0001 or more 0.15 mol% or less of 5 The aromatic polycarbonate according to any one of the above.

The content ratio of the compound represented by Formula (12) and the compound represented by Formula (13) to the compound represented by Formula (9) is 0.002 to 0.12 mol%, respectively. The aromatic polycarbonate according to any one of claims 1 to 4, wherein

Conforming to JIS K7210, aromatic according to any one of claims 1 to 7 flow rate ratio represented by the following formula (6) (MVR-R) is equal to or in the range of 15 to 30 Polycarbonate.
MVR-R = MVR (21.6) / MVR (2.16) Formula (6)

Aromatic polycarbonate according to any one of claims 1 to 8 content of coal diester compound is characterized in that 200 wt ppm or less.

An aromatic polycarbonate composition containing an aromatic polycarbonate and the dye according to any one of claims 1 to 9, a shall be selected from the group dyes composed of Phthalocyanine Blue dyes and anthraquinone dyes, And the content of this dye is 0.01 weight ppm or more and 100 weight ppm or less, The aromatic polycarbonate composition characterized by the above-mentioned .

A method for producing an aromatic polycarbonate according to any one of the carbon acid diester and an aromatic dihydroxy compound is reacted of claims 1 to 9, selected from the group consisting of alkali metal compounds and alkaline earth metal compounds and the compound, how you characterized by the presence in the reaction system to 1.1 or more 5μmol below as metal amount with respect to the aromatic dihydroxy compound mole.

The A alkali metal compound and compound selected from the group consisting of alkaline earth metal compound, be present in the reaction system so that 1.3 to 3.8 [mu] mol or less as a metal amount for the aromatic dihydroxy compound method person according to claim 11, wherein.

The transesterification reaction is carried out using a reactor having two or more polymerization tanks connected in series, and the final polymerization tank is a horizontal type, and the reaction temperature in the final polymerization tank is 280 ° C. or higher and 300 ° C. or lower. method person according to claim 11 or 12, characterized in.

Hollow container obtained by blow-molding the aromatic polycarbonate according to any one of claims 1 to 9.

A hollow container obtained by blow molding the aromatic polycarbonate composition according to claim 10 .

The hollow container according to claim 14 or 15, wherein the hollow container is a dairy product bottle, a soft drink bottle, or a water bottle.

A molded article obtained by extruding the composition containing the polycarbonate according to any one of claims 1 to 9 .

The extruded product according to claim 17, wherein the extruded product is a sheet.

2. The extruded product is formed by profile extrusion.
7. Extruded product according to 7.

The extruded product according to claim 18, wherein the extruded product is a twin wall sheet or a multi-wall sheet.