JPS62227927A - Polycarbonate copolymer and its production - Google Patents
Polycarbonate copolymer and its productionInfo
- Publication number
- JPS62227927A JPS62227927A JP7136786A JP7136786A JPS62227927A JP S62227927 A JPS62227927 A JP S62227927A JP 7136786 A JP7136786 A JP 7136786A JP 7136786 A JP7136786 A JP 7136786A JP S62227927 A JPS62227927 A JP S62227927A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- dihydroxydiphenyl
- carbonate
- copolymer
- bisphenol compound
- 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
- 229920000515 polycarbonate Polymers 0.000 title claims description 25
- 239000004417 polycarbonate Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 30
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 bisphenol compound Chemical class 0.000 claims abstract description 12
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical group C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- IZJIAOFBVVYSMA-UHFFFAOYSA-N bis(4-methylphenyl) carbonate Chemical compound C1=CC(C)=CC=C1OC(=O)OC1=CC=C(C)C=C1 IZJIAOFBVVYSMA-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical group OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
末完ＩＪＩＩはポリカーボネート系共重合体およびその
製造方法に関し、詳しくは２種類の特定の繰返し単位を
一定割合で有し、透明性がよく、しかも耐熱性にすぐれ
たポリカーボネート系共重合体およびその効率のよい製
造方法に関する。[Detailed Description of the Invention] [Industrial Field of Application] Suikan IJII relates to polycarbonate copolymers and their production methods, and more specifically, they have two types of specific repeating units in a certain proportion, have good transparency, Moreover, the present invention relates to a polycarbonate copolymer having excellent heat resistance and an efficient method for producing the same.
［従来の技術及び発明が解決しようとする問題点］
従来から２．２−ビス（４′−ヒドロキシフェニル）プ
ロパン（通称ビスフェノールＡ）から製造されるポリカ
ーボネート樹脂はすぐれた機械的性質を有しているため
、床几な用途に供せられている。しかし、様々な用途の
拡大に伴ってポリカーボネート樹脂に対する要求性能が
厳しくなり、よりすぐれた性能を有するポリカーボネー
ト重合体が要望されている。[Prior art and problems to be solved by the invention] Conventionally, polycarbonate resins produced from 2,2-bis(4'-hydroxyphenyl)propane (commonly known as bisphenol A) have excellent mechanical properties. Because of this, it is used for floor storage purposes. However, with the expansion of various uses, the performance requirements for polycarbonate resins have become stricter, and polycarbonate polymers with even better performance are desired.
そこで本発明者は、このような状況に鑑み種々検討を重
ねた。In view of this situation, the inventors of the present invention have conducted various studies.
［問題点を解決するための手段］
その結果、従来のポリカーボネートに対し、特定の共重
合体成分を特定割合で導入することによって、ポリカー
ボネートのすぐれた透明性を損うことなく、耐熱性の向
りをはかることができることを見出した。本発明はかか
る知見に基いて完成したものである。[Means for solving the problem] As a result, by introducing a specific copolymer component in a specific ratio to conventional polycarbonate, it is possible to improve heat resistance without impairing the excellent transparency of polycarbonate. We found that it is possible to measure the The present invention was completed based on this knowledge.
すなわち、本発明は。That is, the present invention.
矛
で表わされる繰返し単位［Ｉ］および
一般式
［式中、Ｒ１、Ｒ２はそれぞれ水素原子、炭素数１〜５
のアルキル基またはハロゲン原子を示し、）７３ 、
Ｒ４はそれぞれ水素原子、炭素数１〜５のアルキル基ま
たはアリール基を示す。］で表わされる繰返し単位［１
１］を有するとともに、前記繰返し中位［Ｉ］のモル分
率が５％以Ｌ４０％未満であり、かつ塩化メチレンを溶
媒とする０、５８／ｄｊ！濃度の溶液の２０℃における
還元粘度［ηｓｐ／Ｃ１が０．３ｄｉ）／ｇ以りである
ポリカーボネート系共重合体を提供するものである。ま
た、本発明は、
で表わされる４、４′−ジヒドロキシジフェニル。The repeating unit [I] represented by a spear and the general formula [wherein R1 and R2 are each a hydrogen atom and a carbon number of 1 to 5]
represents an alkyl group or a halogen atom, )73,
R4 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group. ] is a repeating unit [1
1], the mole fraction of the repeating intermediate [I] is 5% or more and less than L40%, and 0.58/dj! using methylene chloride as a solvent! The object of the present invention is to provide a polycarbonate copolymer having a reduced viscosity [ηsp/C1 of 0.3 di)/g or more at 20° C. in a solution of a concentration of the present invention. Further, the present invention provides 4,4'-dihydroxydiphenyl represented by:
一般式
［式中、１１７１ 、 Ｒ２、Ｒ３、Ｒ４は前記と同じ
ものを示す。］
で表わされるビスフェノール化合物および炭酸エステル
形成性誘導体を反応させることによってＬ記ポリカーボ
ネート系共重合体を製造する方法をも提供する。General formula [wherein 1171, R2, R3, and R4 are the same as above. ] Also provided is a method for producing a polycarbonate copolymer represented by L by reacting a bisphenol compound represented by the following and a carbonate-forming derivative.
本発明のポリカーボネート系共重合体は、前述の如く繰
返し単位［Ｉ］および［ＩＩ］からなる共重合体であり
、これらの割合は繰返し中位［Ｉ］のモル分率が５％以
Ｉ：、４０％未満となるように調節されている。ここで
繰返し中位［Ｉ］のモル分率が５％未満では得られるポ
リカーボネート系共重合体の１耐熱性向Ｆ効果が小さく
なり、一方、繰返し中位［Ｉ］のモル分率が４０％以り
になると得られるポリカーボネート系共重合体の透明性
が低ドする。As mentioned above, the polycarbonate copolymer of the present invention is a copolymer consisting of repeating units [I] and [II], and the molar fraction of the repeating middle [I] is 5% or more I: , is adjusted to be less than 40%. Here, if the mole fraction of the middle repeat [I] is less than 5%, the 1 heat resistance property F effect of the obtained polycarbonate copolymer will be small; When the temperature increases, the transparency of the polycarbonate copolymer obtained decreases.
また、本発明のポリカーボネート系共重合体の重合度は
、用途等に応じて適宜室めればよいが。Further, the degree of polymerization of the polycarbonate copolymer of the present invention may be adjusted as appropriate depending on the use and the like.
塩化メチレンを溶媒とする０、５ｇ／ｄＮ ｅ度の溶液
の２０℃における還元粘度［ηｓｐ／ｃｌが０．３ｄｉ
’／ｇ以ト、好ましくは０．３〜１．ＯｄＩ！／ｇの共
重合体となるように重合させるべきである。ここで、還
元粘度が０．３ｄρ／ｇ未満であると、得られる共重合
体は機械的強度の低いものとなる。Reduced viscosity [η sp/cl is 0.3 di
'/g or less, preferably 0.3 to 1. OdI! /g of copolymer. Here, if the reduced viscosity is less than 0.3 dρ/g, the resulting copolymer will have low mechanical strength.
Ｌ記・般式［ｒＩ］で表わされる繰返し単位としては、
Ｒ１−Ｒ４の種類９位置により様々なものがあるが、具
体的な謹返し単位の構造を示せば。As a repeating unit represented by L/general formula [rI],
There are various types depending on the type and position of R1-R4, but the specific structure of the repeating unit is shown below.
などをあげることができる。etc. can be given.
本発明におけるポリカーボネート系共重合体は、ヒ記繰
返し単位［Ｉ］ と［１１１を有するものであり、これ
らのランダム共重合体、ブロック共重合体、交互共重合
体など様々なものがある。The polycarbonate copolymer in the present invention has repeating units [I] and [111], and there are various types thereof such as random copolymers, block copolymers, and alternating copolymers.
本発明のポリカーボネート系共重合体は様々な方法によ
り製造することができるが、前述の本発明の方法によれ
ば効率よくかつ高品質のポリカーボネート系共重合体が
製造される。The polycarbonate copolymer of the present invention can be produced by various methods, but according to the method of the present invention described above, a polycarbonate copolymer of high quality can be produced efficiently.
本発明の方法では、前記式［ＩＩＩ］で表わされる４、
４′−ジヒドロキシジフェニルと前記一般式［ＩＶ］で
表わされるビスフェノール化合物および炭酸エステル形
成性誘導体を反応系に導入し、これを反応させる。ここ
で４，４′−ジヒドロキシジフェニルと ・般式［ｒＶ
］ で表わされるビスフェノール化合物の供給割合は、
特に制限はないが、この４．４′−ジヒドロキシジフェ
ニルが緑返し中位［Ｉ］を形成し、 ・般式［ＩＶ］で
表わされるビスフェノール化合物が繰返し単位［ｒｌ］
を形成することを考慮すると、４．４′−ジヒドロキシ
ジフェニル／ビスフェノール化合物＝５／９５〜４０／
６０ （モル比）、好ましくは１０／９０〜３５／８
５ （モル比）とすべきである。また、炭酸エステル
形成性誘導体の導入量は、前述の４．４′−ジヒドロキ
シジフェニルと一般式［ＩＶ］で表わされるビスフェノ
ール化合物の合計モル数あるいはそれ以にとすることが
望ましい。なお、この炭酸エステル形成性誘導体の種類
は、製造すべきポリカーボネート系共重合体の用途等に
応じて適宜選定すればよいが、 ・般にはジフェニルカ
ーボネート、ジ−ｐ−１リルカーポネート、フェニル−
ｐ−）リルカーポネート、ジーｐ−クロロフェニルカー
ボネートあるいはジナフチルカーボネートなどのジアリ
ールカーボネート、さらにはホスゲン、プロムホスゲン
などの炭酸のハロゲン化物等が用いられ、そのうちジフ
ェニルカーボネートあるいはホスゲンが好ましい。In the method of the present invention, 4 represented by the above formula [III],
4'-dihydroxydiphenyl, the bisphenol compound represented by the general formula [IV], and the carbonate-forming derivative are introduced into a reaction system and allowed to react. Here, 4,4'-dihydroxydiphenyl and the general formula [rV
] The supply ratio of bisphenol compounds expressed as
Although there is no particular restriction, this 4,4'-dihydroxydiphenyl forms the green center [I], and the bisphenol compound represented by the general formula [IV] is the repeating unit [rl].
Considering the formation of 4,4'-dihydroxydiphenyl/bisphenol compound = 5/95 to 40/
60 (molar ratio), preferably 10/90 to 35/8
5 (molar ratio). Further, the amount of the carbonate-forming derivative introduced is desirably equal to or greater than the total number of moles of the aforementioned 4,4'-dihydroxydiphenyl and the bisphenol compound represented by the general formula [IV]. The type of carbonate ester-forming derivative may be selected as appropriate depending on the use of the polycarbonate copolymer to be produced, but generally diphenyl carbonate, di-p-1 lyl carbonate, phenyl −
Diaryl carbonates such as p-)lyl carbonate, di-p-chlorophenyl carbonate or dinaphthyl carbonate, and halides of carbonic acid such as phosgene and promphosgene are used, of which diphenyl carbonate or phosgene is preferred.
これら４．４′−ジヒドロキシジフェニル、・般式［ｒ
Ｖ］で表わされるビスフェノール化合物および炭酸エス
テル形成性誘導体の反応は、公知の触媒の存在ド、溶融
状態で行なうことが好ましく、反応温度は通常は１６０
℃以し、好ましくは２００℃以り、更に好ましくは２５
０℃〜３５０℃程度である。These 4,4'-dihydroxydiphenyl, general formula [r
The reaction between the bisphenol compound represented by V] and the carbonate-forming derivative is preferably carried out in a molten state in the presence of a known catalyst, and the reaction temperature is usually 160°C.
℃ or higher, preferably 200℃ or higher, more preferably 25℃
The temperature is about 0°C to 350°C.
また、反応の圧力は任意であるが、反応が進行するにし
たがって減圧することが望ましい。Further, although the reaction pressure is arbitrary, it is desirable to reduce the pressure as the reaction progresses.
［発明の効果］
このようにして得られる本発明のポリカーボネート系共
重合体は、透明性が良好でしかも耐熱性のすぐれたもの
である。さらに耐薬品性１機械的強度等も良好である。[Effects of the Invention] The polycarbonate copolymer of the present invention thus obtained has good transparency and excellent heat resistance. Furthermore, chemical resistance, mechanical strength, etc. are also good.
従って、本発明のポリカーボネート系共重合体は各種産
業用機器素材として幅広くかつ有効に利用でき、特に光
学機器素材として有用である。Therefore, the polycarbonate copolymer of the present invention can be widely and effectively used as a material for various industrial equipment, and is particularly useful as a material for optical equipment.
［実施例］ 次に、本発明を実施例により詳しく説明する。[Example] Next, the present invention will be explained in detail with reference to examples.
実施例１
邪魔板を備えた内容積ｌＩ２の反応器に、４．４’−ジ
ヒドロキシジフェニル１２．２ ｇ （０，０７５モル
）と２．２−ビス（４′−ヒドロキシフェニル）プロパ
ン３９．９ ｇ （０，１７５モル）とを６％濃度の水
酸化ナトリウム水溶液４６０ａＲに溶解した溶液を入れ
、次いで塩化メチレン２５０層ｐを加えて激しく攪拌し
ながらホスゲンガスを９００ｍβ／分の割合で１３分間
吹き込んだ。次いで得られた反応生成物を静置分離し、
有機層に屯合度２〜３であり、分子末端にクロロホーメ
ート基を有するポリカーボネート前駆体の塩化メチレン
溶液を得た。Example 1 12.2 g (0,075 mol) of 4,4'-dihydroxydiphenyl and 39.9 g of 2,2-bis(4'-hydroxyphenyl)propane were placed in a reactor with an internal volume of lI2 equipped with baffles. A solution prepared by dissolving G (0,175 mol) in a 6% sodium hydroxide aqueous solution 460aR was added, and then 250 layers of methylene chloride was added, and while stirring vigorously, phosgene gas was blown in at a rate of 900 mβ/min for 13 minutes. . Then, the obtained reaction product was separated by standing,
A methylene chloride solution of a polycarbonate precursor having a concentration of 2 to 3 in the organic layer and having a chloroformate group at the molecular end was obtained.
次に、このポリカーボネート前駆体の塩化メチレン溶液
３００Ｉｌｉ＋をさらに塩化メチレンで希釈して全体を
４５０ｍＪとした。これに分子量調節剤としてｐ −ｔ
ｅｒｔ−ブチルフェノール２．０ｇを加えた後、２規定
の水酸化ナトリウム水溶液に４．４′−ジヒドロキシジ
フェニル４．６ｇと２，２−ビス（４′−ヒドロキシフ
ェニル）プロパン １５．３ ｇを溶解させた溶液を加
えて混合した。この混合液を攪拌ドに重合触媒として５
重、ｒ、″Ｌ％濃度のトリエチルアミン水溶液１ｍｊ
！を加え、２８°Ｃにおいて１時間重縮合反応を行なっ
た。反応路ｒ後、生成物を塩化メチレン１ｆｆ’？ｌ’
！釈し、水１．５ｆｆ、水０．５Ｎ 、 ０．０１規定
の塩酸０．５２で順次洗浄した。このようにして得られ
た有機層を２１２のメタノール中に注入して白色の共重
合体を得た。Next, 300 Ili+ of the methylene chloride solution of this polycarbonate precursor was further diluted with methylene chloride to give a total of 450 mJ. This was added with p-t as a molecular weight regulator.
After adding 2.0 g of ert-butylphenol, 4.6 g of 4.4'-dihydroxydiphenyl and 15.3 g of 2,2-bis(4'-hydroxyphenyl)propane were dissolved in a 2N aqueous sodium hydroxide solution. The solution was added and mixed. Stir this mixture as a polymerization catalyst.
1 mj of triethylamine aqueous solution with a concentration of 1 mj
! was added, and a polycondensation reaction was carried out at 28°C for 1 hour. After reaction route r, the product is converted into methylene chloride 1ff'? l'
! It was washed sequentially with 1.5 ff of water, 0.5 N of water, and 0.52 of 0.01N hydrochloric acid. The organic layer thus obtained was poured into 212 methanol to obtain a white copolymer.
ここで得られた共重合体は、塩化メチレンを溶媒とする
０、５ｇ／ｄｉ’ｃ度の溶液の２０’Ｃにおける還元粘
度［７Ｊｓｐ／ｃ］が０．５８ｄＩ！／ｇであった。ま
た、この共重合体の赤外線吸収スペクトル分析の結果中
１５６０ｃ履１と１４９０ｃｍ ＋の位置にベンゼン環
に基く吸収、 １１３５０ＣＩｌ ｌの位置にカルボニ
ル基に基づく吸収、 １２４０ｃａ ｌの位置にエーテ
ル結合に基づく吸収が認められた。また、核磁気共鳴ス
ペクトル分析の結果、繰返し中位［Ｉ］のモル分率が３
０％であった。The copolymer obtained here has a reduced viscosity [7 Jsp/c] of 0.5 g/di'c degree solution at 20'C in methylene chloride as a solvent of 0.58 dI! /g. In addition, in the results of infrared absorption spectrum analysis of this copolymer, absorption based on benzene ring at 1560c1 and 1490cm+, absorption based on carbonyl group at 11350C11, and absorption based on ether bond at 1240C11. was recognized. In addition, as a result of nuclear magnetic resonance spectroscopy, the mole fraction of the repeating middle [I] was 3
It was 0%.
この共重合体の熱的性質についてはガラス転移温度が１
６０°Ｃであった。また、透明性についてはＪＩＳ−に
−６７１９に準拠して全光線透過率を測定したところ６
０％であった。これらの結果をまとめて第１表に示す。Regarding the thermal properties of this copolymer, the glass transition temperature is 1
The temperature was 60°C. Regarding transparency, total light transmittance was measured in accordance with JIS-6719.
It was 0%. These results are summarized in Table 1.
実施例２
ポリカーボネート前駆体合成に使用する４、４’−ジヒ
ドロキシジフェニルの星を ９．３ｇ （０，０５モル
）、２．２−ビス（４′−ヒドロキシフェニル）プロパ
ンの量を４５．８ ｇ （０，２モル）としたほかは実
施例１と同様にして共重合体を得た。この共重合体の性
質を第１表に示す。Example 2 The amount of 4,4'-dihydroxydiphenyl star used in polycarbonate precursor synthesis was 9.3 g (0.05 mol), and the amount of 2,2-bis(4'-hydroxyphenyl)propane was 45.8 g. A copolymer was obtained in the same manner as in Example 1 except that the amount was changed to (0.2 mol). The properties of this copolymer are shown in Table 1.
実施例３
ポリカーボネート前駆体合成に使用する４、４’−ジヒ
ドロキシジフェニルの量を８．９８ｇ （０，０３７５
モル）、２．２−ビス（４′−ヒドロキシフェニル）プ
ロパンの州を４８．５ ｇ （０，２１２５モル）とし
たほかは実施例１と同様にして共重合体を得た。この共
重合体の性質を第１表に示す。Example 3 The amount of 4,4'-dihydroxydiphenyl used in polycarbonate precursor synthesis was 8.98 g (0,0375
A copolymer was obtained in the same manner as in Example 1, except that the amount of 2.2-bis(4'-hydroxyphenyl)propane was 48.5 g (0,2125 mol). The properties of this copolymer are shown in Table 1.
実施例４
ポリカーボネート前駆体合成に使用する４、４′−ジヒ
ドロキシジフェニルの埴を４．ｌ３５ｇ （０，０２５
モル）、２．２−ビス（４′−ヒドロキシフェニル）プ
ロパンの量を５１．３ ｇ （０，２２５モル）とした
ほかは実施例１と同様にして共重合体を得た。この共重
合体の性質を第１表に示す。Example 4 4,4'-dihydroxydiphenyl clay used in polycarbonate precursor synthesis was prepared by 4. l35g (0,025
A copolymer was obtained in the same manner as in Example 1, except that the amount of 2.2-bis(4'-hydroxyphenyl)propane was changed to 51.3 g (0,225 mol). The properties of this copolymer are shown in Table 1.
比較例１
４．４′−ジヒドロキシジフェニルを全く使用しなかっ
たこと以外は実施例１と同様にしてポリカーボネートを
得た。このものの性質を第１表に示す。Comparative Example 1 A polycarbonate was obtained in the same manner as in Example 1 except that 4.4'-dihydroxydiphenyl was not used at all. The properties of this product are shown in Table 1.
比較例２
ポリカーボネート前駆体合成に使用する４、４′−ジヒ
ドロキシジフェニルの星を２３．２５ ｇ （０，１２
５モル）、２．２−ビス（４′−ヒドロキシフェニル）
プロパンの量を２８．５ ｇ （０，１２５モル）とし
たほかは実施例１と同様にして共重合体を得た。この共
重合体の性質を第１表に示す。Comparative Example 2 23.25 g (0,12
5 mol), 2,2-bis(4'-hydroxyphenyl)
A copolymer was obtained in the same manner as in Example 1 except that the amount of propane was changed to 28.5 g (0.125 mol). The properties of this copolymer are shown in Table 1.
第 １ 表Chapter 1 Table
Claims (4)
〜５のアルキル基またはハロゲン原子を示し、Ｒ＾３、
Ｒ＾４はそれぞれ水素原子、炭素数１〜５のアルキル基
またはアリール基を示す。］ で表わされる繰返し単位［II］を有するとともに、前記
繰返し単位［ I ］のモル分率が５％以上４０％未満で
あり、かつ塩化メチレンを溶媒とする０．５ｇ／ｄｌ濃
度の溶液の２０℃における還元粘度［η＿Ｓ＿Ｐ／ｃ］
が０．３ｄｌ／ｇ以上であるポリカーボネート系共重合
体。(1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Repeating unit [I] represented by and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are hydrogen atoms, respectively] , carbon number 1
~5 alkyl group or halogen atom, R^3,
R^4 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group. ], the molar fraction of the repeating unit [I] is 5% or more and less than 40%, and 20% of a solution with a concentration of 0.5 g/dl using methylene chloride as a solvent. Reduced viscosity at °C [η_S_P/c]
is 0.3 dl/g or more.
式 ▲数式、化学式、表等があります▼ ［式中、Ｒ＾１、Ｒ＾２はそれぞれ水素原子、炭素数１
〜５のアルキル基またはハロゲン原子を示し、Ｒ＾３、
Ｒ＾４はそれぞれ水素原子、炭素数１〜５のアルキル基
またはアリール基を示す。］ で表わされるビスフェノール化合物および炭酸エステル
形成性誘導体を反応させることを特徴とする 式 ▲数式、化学式、表等があります▼ で表わされる繰返し単位［ I ］および 一般式 ▲数式、化学式、表等があります▼ ［式中、Ｒ＾１、Ｒ＾２、Ｒ＾３、Ｒ＾４は前記と同じ
ものを示す。］ で表わされる繰返し単位［II］を有するとともに、前記
繰返し単位［ I ］のモル分率が５％以上４０％未満で
あり、かつ塩化メチレンを溶媒とする０．５ｇ／ｄｌ度
の溶液の２０℃における還元粘度［η＿Ｓ＿Ｐ／ｃ］が
０．３ｄｌ／ｇ以上であるポリカーボネート系共重合体
の製造方法。(2) 4,4'-dihydroxydiphenyl represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are respectively Hydrogen atom, carbon number 1
~5 alkyl group or halogen atom, R^3,
R^4 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group. A formula characterized by reacting a bisphenol compound represented by ▼ [In the formula, R^1, R^2, R^3, and R^4 are the same as above. ], the molar fraction of the repeating unit [I] is 5% or more and less than 40%, and 20% of a 0.5 g/dl solution using methylene chloride as a solvent. A method for producing a polycarbonate copolymer having a reduced viscosity [η_S_P/c] of 0.3 dl/g or more at °C.
ェノール化合物を前者／後者＝５／９５〜４０／６０（
モル比）の割合で加えるとともに、炭酸エステル形成性
誘導体を前記４、４′−ジヒドロキシジフェニルとビス
フェノール化合物の合計モル数あるいはそれ以上の割合
で加えて反応させる特許請求の範囲第２項記載の製造方
法。(3) 4,4'-dihydroxydiphenyl and bisphenol compounds, former/latter = 5/95 to 40/60 (
4,4'-dihydroxydiphenyl and bisphenol compound in a molar ratio), and the carbonate ester-forming derivative is added in a ratio of the total number of moles of the 4,4'-dihydroxydiphenyl and the bisphenol compound or more. Method.
ネート、ジ−ｐ−トリルカーボネート、フェニル−ｐ−
トリルカーボネート、ジ−ｐ−クロロフェニルカーボネ
ート、ジナフチルカーボネート、ホスゲンあるいはプロ
ムホスゲンである特許請求の範囲第２項記載の製造方法
。(4) The carbonate ester-forming derivative is diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-
3. The manufacturing method according to claim 2, wherein tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate, phosgene or promphosgene is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7136786A JPH0692480B2 (en) | 1986-03-31 | 1986-03-31 | Polycarbonate copolymer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7136786A JPH0692480B2 (en) | 1986-03-31 | 1986-03-31 | Polycarbonate copolymer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62227927A true JPS62227927A (en) | 1987-10-06 |
| JPH0692480B2 JPH0692480B2 (en) | 1994-11-16 |
Family
ID=13458459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7136786A Expired - Lifetime JPH0692480B2 (en) | 1986-03-31 | 1986-03-31 | Polycarbonate copolymer and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692480B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01178519A (en) * | 1988-01-11 | 1989-07-14 | Daicel Chem Ind Ltd | Resin for optical material |
| US5401826A (en) * | 1991-10-29 | 1995-03-28 | General Electric Plastics Japan | Method for the preparation, of copolymeric polycarbonates |
| US5604063A (en) * | 1991-11-14 | 1997-02-18 | Hitachi Chemical Company, Ltd. | Composition for charge transport layer and electrophotographic member using same |
| EP1277781A3 (en) * | 2001-07-16 | 2003-05-21 | Bayer Aktiengesellschaft | Process for preparing copolycarbonates |
| JP2004510040A (en) * | 2000-09-26 | 2004-04-02 | バイエル アクチェンゲゼルシャフト | New copolycarbonates and their use |
| 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 |
| DE112009002395T5 (en) | 2008-10-07 | 2012-01-19 | Idemitsu Kosan Co. Ltd. | A transparent flame retardant resin composition of an aromatic polycarbonate and molded products thereof |
| JP2012025795A (en) * | 2010-07-20 | 2012-02-09 | Mitsubishi Gas Chemical Co Inc | Polycarbonate resin and laminate molding member using the same |
-
1986
- 1986-03-31 JP JP7136786A patent/JPH0692480B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01178519A (en) * | 1988-01-11 | 1989-07-14 | Daicel Chem Ind Ltd | Resin for optical material |
| US5401826A (en) * | 1991-10-29 | 1995-03-28 | General Electric Plastics Japan | Method for the preparation, of copolymeric polycarbonates |
| US5604063A (en) * | 1991-11-14 | 1997-02-18 | Hitachi Chemical Company, Ltd. | Composition for charge transport layer and electrophotographic member using same |
| JP2004510040A (en) * | 2000-09-26 | 2004-04-02 | バイエル アクチェンゲゼルシャフト | New copolycarbonates and their use |
| EP1277781A3 (en) * | 2001-07-16 | 2003-05-21 | Bayer Aktiengesellschaft | Process for preparing copolycarbonates |
| US6753405B2 (en) | 2001-07-16 | 2004-06-22 | Bayer Aktiengesellschaft | Preparation of copolycarbonates |
| KR100894600B1 (en) * | 2001-07-16 | 2009-04-24 | 바이엘 악티엔게젤샤프트 | Preparation of Copolycarbonates |
| 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 |
| DE112009002395T5 (en) | 2008-10-07 | 2012-01-19 | Idemitsu Kosan Co. Ltd. | A transparent flame retardant resin composition of an aromatic polycarbonate and molded products thereof |
| JP2012025795A (en) * | 2010-07-20 | 2012-02-09 | Mitsubishi Gas Chemical Co Inc | Polycarbonate resin and laminate molding member using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0692480B2 (en) | 1994-11-16 |
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