KR0183433B1 - Process for preparing branched polycarbonate - Google Patents
Process for preparing branched polycarbonate Download PDFInfo
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- KR0183433B1 KR0183433B1 KR1019960019827A KR19960019827A KR0183433B1 KR 0183433 B1 KR0183433 B1 KR 0183433B1 KR 1019960019827 A KR1019960019827 A KR 1019960019827A KR 19960019827 A KR19960019827 A KR 19960019827A KR 0183433 B1 KR0183433 B1 KR 0183433B1
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- branched polycarbonate
- polycarbonate resin
- hydroxyphenyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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Abstract
본 발명은 브렌치드 폴리카보네이트의 제조방법에 관한 것으로서, 더욱 상세하게는 비스페놀 A로부터 폴리카보네이트 수지를 제조하는 데 있어서 브렌칭제로서 페놀유도체의 변형된 구조를 갖는 화합물을 첨가함으로써 용융점도, 열분해온도 등의 물성이 우수하여 블로우 성형용으로 적합한 브렌치드 폴리카보네이트 수지를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a branched polycarbonate, and more particularly, in preparing a polycarbonate resin from bisphenol A, by adding a compound having a modified structure of a phenol derivative as a branching agent, such as melt viscosity and thermal decomposition temperature. The present invention relates to a method for producing a branched polycarbonate resin having excellent physical properties and suitable for blow molding.
Description
본 발명은 브렌치드 폴리카보네이트의 제조방법에 관한 것으로서, 더욱 상세하게는 비스페놀 A로부터 폴리카보네이트 수지를 제조하는 데 있어서 브렌칭제로서 페놀유도체의 변형된 구조를 갖는 화합물을 첨가함으로써 용융점도, 열분해온도 등의 물성이 우수하여 불로우 성형용으로 적합한 브렌치드 폴리카보네이트 수지를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a branched polycarbonate, and more particularly, in preparing a polycarbonate resin from bisphenol A, by adding a compound having a modified structure of a phenol derivative as a branching agent, such as melt viscosity, thermal decomposition temperature and the like. It relates to a method for producing a branched polycarbonate resin having excellent physical properties and suitable for blow molding.
폴리카보네이트 수지는 다양한 온도범위에서 투명성, 강도, 수치안정성 및 충격강도 등의 물성이 우수한 고내열성 엔지니어링 플라스틱이다.Polycarbonate resin is a high heat resistant engineering plastic with excellent physical properties such as transparency, strength, numerical stability and impact strength at various temperature ranges.
그러나, 일반 선형(linear) 폴리카보네이트 수지는 우수한 물리적 성질에도 불구하고, 이를 블로우 성형에 응용하기 위해 필요한 요건, 즉 높은 용융강도(melt strength), 높은 전단응력도(shear sensitivity) 및 용융토출량비(melt index ratio)가 13이상이 되어야만 하는 요건을 충족시키지 못하고 있다.However, despite the good physical properties of ordinary linear polycarbonate resins, the requirements for applying them to blow molding are: high melt strength, high shear sensitivity and melt discharge ratio. It does not meet the requirement that the index ratio be 13.
이와같은 이유로 선형 폴리카보네이트 수지보다는 브렌치드 폴리카보네이트 수지가 블로우 성형용으로 적합한바, 통상 브렌치드 폴리카보네이트 수지는 다가 알코올, 다가 카르복실산 및 다가아실클로라이드 중 선택된 1 종 이상의 화합물과 비스페놀 A 및 포스겐을 혼합 반응시켜 얻을 수 있다.For this reason, branched polycarbonate resins, rather than linear polycarbonate resins, are suitable for blow molding. In general, branched polycarbonate resins include bisphenol A and phosgene and at least one compound selected from polyhydric alcohols, polycarboxylic acids and polyacyl chlorides. It can obtain by mixing reaction.
이와 같은 브렌치드 폴리카보네이트 수지의 제조예로 미국특허 제 3,544,514 호와 미국특허 제 4,474,999 호에서는 알코올기가 3개 이상인 다가페놀로서 1,1,1-트리스(4-하이드록시페닐)에탄 또는 1,3,5-트리스(4-하이드록시페닐)벤젠을 주로 사용하여 폴리카보네이트 수지를 제조하였으며, 또한 미국특허 제 4,001,184 호에서는 싸이아누릭 클로라이드(cyanuric chloride)를 사용하여 폴리카보네이트 수지를 제조하는 방법을 개시하고 있다.As examples of the production of such branched polycarbonate resins, U.S. Patent Nos. 3,544,514 and 4,474,999 describe polyhydric phenols having three or more alcohol groups as 1,1,1-tris (4-hydroxyphenyl) ethane or 1,3. Polycarbonate resin was prepared mainly using, 5-tris (4-hydroxyphenyl) benzene, and US Patent No. 4,001,184 discloses a method of preparing polycarbonate resin using cyanuric chloride. Doing.
그러나, 이와같은 브렌칭제를 첨가하여 제조된 브렌치드 폴리카보네이트 수지는 열분해 온도가 낮아 황변현상이 발생하고 반응성에 문제가 있다.However, the branched polycarbonate resin prepared by adding such a branching agent has a low pyrolysis temperature, resulting in yellowing and problems in reactivity.
따라서, 본 발명자들은 상기와 같은 브렌칭제를 첨가하여 브렌치드 폴리카보네이트 수지를 제조하는 방법의 문제점을 해결하기 위하여 부렌칭제로서 페놀 유도체로부터 변형된 구조를 가지는 화합물을 첨가한 결과 용융점도 및 열분해온도가 높고, 용융토출량비가 20 이상인 브렌치드 폴리카보네이트 수지를 제조함을 알게되어 본 발명을 완성하였다.Accordingly, the present inventors have added a compound having a structure modified from a phenol derivative as a sub-bending agent in order to solve the problem of the method for producing a branched polycarbonate resin by adding the above-mentioned branching agent as a result of melting viscosity and thermal decomposition temperature The present invention was completed to find a branched polycarbonate resin having a high melt discharge ratio of 20 or more.
본 발명은 용융강도 및 열분해온다가 높고 용융토출량비가 13 이상이어 블로우 성형용으로 적합한 브렌치드 폴리카보네이트 수지를 제조하는 방법을 제공하는 데 그 목적이 있다.An object of the present invention is to provide a method for producing a branched polycarbonate resin suitable for blow molding because the melt strength and thermal decomposition temperature is high and the melt discharge ratio is 13 or more.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 비스페놀 A, 브렌칭제 및 분자량조절제로부터 브렌치드 폴리카보네이트 수지를 제조하는 방법에 있어서, 상기 브렌칭제로서 2-(4-하이드록시페닐)-4-하이드록시 페놀, 2,4-(4-하이드록시페닐)-페놀 및 2,5-(4-하이드록시페닐)-페놀 중에서 선택된 1종 이상의 것을 비스페놀 A에 대하여 0.05∼1.0 몰% 되도록 첨가하는 것을 그 특징으로 한다.The present invention provides a method for producing a branched polycarbonate resin from bisphenol A, a branching agent and a molecular weight regulator, wherein the branching agent is 2- (4-hydroxyphenyl) -4-hydroxy phenol, 2,4- (4 At least one selected from -hydroxyphenyl) -phenol and 2,5- (4-hydroxyphenyl) -phenol is added so as to be 0.05 to 1.0 mol% with respect to bisphenol A.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 페놀 유도체로부터 변형된 구조를 갖는 화합물을 브렌칭제로 첨가함으로써 블로우 성형용으로 적합한 브렌치드 폴리카보네이트 수지의 제조방법에 관한 것이다.The present invention relates to a process for producing a branched polycarbonate resin suitable for blow molding by adding a compound having a structure modified from a phenol derivative as a branching agent.
본 발명에 따른 브렌치드 폴리카보네이트 수지의 제조는 3단계로 이루어지는 바, 먼저 제1단계는 말단기가 클로로포메이트인 비스페놀 A, 브렌칭제 및 포스겐을 반응시켜 올리고머를 합성하는 단계이다.The preparation of the branched polycarbonate resin according to the present invention consists of three steps. First, the first step is a step of synthesizing an oligomer by reacting bisphenol A, a branching agent, and phosgene having a chloroformate.
이때, 브렌칭제로는 2-(4-하이드록시페닐)-4- 하이드록시 페놀, 2,4-(4-하이드록시페닐)-페놀 및 2,5-(4-하이드록시페닐)-페놀 중에서 선택된 1 종 이상의 것을 상기의 비스페놀 A에 대하여 0.05∼1.0 몰% 되도록 첨가한다.In this case, as the branching agent, among 2- (4-hydroxyphenyl) -4-hydroxy phenol, 2,4- (4-hydroxyphenyl) -phenol and 2,5- (4-hydroxyphenyl) -phenol At least one selected is added so as to be 0.05 to 1.0 mol% based on the bisphenol A.
이와 같은 브렌칭제는 선형 고분자간의 가교역할을 하는 것으로서, 그 함량이 비스페놀 A에 대하여 0.05 몰% 미만이면 통상의 선형 폴리카보네이트와 동일한 물성을 나타내고 1.0 몰%를 초과하는 경우 반응중 가교반응이 발생하여 원하는 수지를 얻을 수 없는 문제가 있다.Such a branching agent acts as a crosslinking agent between the linear polymers. When the content of the branching agent is less than 0.05 mol% with respect to bisphenol A, the branching agent exhibits the same physical properties as that of the conventional linear polycarbonate, and when it exceeds 1.0 mol%, a crosslinking reaction occurs during the reaction. There is a problem that a desired resin cannot be obtained.
그 다음, 2단계 반응으로서 분자량조절제와 3차 아민 화합물을 첨가하여 분자량을 증가시킨다.Then, the molecular weight is increased by adding a molecular weight modifier and a tertiary amine compound as a two-step reaction.
분자량조절제로는 파라-t-부틸페놀, 페놀 또는 3,5-디-t-부틸페놀을 사용할 수 있으며, 3차 아민 화합물로는 트리에틸아민, 디메틸프로필아민 또는 디에틸메틸아민을 사용할 수 있다.Para-t-butylphenol, phenol or 3,5-di-t-butylphenol may be used as the molecular weight regulator, and triethylamine, dimethylpropylamine or diethylmethylamine may be used as the tertiary amine compound. .
마지막으로, 제3단계 반응으로서 수산화나트륨을 첨가하여 중축합반응을 촉진시켜 원하는 분자량을 갖는 브렌치드 폴리카보네이트를 제조한다.Finally, sodium hydroxide is added as a third step to promote the polycondensation reaction to prepare a branched polycarbonate having a desired molecular weight.
본 발명에서 요구하는 수지의 분자량은 20000∼30000이며, 중축합 반응시 반응 온도는 25∼45。C 인 바, 바람직하기로는 실온이다.The molecular weight of the resin required in the present invention is 20000 to 30000, the reaction temperature during the polycondensation reaction is 25 to 45 ° C., preferably room temperature.
상기 제1단계에서 얻은 분자량은 1000∼2000 정도이며, 2단계에서는 3000∼6000 정도로 얻어진다.The molecular weight obtained in the first step is about 1000 to 2000, and in the second step is about 3000 to 6000.
이와 같이 브렌칭제로서 페놀 유도체의 변형된 구조를 갖는 화합물을 첨가하여 제조된 브렌치드 폴리카보네이트 수지는 용융강도 및 열분해온도가 높고 용융토출량비가 13 이상이어서 블로우 성형용으로 적합하다.The branched polycarbonate resin prepared by adding a compound having a modified structure of a phenol derivative as a branching agent is suitable for blow molding because its melt strength and thermal decomposition temperature are high and the melt discharge ratio is 13 or more.
이하, 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.
[실시예 1]Example 1
비스페놀 A 50g(0.264 mol)을 5.6%(w/w) 수산화나트륨 수용액 330㎖(18.46g, 0.462mol)에 녹여 1ℓ 둥근바닥 플라스크에 넣었다. 포스겐 26.1g(0.264mol)을 메틸렌클로라이드 200㎖ 에 포집하여 테프론 튜브를 통하여 천천히히 투입하면서 250 rpm하에서 반응시키고, 이때 외부온도는 0C로 유지하였다. 그리고, 질소기체 분위기하에서 약 30분간 반응시켜 분자량이 약 3000인 올리고머를 얻었다.50 g (0.264 mol) of bisphenol A was dissolved in 330 ml (18.46 g, 0.462 mol) of 5.6% (w / w) aqueous sodium hydroxide solution and placed in a 1 L round bottom flask. 26.1 g (0.264 mol) of phosgene was collected in 200 ml of methylene chloride and reacted at 250 rpm while slowly introduced through a Teflon tube, and the external temperature was maintained at 0C. Then, the mixture was reacted for about 30 minutes in a nitrogen gas atmosphere to obtain an oligomer having a molecular weight of about 3000.
브렌치드 폴리카보네이트를 중합하기 위하여 브렌칭제로 2-(4-하이드록시페닐)-4-하이드록시페놀 0.22g(비스페놀A에 대하여 0.5 몰%)을 5.6%(w/w)인 수산화나트륨 2.6㎖에 용해시켜 중축합반응을 진행시켰다. 그리고 나서, 분자량이 20,000∼30,000정도인 고분자를 얻기 위하여 분자량조절제로 파라-t-부틸페놀 0.94g을 가하고 반응촉매로 트리에틸아민 0.014g을 넣고 약 30분간 반응시킨후 수상층과 유기층을 정체분리한 후 유기층에 순수 60g과 메틸렌클로라이드 80㎖ 를 넣고 수산화나트륨 8g과 트리에틸아민 0.025g을 넣은 후 약 2시간 반응시켰다.2.6 ml of sodium hydroxide with 5.6% (w / w) of 0.22 g of 2- (4-hydroxyphenyl) -4-hydroxyphenol (0.5 mol% relative to bisphenol A) as a branching agent to polymerize the branched polycarbonate Dissolved in the polycondensation reaction. Then, in order to obtain a polymer having a molecular weight of about 20,000 to 30,000, 0.94 g of para-t-butylphenol was added as a molecular weight regulator, 0.014 g of triethylamine was added as a reaction catalyst, and reacted for about 30 minutes. 60 g of pure water and 80 ml of methylene chloride were added to the organic layer, and 8 g of sodium hydroxide and 0.025 g of triethylamine were added thereto and reacted for about 2 hours.
그 다음, 메틸렌클로라이드 120㎖를 가하여 고분자를 축출하고 0.1 노르말 염산으로 3회 세척한 후 순수로 중성이 될 때까지 세척하였다. 그리고, 아세톤과 순수를 1 : 1로 800㎖에 천천히 적가하여 고분자를 입자화하였다.Then, 120 ml of methylene chloride was added to dislodge the polymer, washed three times with 0.1 normal hydrochloric acid, and washed with pure water until neutral. Then, acetone and pure water were slowly added dropwise to 1: 1 in 800 ml to granulate the polymer.
[실시예 2∼4]EXAMPLES 2-4
상기 실시예 1과 동일한 방법으로 브렌치드 폴리카보네이트 수지를 제조하되, 다만 브렌칭제의 함량을 다음 표에 나타낸 바와 같이 변화시켰다.A branched polycarbonate resin was prepared in the same manner as in Example 1, except that the content of the branching agent was changed as shown in the following table.
[실시예 5∼12]EXAMPLES 5-12
상기 실시예 1과 동일한 방법으로 브렌치드 폴리카보네이트 수지를 제조하되, 실시예 5∼8은 브렌칭제로 2,4-(4-하이드록시페닐)-페놀을 첨가하였고, 실시예 9∼12는 브렌칭제로 2,5-(4-하이드록시페닐)-페놀을 사용하였으며, 그 함량을 다음 표에 나타낸 바와 같이 달리하였다.A branched polycarbonate resin was prepared in the same manner as in Example 1, except that Examples 5 to 8 added 2,4- (4-hydroxyphenyl) -phenol as the branching agent, and Examples 9 to 12 were 2,5- (4-hydroxyphenyl) -phenol was used as a title, and its content was changed as shown in the following table.
[비교예 1∼4][Comparative Examples 1 to 4]
상기 실시예 1과 동일한 방법으로 브렌치드 폴리카보네이트 수지를 제조하되, 브렌칭제로 2-(4-하이드록시페닐)-4-하이드록시페놀을 사용하고 그 함량을 다음 표에 나타낸 바와 같이 달리하였다.A branched polycarbonate resin was prepared in the same manner as in Example 1, except that 2- (4-hydroxyphenyl) -4-hydroxyphenol was used as a branching agent, and its content was changed as shown in the following table.
[실험예]Experimental Example
상기 실시예 1∼12 및 비교예 1∼4에 따라 제조된 폴리카보네이트 수지를 130。C에서 24시간 동안 건조하여 유리전이온도, 열분해온도, 분자량 및 용융점도비(MIR,Melting Index Ratio)를 측정하였으며, 그 결과를 다음 표에 나타내었다.The polycarbonate resins prepared according to Examples 1 to 12 and Comparative Examples 1 to 4 were dried at 130 ° C. for 24 hours to measure glass transition temperature, pyrolysis temperature, molecular weight, and melt viscosity ratio (MIR, Melting Index Ratio). The results are shown in the following table.
여기서, 유리전이온도는 시차주사열량계(DSC)를 이용하여 측정하였고, 분자량은 겔 투과크로마토그라피법을 이용하여 측정하였다. 열분해온도는 TGA(Thermal Gravic Analysis)에 의해 측정하였고, 용융점도비는 용융지수계(Melt Indexer)를 이용하여 260C에서 21.6㎏과 2.16㎏의 추를 사용하여 ASTM D 1238에 따라 측정하였다.Here, the glass transition temperature was measured using a differential scanning calorimeter (DSC), the molecular weight was measured using a gel permeation chromatography method. The pyrolysis temperature was measured by TGA (Thermal Gravic Analysis), and the melt viscosity ratio was measured according to ASTM D 1238 using a weight of 21.6 kg and 2.16 kg at 260C using a Melt Indexer.
(주)(week)
(1) 2-(4-하이드록시페닐)-4-하이드록시 페놀(1) 2- (4-hydroxyphenyl) -4-hydroxy phenol
(2) 2,4-(4-하이드록시페닐)-페놀(2) 2,4- (4-hydroxyphenyl) -phenol
(3) 2,5-(4-하이드록시페닐)-페놀(3) 2,5- (4-hydroxyphenyl) -phenol
* 가교반응으로 인하여 측정불가* Measurement not possible due to crosslinking reaction
상기 표의 결과로부터 본 발명의 브렌치드 폴리카보네이트 수지는 용융점도비가 13이상이며, 열분해온도가 500C 이상이어 블로우 성형용으로 적합함을 알 수 있다.From the results of the table, it can be seen that the branched polycarbonate resin of the present invention has a melt viscosity ratio of 13 or more and a thermal decomposition temperature of 500C or more, which is suitable for blow molding.
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| KR0183433B1 true KR0183433B1 (en) | 1999-05-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100413534B1 (en) * | 2001-05-08 | 2003-12-31 | 학교법인 포항공과대학교 | Method for preparing aromatic polycarbonate |
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| KR100446472B1 (en) * | 1997-09-04 | 2004-12-03 | 주식회사 삼양사 | Preparation method of branched polycarbonate resin using water-soluble branching agent instead of organic branching agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100413534B1 (en) * | 2001-05-08 | 2003-12-31 | 학교법인 포항공과대학교 | Method for preparing aromatic polycarbonate |
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