KR0180827B1 - Method for manufacturing branched polycarbonate - Google Patents
Method for manufacturing branched polycarbonate Download PDFInfo
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- KR0180827B1 KR0180827B1 KR1019960017632A KR19960017632A KR0180827B1 KR 0180827 B1 KR0180827 B1 KR 0180827B1 KR 1019960017632 A KR1019960017632 A KR 1019960017632A KR 19960017632 A KR19960017632 A KR 19960017632A KR 0180827 B1 KR0180827 B1 KR 0180827B1
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- 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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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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Abstract
본원 발명은 용기 및 시트원료로 쓰이는 분지 폴리카보네이트 제법에 관한 것으로 2가 페놀류를 알카리 수용액에 넣어 2가의 페놀염의 수용액을 만들고 포스겐 가스를 주입시킨 유기용매 메틸렌클로라이드에 분지제와 분자량 조절제를 계면중합 반응시켜 분지된 폴리카보네이트로 제조함에 있어서, 분지제로 2,2'-비스-(3-페닐하이드록시-4-하이드록시페닐)-(4-하이드록시페닐)-프로판을 0.1∼1.5몰% 사용함을 특징으로 하는 분지 폴리카보네이트 제법에 관한 발명으로 이와같이 하여 얻은 폴리카보네이트 수지는 강도 특성을 가지므로 전기부품 기계부품 및 용기등의 산업용 수지로 광범위 하게 사용되어질 수 있다.The present invention relates to a branched polycarbonate manufacturing method used as a container and a sheet material, and a biphasic polymerization reaction of a branching agent and a molecular weight modifier in an organic solvent methylene chloride in which dihydric phenols are added to an aqueous alkali solution to make an aqueous solution of a divalent phenol salt and phosgene gas is injected. In the preparation of branched polycarbonate, 0.1 to 1.5 mol% of 2,2'-bis- (3-phenylhydroxy-4-hydroxyphenyl)-(4-hydroxyphenyl) -propane was used as the branching agent. The polycarbonate resin obtained in this way has a strength characteristic and can be widely used in industrial resins such as electrical parts, machine parts, and containers.
Description
본 발명은 용기(Bottles)와 시트(Sheets) 원료로 쓰이는 분지 폴리카보네이트(Branched Polycarbonate)의 제조방법에 관한 것이다.The present invention relates to a process for producing branched polycarbonates used as raw materials for bottles and sheets.
폴리카보네이트 수지는 강도(Strength), 특히 충격강도(Impact resistance)와 투명도(Transparency)가 우수한 특성을 가지고 있으므로 전기부품, 기계부품 및 용기등 산업용 수지로서 광범위하게 쓰이고 있다.Polycarbonate resins are widely used as industrial resins such as electrical parts, mechanical parts and containers because they have excellent strength, particularly impact resistance and transparency.
그러나, 직선형 폴리카보네이트 수지(Linear Polycarbonate resin)는 용융시 거의 뉴톤 유체(Newtonian Fluid)로의 거동을 보이며, 그 점도는 전단 변형속도(Shear rate)에 따라가지 못한다. 뿐만 아니라 용융탄성과 용융강도가 좋지 않기 때문에 폴리카보네이트를 사용하여 익스트루젼 몰딩(Extrusion molding)을 할 때, 특히 익스트루젼 몰딩기계를 사용하여 브로우 몰딩(Blow molding)을 하면 안정한 크기의 큰 페리손(Parison)을 만들기 어렵다.However, linear polycarbonate resins exhibit almost the behavior of Newtonian Fluid upon melting, and their viscosity does not depend on shear rate. In addition, due to the poor melt elasticity and melt strength, it is possible to perform extrusion molding using polycarbonate, especially when blow molding using an extrusion molding machine. It's hard to make a hand.
이와같은 어려운 점을 해결하기 위해 (1) 분자량이 상이한 두가지 형태의 폴리카보네이트를 섞는 방법, (2) 분지 폴리카보네이트(Branched polycarbonate)를 사용하는 방법등이 소개되어 왔다. 분지 폴리카보네이트를 만드는 방법은 우선 2가 페놀류와 다기능 물질(Polyfuntional compound)에 포스겐(Phosgene) 가스를 넣은 후, 분자량 조절제인 1가 페놀류로 분자량을 조절하여 합성하는 방법이 알려져 있다. 그러나 이 방법은 다기능 물질의 반응성이 작아 선호되는 방법이 아니다.In order to solve this difficulty, (1) a method of mixing two types of polycarbonates having different molecular weights, and (2) a method of using branched polycarbonates have been introduced. A method of making a branched polycarbonate is known by first adding a phosgene gas into a dihydric phenol and a polyfuntional compound, and then controlling the molecular weight with a monohydric phenol, which is a molecular weight modifier. However, this method is not preferred because of its low reactivity.
따라서, n=5 내지 15정도인 폴리카보네이트 올리고머를 준비한 후, 아민류의 촉매하에서 다가 페놀을 반응시키는 방법이 제안되어 왔으나, 이 또한 반응성을 조절하기 어렵고 포스겐 가스 투입시 pH=3 내지 6사이로 맞춰 반응시키면 2가 페놀은 침전물로 되기 쉬워 반응이 완전히 끝나도록 하기에는 매우 어려웠다. 따라서 사용할 수 있는 반응장치에도 한계가 있고 관형반응관(Tubular reactor) 역시 사용할 수가 없었다.Therefore, a method of preparing polycarbonate oligomer having n = 5 to 15 and then reacting polyhydric phenol under amine catalysts has been proposed, but it is also difficult to control the reactivity and the reaction is adjusted to pH = 3 to 6 when phosgene gas is injected. The dihydric phenols tend to precipitate, making it very difficult to complete the reaction. Therefore, there are limitations to the reactors that can be used, and tubular reactors cannot be used.
본 발명에서 사용하는 폴리카보네이트 올리고머는 2가 페놀류에 알칼리 수용액을 넣어 2가의 페놀류염 수용액을 만들고, 포스겐 가스를 주입한 유기용매인 메틸렌클로라이드(MC, Methylene chloride)와 교반하여 합성한다.The polycarbonate oligomer used in the present invention is prepared by adding an aqueous alkali solution to the dihydric phenols to form a dihydric phenol salt solution, followed by stirring with methylene chloride (MC, Methylene chloride), an organic solvent injected with phosgene gas.
이 때에 사용되는 2가 페놀류는 보통 다음 형태의 분자를 사용한다.The dihydric phenols used at this time usually use the following type of molecule.
여기에서 R1, R2, R3, R4는 수소, 페닐, 할로겐 원소, C1∼C3에 해당하는 알킬기이고, R5는 C0∼C5에 해당하는 알킬기, -O-, -S-, -SO2-, -CO- 등이다.Wherein R 1 , R 2 , R 3 and R 4 are hydrogen, phenyl, a halogen element, an alkyl group corresponding to C 1 to C 3 , and R 5 is an alkyl group corresponding to C 0 to C 5 , -O-,- S-, -SO 2- , -CO- and the like.
전형적인 2가 페놀류들의 예는 다음과 같다.Examples of typical dihydric phenols are as follows.
2,2-비스(4-하이드록시페놀)-프로판(일명 Bisphenol A), 1,1-비스(4-하이드록시페놀)-사이클로헥산, 4,4-디하이드록시디페놀, 2,4-비스(4-하이드록시페놀)-2-메틸-부탄, α,α'-비스(4-하이드록시페놀)-p-디이소프로필벤젠, 2,2-비스(3-메틸-4-하이드록시페놀)-프로판, 2,2-비스(3-클로로-4-하이드록시페놀)-프로판, 비스(3,5-디메틸-4-하이드록시페닐)-메탄, 2,2-비스(3,5-디메틸-4-하이드록시페닐)-프로판, 비스(4-하이드록시페닐)설폰, 비스(3,5-디메틸-4-하이드록시페닐)설폰, 2,4-비스(3,5-디메틸-4-하이드록시페닐)-2-메탄부탄, 1,1-비스(3,5-디메틸-4-하이드록시페닐)-사이클로헥산, α,α'-비스(3,5-디메틸-4-하이드록시페닐)-p-디이소프로필벤젠, 2,2-비스(3,5-디클로로-4-하이드록시페닐)-프로판, 그리고 2,2-비스(3,5-디브로모-4-하이드록시페닐)-프로판 등이다.2,2-bis (4-hydroxyphenol) -propane (aka Bisphenol A), 1,1-bis (4-hydroxyphenol) -cyclohexane, 4,4-dihydroxydiphenol, 2,4- Bis (4-hydroxyphenol) -2-methyl-butane, α, α'-bis (4-hydroxyphenol) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxy Phenol) -propane, 2,2-bis (3-chloro-4-hydroxyphenol) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5 -Dimethyl-4-hydroxyphenyl) -propane, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl- 4-hydroxyphenyl) -2-methanebutane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, α, α'-bis (3,5-dimethyl-4-hydroxy Oxyphenyl) -p-diisopropylbenzene, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) -propane, and 2,2-bis (3,5-dibromo-4-hydroxy Oxyphenyl) -propane and the like.
특히 이중에서 자주 사용되는 2가 페놀류는 2,2-비스(4-하이드록시페닐)-프로판(Bisphenol A), 2,2-비스(3,5-디메틸-4-하이드록시페닐)-프로판, 2,2-비스(3,5-디브로모-4-하이드록시페닐)-프로판, 그리고 1,1-비스(4-하이드록시페닐)-사이클로헥산 등이다. 이들 2가 페놀류들은 단독으로 또는 서로 조합해서 사용할 수 있다.Especially dihydric phenols which are frequently used among them are 2,2-bis (4-hydroxyphenyl) -propane (Bisphenol A), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, and the like. These dihydric phenols can be used individually or in combination with each other.
폴리카보네이트 올리고머의 고분자화 정도는, 즉, 폴리카보네이트 올리고머의 분자량은 페놀, p-tert-브틸페놀, 이소프로필페놀 등의 분자량 조절제를 사용하여 바라는 수준으로 조정할 수 있는데, 이때 n수는 보통 20 또는 그 보다 작으며 n=2 내지 10일 때 더 좋은 효과를 보여준다.The degree of polymerization of the polycarbonate oligomer, that is, the molecular weight of the polycarbonate oligomer can be adjusted to a desired level using a molecular weight modifier such as phenol, p-tert-butyl phenol, isopropyl phenol, where n number is usually 20 or It is smaller than that and shows a better effect when n = 2 to 10.
또한, 분지제는 다음과 같은 작용기를 적어도 3개 이상을 함유하여야 한다. 즉, 하이드록시기(-OH), 카르복시기(-COOH), 아미노기(-NH2), 산할로겐(-COCI), 포밀기(-CHO) 등이다.In addition, the branching agent should contain at least three or more of the following functional groups. That is, a hydroxyl group (-OH), carboxyl group (-COOH), amino group (-NH 2), acid halide (-COCI), formyl group (-CHO) or the like.
작용기가 3개 이상인 분지제의 전형적인 예는 다음과 같다.Typical examples of branching agents having three or more functional groups are as follows.
멜리틱산(Mellitic acid), 트리멜리틱산(Trimellitic acid), 트리멜리틱산 클로라이드[Trimellitic acid chloride], 무수트리멜리틱산[Trimellitic acid anhydride], 피로멜리틱산[Pyromellitic acid], 리소사이클릭산[Resorcyclic acid], 리소신알데하이드[Resorcinaldehyde], 트리멜리틸트리클로라이드(Trimellitiltrichloride), 트리하이드록시플레번 유도체 즉, 2,4,4-트리메틸-2,4-7-트리하이드록시플레번, 플로로글루신(Phloroglucin)등을 들 수 있다.Mellitic acid, trimellitic acid, trimellitic acid chloride, trimellitic acid anhydride, pyromellitic acid, resorcyclic acid ], Resorcinaldehyde, trimellitiltrichloride, trihydroxyflavone derivatives, ie 2,4,4-trimethyl-2,4-7-trihydroxyflavone, phloroglucin (Phloroglucin) etc. are mentioned.
본 발명은 2가 페놀류를 알카리 수용액에 넣어 2가의 페놀염의 수용액을 만들고 포스겐 가스를 주입시킨 유기용매 메틸렌클로라이드에 분지제와 분자량 조절제를 계면중합시켜 분지된 폴리카보네이트를 제조함에 있어서, 분지제로 2,2'-비스(3-페닐하이드록시-4-하이드록시페닐)-(4-하이드록시페닐)-프로판을 쓰고 그 사용량은 0.1∼1.5몰%임을 특징으로 하는 분지된 폴리카보네이트의 제조방법에 관한 것이다.The present invention is to prepare a branched polycarbonate by interfacial polymerization of a branching agent and a molecular weight control agent in an organic solvent methylene chloride in which dihydric phenols are added to an aqueous alkali solution to form an aqueous solution of a divalent phenol salt and injected with phosgene gas. 2'-bis (3-phenylhydroxy-4-hydroxyphenyl)-(4-hydroxyphenyl) -propane, and the amount thereof is 0.1 to 1.5 mol%. will be.
본 발명에서는 폴리카보네이트 올리고머의 끝부분이 클로로포메이트(Chloroformate) 형태로 된 것과 3개 이상의 작용기를 함유하는 분지제(Branching agent)로 2,2'-비스(3-페닐하이드록시-4-하이드록시페닐)-(4-하이드록시페닐)-프로판을 사용하며, 그 사용량은 0.1∼1.5몰%이다. 만약 사용량이 0.1몰% 미만일때는 분지효과가 없어지는 문제점이 있으며, 1.5몰%를 초과하면 젤라틴이 일어나는 문제점이 있다. 또한 반응에서 상전이 촉매제로는 트리에틸아민[(CH3CH2)3N], 트리프로필아민[(CH3CH2CH2)3N], 트리이소프로필아민{[(CH3)2CH]3N}, 등이 사용된다. 폴리카보네이트 올리고머와 분지제와의 반응에서 여러 반응 조건들이 있지만, 일반적으로 반응온도는 5 내지 40℃이고, 더 좋게는 10 내지 30℃이다. 반응시간은 보통 10분 내지 3시간인데, 더 좋게는 20분 내지 1시간 30분 동안 교반한다.In the present invention, the end portion of the polycarbonate oligomer is in the form of chloroformate and is a branching agent containing three or more functional groups. Hydroxyphenyl)-(4-hydroxyphenyl) -propane is used, and the amount is 0.1-1.5 mol%. If the amount is less than 0.1 mol% there is a problem that the branching effect disappears, if it exceeds 1.5 mol% there is a problem that gelatin occurs. In addition, as the phase transfer catalyst in the reaction, triethylamine [(CH 3 CH 2 ) 3 N], tripropylamine [(CH 3 CH 2 CH 2 ) 3 N], triisopropylamine {[(CH 3 ) 2 CH] 3 N}, and the like. Although there are various reaction conditions in the reaction of the polycarbonate oligomer with the branching agent, the reaction temperature is generally 5 to 40 ° C., more preferably 10 to 30 ° C. The reaction time is usually 10 minutes to 3 hours, more preferably 20 minutes to 1 hour 30 minutes.
폴리카보네이트 올리고머의 분지제와의 반응에서 얻어진 물질은 알칼리 수용액(수상비 15 내지 20±1%)과 아민류의 촉매하에서 계면중축합 반응을 하는데, 여기에서 사용되는 2가 페놀류는 앞에서 언급한 것들이 사용되며 전형적인 예의 하나는 비스페놀 A(Bisphenol A)이다. 그리고 분지제로 사용하는 3가 이상의 다기능 물질(Trifuntional compound) 또한 앞에서 언급한 물질들을 많이 사용한다.The material obtained in the reaction with the branching agent of the polycarbonate oligomer is subjected to the interfacial polycondensation reaction under an aqueous alkali solution (aqueous water ratio of 15 to 20 ± 1%) and a catalyst of amines, and the dihydric phenols used herein are those mentioned above. One typical example is bisphenol A. Trifuntional compounds, which are used as branching agents, also use many of the aforementioned substances.
계면중축합 반응은 보통 10 내지 40℃, 약 1시간 30분 동안, 250∼500rpm의 교반속도로 반응을 시키는데, 더 좋게는 약 30분간, 25℃, 500rpm 교반속도로 반응을 시키면 용기나 시트를 만들 수 있는 분지 폴리카보네이트가 만들어진다.The interfacial polycondensation reaction is usually performed at a stirring speed of 250 to 500 rpm for 10 to 40 ° C. for about 1 hour and 30 minutes. More preferably, the reaction is performed at 25 ° C. and 500 rpm stirring speed for about 30 minutes. Branched polycarbonates are made.
본 발명에서 합성된 분지 폴리카보네이트는 분자량이 20,000∼35,000이고, 보통의 직선형 폴리카보네이트를 녹이는 용매에도 잘 녹는다.The branched polycarbonate synthesized in the present invention has a molecular weight of 20,000 to 35,000 and is well soluble in a solvent for dissolving ordinary linear polycarbonate.
본 발명에서 3가 이상의 다기능 물질과 2가 페놀과의 반응 사이에는 어떤 부반응도 없으며 반응성은 굉장히 크다. 그리고 기존의 폴리카보네이트와 비교해서 본 발명에서 제시하는 방법대로 만든 분지 폴리카보네이트는 좋은 용융 성질을 보이며, 전단변형속도(Shear rate)에 대한 용융 점도의 의존성은 매우 크다. 이 분지 폴리카보네이트의 장점중에 하나는 바이러스 효과(Barus Effect)가 크고 처짐 현상이 작고, 또다른 다른 장점은 파괴강도가 매우 좋다는 것이다.In the present invention, there is no side reaction between the reaction of the trivalent or higher multifunctional substance and the dihydric phenol, and the reactivity is very large. In addition, the branched polycarbonate made according to the method of the present invention compared to the existing polycarbonate shows good melting properties, and the dependence of the melt viscosity on the shear rate is very large. One of the advantages of this branched polycarbonate is its high Barus Effect, low deflection, and another great strength.
따라서 본 발명에서 제시하고 있는 방법대로 만든 분지 폴리카보네이트는 익스트루젼 몰딩, 특히 익스트루젼 몰딩기를 사용한 브로우 몰딩에 아주 적합하여 양질의 시트와 용기 그리고 그밖의 성형품들을 만들 수 있다.Thus, the branched polycarbonates made according to the method presented in the present invention are well suited for extrusion molding, in particular for brow molding using an extrusion molding machine, so that high quality sheets, containers and other molded articles can be produced.
이와같은 본 발명을 실시예와 비교예에 의거하여 더욱 상세히 설명하면 다음과 같다.The present invention will be described in more detail based on Examples and Comparative Examples as follows.
[실시예 1]Example 1
2,2-비스(4-하이드록시페놀)-프로판(일명 비스페놀 A) 115g, 가성소다 41.33g, 순수 647.5mL를 섞어 BPA-Na 용액을 만들고, 메틸렌클로라이드 용매 388.5mL에 카보닐다이크로라이드(일명 CDC) 가스 59.9g을 포집하여 2L 실린더 반응기에 함께 넣어 5 내지 10분간 교반하면 분자량이 1,000 정도의 소중합체가 얻어진다. 연이어 가성소다 0.1205g과 순수 10mL에 녹인 분지제 2,2'-비스(3-페닐하이드록시-4-하이드록시페닐)-(4-하이드록시페닐)-프로판 0.2604g을 2단계로 실린더 반응기에 넣고 분자량 조절제 파라-t-브틸페놀 1.892g, 촉매로 트리에틸아민 0.0346g을 넣고 30분간 교반속도 500rpm으로 반응시키면 분자량이 2,000∼3,000 정도의 소중합체가 만들어진다. 이후, 경액층과 중액층을 분리하고 중액층에 메틸렌클로라이드 160mL를 더 넣고 가성소다 16g, 순수 12mL, 트리에틸아민 0.0069g을 넣고 교반속도 500rpm으로 1시간 정도 교반을 하고, 다시 트리에틸아민 0.0796g을 더 넣으면서 30분 내지 2시간 동안 교반을 더 하면 반응은 완결된다.115 g of 2,2-bis (4-hydroxyphenol) -propane (aka bisphenol A), 41.33 g of caustic soda and 647.5 mL of pure water are mixed to form a BPA-Na solution, and carbonyl dichloride (388.5 mL of methylene chloride solvent) 59.9 g of CDC) gas was collected, put together in a 2 L cylinder reactor, and stirred for 5 to 10 minutes to obtain an oligomer having a molecular weight of about 1,000. Subsequently, 0.1205 g of caustic soda and 0.2604 g of 2,2'-bis (3-phenylhydroxy-4-hydroxyphenyl)-(4-hydroxyphenyl) -propane dissolved in 10 mL of pure water were added to the cylinder reactor in two stages. 1.892 g of a molecular weight regulator para-t-butyl alcohol and 0.0346 g of triethylamine as a catalyst were added and reacted at a stirring speed of 500 rpm for 30 minutes to produce an oligomer having a molecular weight of 2,000 to 3,000. Thereafter, the hard layer and the middle layer were separated, and 160 mL of methylene chloride was added to the middle layer, 16 g of caustic soda, 12 mL of pure water, and 0.0069 g of triethylamine were added. The mixture was stirred at a stirring speed of 500 rpm for about 1 hour, followed by 0.0796 g of triethylamine. Add more stirring for 30 minutes to 2 hours while adding the reaction is complete.
반응이 완결되면 교반을 중단하고 순수와 메틸렌클로라이드 두 용매로 중액을 희석시킨다. 세정은 알칼리, 산, 순수로 연속 세정을 하고, 분지 폴리카보네이트의 입자화는 아세톤과 순수를 0.5 내지 1:1의 비율로 섞은 용매에 세정을 마친 중액을 천천히 떨어뜨리면 작은 입자를 얻을 수 있다. 건조는 100℃에서 4시간, 140℃에서 2시간 한 후, 물성들을 측정하여 표 1에 나타내었다.When the reaction is complete, stirring is stopped and the heavy solution is diluted with two solvents, pure water and methylene chloride. The washing is continuously washed with alkali, acid, and pure water, and the granulation of branched polycarbonate can be obtained by slowly dropping the finished heavy liquid into a solvent mixed with acetone and pure water at a ratio of 0.5 to 1: 1. After drying for 4 hours at 100 ℃, 2 hours at 140 ℃, it is shown in Table 1 by measuring the physical properties.
[실시예 2∼7]EXAMPLES 2-7
실시예 1과 동일한 방법으로 하되 분지제의 함량을 표 1과 같이하여 실험하여 그 물성결과를 표 1에 나타내었다.In the same manner as in Example 1, but the content of the branching agent as shown in Table 1, the physical properties are shown in Table 1.
[비교예 1∼4][Comparative Examples 1 to 4]
실시예 1과 동일한 방법으로 하되 분지제의 함량을 표 1과 같이하여 실험하여 그 물성결과를 표 1에 나타내었다.In the same manner as in Example 1, but the content of the branching agent as shown in Table 1, the physical properties are shown in Table 1.
※비교예 4의 경우 분지제 양이 많아 Gellation이 됨.※ In case of Comparative Example 4, the amount of branching agent is high, resulting in gelation.
※MIR 측정은 260℃에서 2.16kg과 21.6kg의 추를 사용하여 ASTM D1238에 따라 실시하였다.※ MIR measurement was performed according to ASTM D1238 using a weight of 2.16 kg and 21.6 kg at 260 ° C.
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