KR0148829B1 - The chlorinated method of low molecular weight polyolefin - Google Patents
The chlorinated method of low molecular weight polyolefinInfo
- Publication number
- KR0148829B1 KR0148829B1 KR1019940009658A KR19940009658A KR0148829B1 KR 0148829 B1 KR0148829 B1 KR 0148829B1 KR 1019940009658 A KR1019940009658 A KR 1019940009658A KR 19940009658 A KR19940009658 A KR 19940009658A KR 0148829 B1 KR0148829 B1 KR 0148829B1
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- South Korea
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- molecular weight
- low molecular
- melting point
- chlorination
- resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
본 발명은 고밀도 폴리에틸렌이나 폴리프로필렌 등 저압법에 의한 폴리올레핀 제조공정에서 부산되는 저분자량 수지(Low molecular resin)를 염소화하여 산업적으로 유용한 염소화 저분자량 수지를 제조하는 저분자량 폴리올레핀수지의 염소화 방법에 관한 것이다.The present invention relates to a chlorination method of a low molecular weight polyolefin resin for producing an industrially useful chlorinated low molecular weight resin by chlorination of low molecular resin produced by low pressure polyolefin production process such as high density polyethylene or polypropylene. .
고밀도 폴리에틸렌 생산공정에서 부산되는 저분자량 수지는 융점이 40∼120℃ 사이로 융점범위가 넓고 평균 분자량(average molecular weight)이 약 900정도로서 왁스상 외관을 갖고 있다.The low molecular weight resin produced by the high density polyethylene production process has a waxy appearance with a melting point of 40-120 ° C. with a broad melting point and an average molecular weight of about 900.
폴리프로필렌의 저분자량수지는 융점 범위가 50∼100℃이고 평균분자량 10,000 정도로서 고무상 외관을 갖고 있다.The low molecular weight resin of polypropylene has a melting point range of 50 to 100 ° C. and an average molecular weight of about 10,000 and a rubbery appearance.
이들은 분자량 분포범위가 넓은 혼합물로서 융점범위가 넓어 중합도 별로 재분리하지 않은 상태에서는 산업적인 용도가 거의 없는 실정이다.These mixtures have a wide molecular weight distribution range, and have a wide melting point range, so that there is little industrial use in the state of not re-separating the degree of polymerization.
본 발명의 목적은 상기의 저분자량 수지를 별도로 분리하지 않은 혼합물 상태에서 염소함량 30∼70 중량％ 정도로 염소화 시키므로서 접착성, 난연성 및 내약품성 등을 부여하여 현재 접착제, 인쇄잉크, 도료등의 바인더로 사용되고 있는 클로로프렌 또는 염소화 폴리올레핀수지의 대용(代用)으로 사용할 수 있는 고무상의 바인더 수지를 제공하는데 있다.An object of the present invention is to give the adhesive, flame retardant and chemical resistance by chlorination of about 30 to 70% by weight of chlorine in a mixture state in which the low-molecular weight resin is not separated, and is currently used in binders such as adhesives, printing inks and paints. The present invention provides a rubbery binder resin that can be used as a substitute for chloroprene or chlorinated polyolefin resins.
Description
본 발명은 고밀도 폴리에틸렌이나 폴리프로필렌 등 저압법에 의한 폴리올레핀 제조공정에서 부산되는 저분자량 수지(Low molecular resin)를 염소화하여 산업적으로 유용한 저분자량 염소화 폴리올레핀(polyolefin) 수지를 제조하는 저분자량 폴리올레핀수지의 염소화 방법에 관한 것이다.The present invention provides chlorination of low molecular weight polyolefin resins for producing industrially useful low molecular weight chlorinated polyolefin resins by chlorination of low molecular resins produced by low pressure polyolefin production processes such as high density polyethylene and polypropylene. It is about a method.
고밀도 폴리에틸렌이나 폴리프로필렌 등 저압법에 의한 폴리올레핀의 중합공정에 있어서, 일정범위위 중합도를 갖는 정상규격 제품이외에도 중합도가 낮은 비정상규격품이 상당량 부생되는데 이를 일반적으로 저분자량 수지(Low molecular resin)라고 한다.In the polymerization process of polyolefins by low pressure method such as high density polyethylene and polypropylene, in addition to the normal standard products having a degree of polymerization, a certain amount of abnormal standard products having a low degree of polymerization are by-produced, which is generally referred to as low molecular resin.
고밀도 폴리에틸렌 중합공정에서 부생되는 저분자량 수지는 정상규격품에 비하여 중합도가 각기 다른 저분자량 수지들의 혼합물이다.The low molecular weight resin produced by the high density polyethylene polymerization process is a mixture of low molecular weight resins having different degrees of polymerization compared to normal standards.
상기의 고밀도 폴리에틸렌의 저분자량 수지는 융점이 40∼120℃ 사이로 융점범위가 넓고 평균 분자량(average molecular weight)이 약 900정도로서 왁스상의 외관을 갖고 있다. 폴리프로필렌의 저분자량 수지는 융점이 50∼100℃이고 평균분자량이 약 10,000 정도러서 고무상 외관을 갖고 있다.The low molecular weight resin of the high-density polyethylene has a melting point of 40 to 120 DEG C, a broad melting point range, an average molecular weight of about 900, and a waxy appearance. The low molecular weight resin of polypropylene has a rubbery appearance because its melting point is 50 to 100 ° C. and its average molecular weight is about 10,000.
이들은 분자량 분포범위가 넓은 혼합물로서 융점범위도 넓어 이들을 특정범위의 중합도를 갖는 성분별로 재분리하지 않은 상태에서는 산업적인 용도가 거의 없는 실정이며, 그의 활용정도는 분자량 별로 분리하여 액상저분자량의 것은 연료로 사용되고 중분자량의 것은 폴리에틸렌 왁스로서 이용되고 있는 정도이다.These mixtures have a wide molecular weight distribution range and have a wide melting point, so that they are rarely used industrially unless they are re-isolated for each component having a specific degree of polymerization. The medium molecular weight is used as the polyethylene wax.
본 발명의 목적은 저분자량 수지를 별도로 분리하지 않은 혼합물 상태에서 염소함량 30∼70 중량％ 정도로 염소화 시키므로서 접착성, 난연성 및 내약품성 등을 부여하여 현재 접착제, 인쇄잉크, 도료등의 바인더로 사용되고 있는 클로로프렌 또는 염소화 폴리올레핀수지의 대용(代用)으로 사용할 수 있는 고무상의 바인더 수지를 제공하는데 있다.An object of the present invention is to chlorinate the chlorine content of 30 to 70% by weight in a mixture state in which the low-molecular weight resin is not separated, thereby imparting adhesiveness, flame retardancy, and chemical resistance, and is currently used as a binder for adhesives, printing inks and paints. The present invention provides a rubbery binder resin that can be used as a substitute for chloroprene or chlorinated polyolefin resin.
상기의 고무상 바인더 수지는 접착제, 인쇄잉크, 도료, 난연고무 및 수지개질용으로 유용하게 사용될 수 있다.The rubbery binder resin may be usefully used for adhesives, printing inks, paints, flame retardant rubbers and resins.
일정범위의 분자량 분포를 갖고 있는 폴리올레핀의 염소화 방법에 있어서, 현재까지 제안된 방법은 대체로 다음의 4가지 방법으로 대별될 수 있다.In the method of chlorination of polyolefin having a range of molecular weight distribution, the method proposed to date can be roughly divided into the following four methods.
첫째, 분말상 폴리올레핀을 물속에 현탁시키고 여기에 염소가스를 주입하여 염소화 시키는 수성현탁 염소화법(미국특허 제 21,215,092호 및 일본공개특허공보 소 57-153003호)First, an aqueous suspension chlorination method in which powdered polyolefin is suspended in water and chlorinated by injecting chlorine gas (US Patent No. 21,215,092 and JP 57-153003).
둘째, 분말상 폴리올레핀을 사염화탄소와 같은 용매에 현탁 내지는 용해시킨 상태에서 염소가스를 주입하여 염소화 시키는 용액 염소화법(미국특허 제 20,713,591호 및 일본 공개특허공보 소 57-40509호)Second, a solution chlorination method in which chlorine gas is chlorinated by injecting or dissolving powdered polyolefin in a solvent such as carbon tetrachloride (US Patent No. 20,713,591 and JP 57-40509).
셋째, 폴리올레핀 분말을 질소와 염소의 혼합가스로 유동화시킨 상태에서 염소화 반응을 진행시키는 유동층 염소화법(미국특허 제 4,425,206호)Third, the fluidized bed chlorination method for advancing the chlorination reaction in the state where the polyolefin powder is fluidized with a mixed gas of nitrogen and chlorine (US Patent No. 4,425,206)
넷째, 폴리올레핀 분말을 활석분과 같은 고체상 열매체에 분산시키고 응집방지제와 혼합교반하면서 직접 염소화시키는 벌크 염소화법(대한민국 특허 제 52,530호)Fourth, bulk chlorination method to disperse the polyolefin powder in a solid heat medium such as talc powder and to directly chlorinate while mixing and stirring with an anti-agglomerating agent (Korean Patent No. 52,530)
상기한 방법중 용액 염소화법에서는 사염화탄소를 용매로 사용하고 있는데 이 사염화탄소는 오존층 보호를 위한 국제조약에 의거 1995년 이후는 사용할 수 없게 되어 있으며, 유동화법이나 벌크법은 저분자 폴리올레핀의 넓고 낮은 융점분포 때문에 융점이 일정하지 않아 사용하기가 곤란하며, 수성현탁법이 가능한 방법이기는 하나 종래의 방법으로는 분자량 분포가 넓고 낮은 저중합 폴리올레핀이 반응시키게 되면 융점 이상에서 반응공정중 쉽게 응집되기 때문에 염소화 반응을 계속 진행시킬 수 없다는 문제가 있으며, 낮은 온도에서 염소화 반응시키면 응집문제는 해결할 수 있으나 반응속도가 늦고 최종제품의 용해성이 나빠지는 품질상 문제점이 있다. 본 발명은, 융점이상에서 수성현탁법으로 염소화 반응시킴에 있어서 제품중의 잔류 결정도가 적어 용매에 대한 용해성이 향상되고 고무와 같은 탄성을 갖는 염소화 저분자 폴리올레핀을 제조하는 방법에 관한 것이다.Among the above methods, the solution chlorination method uses carbon tetrachloride as a solvent. The carbon tetrachloride cannot be used after 1995 in accordance with the international treaty for the protection of the ozone layer. The fluidization method and the bulk method are due to the wide and low melting point distribution of low molecular polyolefins. Although the melting point is not constant, it is difficult to use, and although the aqueous suspension method is possible, the chlorination reaction is continued because low-polymerization polyolefins having a wide molecular weight distribution and low molecular weight are easily aggregated in the reaction process above the melting point. There is a problem that it can not proceed, the chlorination reaction at a low temperature can solve the aggregation problem, but there is a quality problem that the reaction rate is slow and the solubility of the final product is bad. The present invention relates to a method for producing a chlorinated low molecular polyolefin having a low elastic crystallinity in a product in the chlorination reaction by an aqueous suspension method at a melting point, solubility in a solvent, and having elasticity such as rubber.
본 발명에서는 유화제가 첨가된 물속에서 저분자량 폴리올레핀을 미세분쇄기(예: 호모믹서)로 분산시켜 유화물(乳化物)을 만들고 이 유화물을 반응기로 옮겨 유화상태를 유지함서 융점이상의 온도에서 염소화반응 시키므로서 원하는 제품을 제조할 수 있었다. 저분자량 폴리올레핀의 염소화 과정중에서는 이들이 응집현상을 일으키는 것이 반응진행에 큰 장애요소가 된다. 이러한 응집현상을 깨트려 주지 않으면 않되는데 이들을 유화상태로 유지시키기 위하여 다음의 3가지 방법을 병행하여 사용하였다.In the present invention, the low molecular weight polyolefin is dispersed in a fine mill (e.g., a homomixer) in water to which an emulsifier is added to make an emulsion, and the emulsion is transferred to a reactor to maintain an emulsified state, thereby chlorinating at a temperature above a melting point. The desired product could be produced. In the chlorination process of low molecular weight polyolefins, the coagulation phenomenon is a major obstacle to the progress of the reaction. This coagulation phenomenon must be broken, but the following three methods were used in parallel to maintain them in an emulsified state.
(유화제의 선정)(Selection of emulsifier)
일반적으로 유화제는 용도에 적합한 일정범위의 HLB(Hydrophile-Lipophile Balance : 친수성 찬유성 바란스)를 갖는바 한 종류의 유화제만으로는 혼합된 저분자량 폴리우레핀 상호간의 응집을 방지할 수 없었으므로 HLB가 다른 2∼3 종의 폴리옥시에틸렌-스테아릴에텔(polyoxyethylene-steary ether)계 유화제를 혼합사용함으로써 응집을 방지할 수 있었다. 염소화 과정중에 이들이 응집현상을 일으키는 것은 반응중 염소화가 진행됨에 따라 이들의 HLB범위가 이동되기 때문에 일정범위의 HLB를 갖는 단일 종의 유화제 만으로는 이들이 이동되는 HLB의 범위를 맞추어 줄 수 없어 분자량 분포도가 넓은 폴리올레핀수지의 부산물인 저분자량 수지의 각분자 표면을 활성화 시키지 못하는 것으로 추정된다.In general, emulsifiers have a range of HLB (Hydrophile-Lipophile Balance) suitable for the application, and one type of emulsifier alone cannot prevent aggregation of mixed low-molecular-weight polyurepines. Aggregation can be prevented by mixing and using 3 types of polyoxyethylene-steary ether emulsifiers. They cause agglomeration during chlorination process because their HLB range is shifted as the chlorination progresses during the reaction, so a single species of emulsifier with a range of HLB alone cannot adjust the range of HLB to which they are transferred. It is estimated that the surface of each molecule of low molecular weight resin, a byproduct of polyolefin resin, cannot be activated.
(유화제의 연속주입)(Continuous Injection of Emulsifier)
유화제 수용액을 반응초기에만 투입하여서는 응집을 방지할 수 없었으나 초기게도 투입하고 반응중에서도 계속해서 주입하므로서 응집방지의 효과를 증대시킬수 있었다.Coagulation could not be prevented by adding the aqueous solution of the emulsifier only at the beginning of the reaction, but it was possible to increase the effect of coagulation prevention by initially adding the solution and continuously injecting it during the reaction.
(강제순환)(Forced circulation)
유리라이닝 교반익 만으로서는 응집되어 반응기 바닥에 쌓이게 되는 응집물을 분쇄하여 분산시켜 줄 수가 없었으나 내산펌프를 이용하여 반응기 바닥에 모이는 응집물을 상하로 강제 순환시켜 기계적으로 분산시켜 주므로서 완전한 응집방지 효과를 얻을 수 있었다.The glass lining agitator blade alone could not pulverize and disperse the aggregates that agglomerated and accumulated on the bottom of the reactor, but by using acid resistant pumps, the aggregates gathered on the bottom of the reactor were forced to circulate up and down to mechanically disperse to obtain a complete anti-aggregation effect. Could.
본 발명에서는 용량이 400ℓ인 유리라이닝 반응기를 사용하였으며 교반익은 직경이 500㎜이고 60∼120RPM으로 가변회전 시켰다. 직경 150㎜인 시경(視鏡)에는 250W 고압수은등으로 조사하였으며 온도는 2중 자켓에 증기 또는 냉각수를 주입하여 조절하였다.In the present invention, a glass lining reactor having a capacity of 400 L was used, and the stirring blade was 500 mm in diameter and was rotated to 60 to 120 RPM. 150 mm in diameter was irradiated with 250W high-pressure mercury lamp and the temperature was controlled by injecting steam or cooling water into the double jacket.
외부순환 펌프는 흡입구경이 50㎜이고 토출구경이 40㎜인 자기펌프를 사용하였고 유화제 수용액 주입펌프는 보일러 청관제 수용액 주입하는 것과 같은 정량펌프를 사용하였다.The external circulating pump used a magnetic pump having a suction diameter of 50 mm and a discharge diameter of 40 mm, and a fixed quantity pump such as an injection of an aqueous solution of a boiler cleaning agent was used as an injection solution of an aqueous solution of a boiler.
이하 본 발명의 실시예를 들어 설명한다.Hereinafter, an embodiment of the present invention will be described.
[실시예 1]Example 1
본 발명의 실시예에서 저분자량 수지(low molecular resin)로서는 지글러-나타 촉매를 사용하는 삼성종합화학(주)의 고밀도 폴리에틸렌 생산공정에서 부생되는 저분자량 고밀도 폴리에틸렌을 원료로 사용하였다. 이것의 평균 분자량은 900이고 융점이 40℃∼120℃ 사이로서 넓은 분자량 분포를 가지고 있었다. 유화제는 한국포리올(주)에서 생산되는 폴리옥시에틸렌-스테아릴에텔(polyoxyethylene-steary ether)중 옥시에틸렌 레디칼이 7인것(상품명:Konion SA-7), 14인것(상품명:Konion SA-14) 및 20인것(상품명:Konion SA-20)을 열수에 녹여 10％ 수용액으로 희석해서 사용하였으며 촉매는 벤조일퍼옥사이드(benzoylperoxide)또는 a a'-아조비스이소부 티로니트릴(a a '-azobisisobutyronitrile)을 원료수지에 대하여 0.1∼0.3중량％첨가하였다.In the embodiment of the present invention, as a low molecular resin, a low molecular weight high density polyethylene which is a by-product of the high density polyethylene production process of Samsung General Chemicals Co., Ltd. using a Ziegler-Natta catalyst was used as a raw material. Its average molecular weight was 900 and had a broad molecular weight distribution with a melting point between 40 ° C and 120 ° C. Emulsifiers have 7 oxyethylene radicals (brand name: Konion SA-7), 14 of polyoxyethylene-steary ether produced by Polyol Co., Ltd. (brand name: Konion SA-14) ) And 20 (trade name: Konion SA-20) were dissolved in hot water and diluted with a 10% aqueous solution. The catalyst used was benzoylperoxide or a a'-azobisisobutyronitrile (aa '-azobisisobutyronitrile). 0.1 to 0.3 weight% of the raw material resin was added.
호모믹서가 설치된 200ℓ드럼에 물 94㎏을 넣고 유화제 Konion SA-7 10％ 수용액 2㎏, SA-14 10％ 수용액 2㎏ SA-20 10％ 수용액 2㎏을 첨가하고 약 80∼90℃로 가열하면서 1차 분쇄하여 평균입경이 10∼20㎜인 덩어리 또는 프레이크(flake)상의 상기의 평균분자량 900이고 융점범위가 40∼120℃인 저분자량 폴리에틸렌 30㎏을 서서히 첨가하였다. 호모믹서를 계속 가동하여 충분히 유화시킨 다음 400ℓ 유리라이닝 반응기에 전량을 이송하고 50℃로 가열하였다. 벤조일퍼옥사이드(benzoylperoxide) 90gr을 첨가하고 염소가스를 시간당 5㎏/시 의 속도로 불소수지 호스를 통하여 주입하면서 반응온도가 10분당 5℃씩 상승되도록 2시간 반응시켰다.94 kg of water was added to a 200 L drum equipped with a homomixer, 2 kg of an aqueous solution of 10% aqueous solution of Konion SA-7 and 2 kg of a 10% aqueous solution of SA-14 were added. Firstly, 30 kg of the low molecular weight polyethylene having an average molecular weight of 900 and a melting point of 40 to 120 ° C. in a lump or flake having an average particle diameter of 10 to 20 mm was gradually added. The homomixer was continuously run to fully emulsify and then transferred to the 400 L glasslining reactor and heated to 50 ° C. 90 gr of benzoylperoxide was added and chlorine gas was injected through a fluororesin hose at a rate of 5 kg / hr for 2 hours to increase the reaction temperature by 5 ° C. per 10 minutes.
반응중 유화제 Konion SA-7, SA-14, SA-20 10％ 수용액을 동일 비율로 혼합한 10％ 수용액을 분당 60㎖/분 의 유량으로 정량펌프를 이용하여 계속해서 주입하였다.During the reaction, a 10% aqueous solution containing 10% aqueous solution of the emulsifier Konion SA-7, SA-14, and SA-20 at the same ratio was continuously injected at a flow rate of 60 ml / min using a metering pump.
반응온도 100℃∼120℃, 내부입력 2∼3㎏/㎠을 유지하면서 염소가스를 시간당 10㎏/시 의 속도로 증가하여 5시간 추가반응시켰다.The chlorine gas was increased at a rate of 10 kg / hr per hour while maintaining a reaction temperature of 100 ° C. to 120 ° C. and an internal input of 2 to 3 kg / cm 2, followed by further reaction for 5 hours.
시경을 통하여 250W 수은증으로 자외선을 계속조사하였으며 반응기 하부에 모이는 응집물을 3마력 내산펌프를 이용하여 반응기 하부노즐에서 상부노즐로 계속 순환시켰다.Ultraviolet light was continuously irradiated with 250W mercury over time, and aggregates collected at the bottom of the reactor were continuously circulated from the lower nozzle to the upper nozzle using a 3-horsepower acid pump.
반응완료 후 제품을 침강시켜 염산용액과 분리하고 2％ 헥사메틸렌테트라아민(hexamethyleneteramine) 수용액 중에 분산시켜 중화한 다음 탈수, 건조하여 염소화 저분자 폴리에틸렌 57㎏을 생산하였다. 분석결과 이들의 염소함량은 47중량％이었다.After completion of the reaction, the product was precipitated, separated from the hydrochloric acid solution, dispersed in a 2% hexamethylene teramine aqueous solution, neutralized, dehydrated and dried to produce 57 kg of chlorinated low molecular weight polyethylene. As a result of analysis, their chlorine content was 47% by weight.
[실시예 2]Example 2
실시예 1과 같은 방법으로 7시간(2시간 +5시간)염소화시킨 후 다시 반응온도를 100∼140℃ 상승시켜 11시간 추가반응시켰다.After 7 hours (2 hours + 5 hours) chlorination in the same manner as in Example 1, the reaction temperature was further increased to 100 to 140 ° C. for 11 hours to further react.
실시예 1과 같이 후처리하여 염소함량 71％인 염소화 저분자 폴리에틸렌 100㎏을 제조하였다.Post-treatment was carried out as in Example 1 to prepare 100 kg of chlorinated low molecular weight polyethylene having a chlorine content of 71%.
[실시예 3]Example 3
실시예 1과 같은 방법으로 대한유화공업(주) 아이소택틱 폴리프로필렌(isotactic PP)제조시 부생되는 아택틱 폴리프로필렌(isotactic PP, 융점50℃∼100℃ 평균 분자량 약 10,000) 30㎏을 사용하여 염소함량 45％인 염소화 아택틱 폴리프로필렌(CAPP-chlorinated atactic polyproplylene) 54㎏을 얻을수 있었다.By using the same method as in Example 1 30kg of atactic polypropylene (isotactic PP, melting point 50 ℃ ~ 100 ℃ average molecular weight of about 10,000) by-produced when manufacturing isotactic polypropylene (isotactic PP) 54 kg of chlorinated atactic polypropylene (CAPP-chlorinated atactic polyproplylene) was obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014171775A1 (en) * | 2013-04-19 | 2014-10-23 | (주) 엘지화학 | Polyethylene with controlled wax content, chlorinated polyethylene thereof, and molded product prepared therefrom |
| US9796797B2 (en) | 2013-04-19 | 2017-10-24 | Lg Chem, Ltd. | Polyethylene with controlled wax content, chlorinated polyethylene thereof and molded article produced from the chlorinated polyethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014171775A1 (en) * | 2013-04-19 | 2014-10-23 | (주) 엘지화학 | Polyethylene with controlled wax content, chlorinated polyethylene thereof, and molded product prepared therefrom |
| US9796797B2 (en) | 2013-04-19 | 2017-10-24 | Lg Chem, Ltd. | Polyethylene with controlled wax content, chlorinated polyethylene thereof and molded article produced from the chlorinated polyethylene |
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