KR20060038100A - Process for increased productivity of aromatic vinyl-block-conjugated diene block copolymer - Google Patents

Process for increased productivity of aromatic vinyl-block-conjugated diene block copolymer Download PDF

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KR20060038100A
KR20060038100A KR1020040087259A KR20040087259A KR20060038100A KR 20060038100 A KR20060038100 A KR 20060038100A KR 1020040087259 A KR1020040087259 A KR 1020040087259A KR 20040087259 A KR20040087259 A KR 20040087259A KR 20060038100 A KR20060038100 A KR 20060038100A
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conjugated diene
polymerization
aromatic hydrocarbon
experimental example
butadiene
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전문석
이진우
이춘화
한보령
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주식회사 엘지화학
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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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers

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Abstract

본 발명은 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조 방법, 상세하게는 공액 디엔 단량체를 2회 이상 분할 투입함에 의해 기존 방향족 탄화수소/공액 디엔 블록 공중합체의 중합 공정을 개선시켜 중합 생산성을 향상시킬 수 있는 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조 방법에 관한 것이다.
The present invention improves the polymerization process of the conventional aromatic hydrocarbon / conjugated diene block copolymer by dividing the method for producing a vinyl aromatic hydrocarbon / conjugated diene block copolymer, specifically, by dividing the conjugated diene monomer at least twice. And a process for preparing vinyl aromatic hydrocarbon / conjugated diene block copolymers.

비닐 방향족 탄화수소, 공액 디엔, 총 고체 함량, 중합 생산성, 분할 투입Vinyl aromatic hydrocarbons, conjugated dienes, total solids content, polymerization productivity, split dosing

Description

비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 중합 생산성 향상을 위한 제조 방법 {Process for Increased Productivity of Aromatic Vinyl-Block-Conjugated Diene Block Copolymer}Process for Increased Productivity of Aromatic Vinyl-Block-Conjugated Diene Block Copolymer

본 발명은 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조 방법, 상세하게는 공액 디엔 단량체를 2회 이상 분할 투입함에 의해 기존 방향족 탄화수소/공액 디엔 블록 공중합체의 중합 공정을 개선시켜 중합 생산성을 향상시킬 수 있는 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조 방법에 관한 것이다.The present invention improves the polymerization process of the conventional aromatic hydrocarbon / conjugated diene block copolymer by dividing the method for producing a vinyl aromatic hydrocarbon / conjugated diene block copolymer, specifically, by dividing the conjugated diene monomer at least twice. And a process for preparing vinyl aromatic hydrocarbon / conjugated diene block copolymers.

비닐 방향족 탄화수소 블록 및 공액 디엔 블록으로 이루어지는 비닐 방향족 탄화수소/공액 디엔 블록 공중합체는 용액 중합으로 제조하므로 주기 시간이 짧은 반면 중합 공정 중에 온도 및 압력 제어가 쉽지 않은 단점이 있다. 따라서 생산성 향상을 위해 반응 용액 중 총 고체 함량(Total Solid Content: TSC)을 증가시키는 것이 필요하나, 총 고체 함량이 증가되면 중합 공정 중에 발열량이 급격히 증가하여 반응열 제어가 어려워지는 문제가 존재하였다. 이에 높은 TSC 에서도 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 중합 공정에서 발생하는 반응열 제어를 쉽 게 함으로써 중합 생산성을 향상시킬 수 있는 개선된 중합 공정이 필요하였다. Vinyl aromatic hydrocarbon / conjugated diene block copolymers composed of vinyl aromatic hydrocarbon blocks and conjugated diene blocks have a short cycle time because they are prepared by solution polymerization, but have difficulty in controlling temperature and pressure during the polymerization process. Therefore, in order to improve productivity, it is necessary to increase the total solid content (TSC) in the reaction solution. However, when the total solid content is increased, the calorific value rapidly increases during the polymerization process, making it difficult to control reaction heat. Therefore, even at high TSC, there was a need for an improved polymerization process that can improve polymerization productivity by facilitating control of reaction heat generated in the polymerization process of vinyl aromatic hydrocarbon / conjugated diene block copolymer.

본 발명자들은 상기의 문제를 해결하고자 예의 연구를 계속한 결과, 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 중합 공정 중에 공액 디엔을 2회 이상 분할 투입하면, 기존 방향족 탄화수소/공액 디엔 블록 공중합체 중합 공정에 비해 높은 TSC에서도 반응열 제어가 용이하여, 중합 생산성이 향상될 수 있음을 발견하여 본 발명을 완성하게 되었다.The present inventors have conducted intensive studies to solve the above problems, and when the conjugated diene is divided into two or more times during the polymerization process of the vinyl aromatic hydrocarbon / conjugated diene block copolymer, the existing aromatic hydrocarbon / conjugated diene block copolymer polymerization process Compared to the high TSC, it is easy to control the reaction heat, and the present inventors have found that polymerization productivity can be improved, thereby completing the present invention.

따라서, 본 발명은 기존 방향족 탄화수소/공액 디엔 블록 공중합체 중합 공정에 비해 높은 TSC에서도 반응열 제어가 용이하여 중합 생산성을 향상시킬 수 있는 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조 방법을 제공하고자 하는 것을 목적으로 한다. Accordingly, the present invention is to provide a method for producing a vinyl aromatic hydrocarbon / conjugated diene block copolymer that can improve the polymerization productivity by controlling the reaction heat even at a high TSC compared to the conventional aromatic hydrocarbon / conjugated diene block copolymer polymerization process. The purpose.

이하에서 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조시 단량체 투입 방법을 변경하여 생산성을 증가시키는 방법에 관한 것이다. 상세하게는 본 발명은 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조방법에 있어서, 사용되는 공액 디엔 단량체를 2회 이상 분할하여 투입하는 것을 특징으로 하는 제조방법에 관한 것이다.The present invention relates to a method of increasing productivity by changing the monomer input method in the production of vinyl aromatic hydrocarbon / conjugated diene block copolymers. Specifically, the present invention relates to a method for producing a vinyl aromatic hydrocarbon / conjugated diene block copolymer, wherein the conjugated diene monomer used is divided into two or more times and added.

또한, 본 발명의 방법에 있어서, 두번째 부터의 공액 디엔 투입은 60 ~ 100 ℃의 중합 온도 및 2.0 ~ 4.0 bar 의 압력 하에서 실시한다. In addition, in the process of the present invention, the conjugated diene input from the second is carried out under a polymerization temperature of 60 to 100 ° C. and a pressure of 2.0 to 4.0 bar.                     

본 발명의 방법에서는 비닐 방향족 탄화수소 단량체로서 스티렌, 메틸스티렌 또는 이들의 혼합물을 사용할 수 있으며, 공액 디엔 단량체로는 부타디엔, 이소프렌 또는 이들의 혼합물을 사용할 수 있다. 공액 디엔 단량체는 중합 공정 중 2회 이상 분할 투입하나, 바람직하게는 2회에 나누어 투입하는 것이 좋다. 이때 첫번째 투입되는 공액 디엔과 두번째 투입되는 공액 디엔은 90~10 : 10~90 (중량비), 바람직하게는 80~50 : 20~50 (중량비) 로 투입하는 것이 유리하다. In the method of the present invention, styrene, methyl styrene or a mixture thereof may be used as the vinyl aromatic hydrocarbon monomer, and butadiene, isoprene or a mixture thereof may be used as the conjugated diene monomer. The conjugated diene monomer is divided into two or more times during the polymerization step, but preferably, divided into two times. In this case, the first conjugated diene and the second conjugated diene are advantageously added at 90 to 10:10 to 90 (weight ratio), preferably at 80 to 50:20 to 50 (weight ratio).

본 발명의 방법에 따라 제조된 블록 공중합체의 중량 평균 분자량은 5,000 ~ 500,000의 범위를 가지며, 비닐 방향족 탄화수소와 공액 디엔의 비율이 5 : 95 ~ 40 : 60일 수 있다. The weight average molecular weight of the block copolymer prepared according to the method of the present invention has a range of 5,000 to 500,000, the ratio of the vinyl aromatic hydrocarbon and conjugated diene may be 5: 95 to 40: 60.

상기 블록 공중합체의 중합은 유기 리튬과 탄화수소 용매가 있는 반응기에 비닐 방향족 탄화수소와 공액 디엔 혼합액을 반응기에 투입하고 단량체 소모가 99% 이상일 때까지 중합을 진행한 후 커플링 반응을 통하여 선형 혹은 방사형 블록 공중합체를 제조하여 실행한다. 이 후 물 또는 알코올을 반응기에 첨가하여 활성 고분자의 활성을 제거한 중합물을 제조한다. 이 때 단량체의 투입은 방향족 탄화수소, 공액 디엔의 순서로 하되, 공액 디엔은 2회 이상 나누어서 투입한다. In the polymerization of the block copolymer, a vinyl aromatic hydrocarbon and a conjugated diene mixture are added to a reactor containing an organic lithium and a hydrocarbon solvent, the polymerization is performed until the monomer consumption is 99% or more, and then a linear or radial block is formed through a coupling reaction. Copolymers are prepared and run. Thereafter, water or alcohol is added to the reactor to prepare a polymer in which the activity of the active polymer is removed. In this case, the monomers are added in the order of aromatic hydrocarbons and conjugated dienes, but the conjugated dienes are divided into two or more times.

이하 하기의 실험예를 통하여 본 발명을 더욱 상세하게 설명하지만, 본 발명의 범위가 실험예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to the following experimental examples, but the scope of the present invention is not limited to the experimental examples.

실험예 1: TSC 증가에 따른 중합 생산성 향상 여부에 대한 실험Experimental Example 1: Experiment whether or not to increase the polymerization productivity according to the increase in TSC

실험예 1-1: TSC가 17.24인 경우 Experimental Example 1-1: TSC is 17.24                     

스티렌과 부타디엔을 단량체로 사용하여 무게 조성비 31/69의 삼중 블록 공중합체를 다음과 같이 제조하였다. 질소로 충전된 20 L 반응기에 용매인 사이클로헥산 9590 g, 스티렌 636g을 투입한 후 60 ℃의 온도에서 n-부틸리튬 2.9g을 첨가하여 스티렌을 중합하였다. 스티렌 중합 후 다시 부타디엔 단량체 1132g을 투입하여 상기 중합된 스티렌 블록 말단에 부타디엔 블록을 생성시켰다. 부타디엔 중합 완료 후 이염화이메틸실란을 투입하여 커플링 반응을 진행시킨 다음, 부틸수산화톨루엔 20.5g을 투입하여 중합 반응을 종결하였다. 이때의 TSC는 17.24 중량비였다. 상기와 같이 제조된 삼중 블록 공중합체의 분자량은 110,000 g/몰이다. 상기 조건으로 삼중 블록 공중합체를 제조할 때 중합 시간과 중합 최고 온도를 측정하였으며, 그 결과를 하기 표 1에 나타내었다.
Using a styrene and butadiene as a monomer, a triblock copolymer having a weight ratio of 31/69 was prepared as follows. 9590 g of solvent cyclohexane and 636 g of styrene were added to a 20 L reactor filled with nitrogen, and styrene was polymerized by adding 2.9 g of n -butyllithium at a temperature of 60 ° C. After the styrene polymerization, 1132 g of butadiene monomer was added again to generate a butadiene block at the end of the polymerized styrene block. After completion of the butadiene polymerization, dimethyl silane dichloride was added to proceed with the coupling reaction, and then 20.5 g of butyl hydroxide toluene was added to terminate the polymerization reaction. At this time, TSC was 17.24 weight ratio. The molecular weight of the triblock copolymer prepared as above is 110,000 g / mol. When the triblock copolymer was prepared under the above conditions, the polymerization time and the polymerization maximum temperature were measured, and the results are shown in Table 1 below.

실험예 1-2: TSC가 16.39인 경우Experimental Example 1-2: TSC is 16.39

상기와 동일한 방법으로 삼중 블록 공중합체의 중합 용액을 제조한다. 단, 단량체와 용매의 비율을 TSC가 16.39 중량비가 되도록 바꾸어 실시하였다. 제조된 삼중 블록 공중합체의 분자량은 110,000 g/몰이었다. 중합 시간과 온도 변화를 측정하여 그 결과를 표 1에 나타내었다. A polymerization solution of the triple block copolymer is prepared in the same manner as above. However, the ratio of monomer and solvent was changed so that TSC might be 16.39 weight ratio. The molecular weight of the prepared triblock copolymer was 110,000 g / mol. The polymerization time and temperature change were measured and the results are shown in Table 1.

실험예 1Experimental Example 1 중합 시간(분)Polymerization time (minutes) 중합 최고 온도(℃)Polymerization maximum temperature (℃) 1-11-1 1717 122122 1-21-2 1818 118118

상기 표 1 에서 보듯이 공액 디엔을 분할 투입하지 않았을 때 TSC가 높은 경우 반응 시간은 1분 정도 줄었으나, 중합 최고 온도는 4 ℃ 정도 상승하였다.
As shown in Table 1, when TSC was high when the conjugated diene was not separately added, the reaction time was decreased by about 1 minute, but the maximum polymerization temperature was increased by about 4 ° C.

실험예 2: 높은 TSC에서 공액 디엔의 분할 투입의 효과에 대한 실험 Experimental Example 2: Experiment on the effect of split dosing of conjugated diene at high TSC

TSC가 17.24이었을 때와 동일한 방법으로 공중합체를 제조하되, 부타디엔을 2회에 걸쳐 분할 투입하였다. 첫번째 분할 투입 부타디엔의 양과 두번째 분할 투입 부타디엔 양의 비율을 20:80, 50:50, 80:20 의 세가지로 하였고, 두번째 부타디엔의 투입 시점은 첫번째 부타디엔 단량체가 모두 소모된 때로 하였다. 각각의 경우에 중합 시간과 중합 최고 온도를 측정하여 그 결과를 표 2 에 나타내었다. The copolymer was prepared in the same manner as when the TSC was 17.24, but the butadiene was divided into two portions. The ratio of the first divided input butadiene and the second divided input butadiene was three ratios of 20:80, 50:50 and 80:20, and the second butadiene was added when the first butadiene monomer was consumed. In each case, the polymerization time and the polymerization maximum temperature were measured and the results are shown in Table 2.

실험예Experimental Example 중합 시간(분)Polymerization time (minutes) 중합 최고 온도(℃)Polymerization maximum temperature (℃) 실험예 1-2Experimental Example 1-2 1818 118118 실험예 1-1Experimental Example 1-1 1717 122122 실험예 2-1(분할투입 20:80)Experimental Example 2-1 (Divided Input 20:80) 26.526.5 116116 실험예 2-2(분할투입 50:50)Experimental Example 2-2 (split 50:50) 2525 112112 실험예 2-3(분할투입 80:20)Experimental Example 2-3 (split 80:20) 20.520.5 116116

상기 표 2 의 결과를 보면 부타디엔을 분할 투입한 경우 중합 최고 온도는 TSC가 동일한 실험예 1-2의 최고 온도에 비해 약 6 ~ 10 ℃ 정도 낮아졌다. 그러나 첫번째 투입된 부타디엔의 양이 적을수록 두번째 부타디엔 투입 시점이 늦어져서 전체적인 중합시간이 길어지는 경향이 나타났다. In the results of Table 2, when the butadiene was separately added, the polymerization maximum temperature was about 6 to 10 ° C. lower than that of TSC in the same experiment example 1-2. However, the smaller the amount of the first butadiene added, the later the second butadiene addition point was delayed and the overall polymerization time tended to be longer.

하기 표 3~5는 부타디엔 분할 투입법에 의해 제조된 스티렌-부타디엔-스티렌 공중합체의 기본 물성과 아스팔트 적용시의 물성을 측정한 결과이다. 하기 표 3은 제조된 스티렌-부타디엔-스티렌 공중합체의 기본 물성 측정 결과를 나타낸다.Tables 3 to 5 below show the results obtained by measuring the basic properties of the styrene-butadiene-styrene copolymers prepared by the butadiene split injection method and the properties of the asphalt application. Table 3 below shows the measurement results of the basic physical properties of the produced styrene-butadiene-styrene copolymer.

실험예 1-1Experimental Example 1-1 실험예 2-1Experimental Example 2-1 실험예 2-2Experimental Example 2-2 실험예 2-3Experimental Example 2-3 실험예 1-2Experimental Example 1-2 커플링 정도(%)Coupling degree (%) 80.080.0 78.078.0 83.083.0 84.684.6 79.179.1 데드(Dead) PS 함량(%)Dead PS Content (%) 2.02.0 1.81.8 1.91.9 1.21.2 3.43.4 인장 강도(kg*f/cm2)Tensile Strength (kg * f / cm 2 ) 352.7352.7 362.5362.5 346.9346.9 346.8346.8 357.9357.9 300% 인장 탄성율(kg/cm2)300% Tensile Modulus (kg / cm 2 ) 28.1828.18 30.5530.55 30.8430.84 29.0129.01 29.529.5 신율(%)% Elongation 823823 773773 748748 846846 826826 경도 (Shore A)Shore A 77.477.4 78.178.1 77.577.5 78.178.1 75.475.4 5% 톨루엔 용액 점도(cst)5% toluene solution viscosity (cst) 13.0213.02 14.0914.09 13.7513.75 12.8812.88 13.4013.40

상기 표 3을 보면 전체적으로 물성의 변화가 가장 심한 것은 신율이었으나, 톨루엔 용액 점도와는 상관관계가 성립되지 않음을 알 수 있다. 결론적으로 부타디엔을 분할 투입했을 경우는 spec. 내 물성을 모두 가지고 있으며, 분할 투입에 따른 물성저하는 없다.In Table 3, the elongation was the most severe change in physical properties, but it did not correlate with the viscosity of toluene solution. In conclusion, if butadiene is added in part, spec. It has all the physical properties and there is no deterioration in properties due to the divided input.

아스팔트 물성에 대해서는 도로 포장용과 방수용 두 가지로 테스트하였으며, 각각의 물성 측정치에 대해 각각 표 4와 표 5에서 그 결과를 나타내었다. 도로 포장용에 사용된 아스팔트는 SK제품 AP-5이고 방수용에 사용된 것은 AP-3이다. 시험 시편의 제조는 아스팔트 500g에 도로 포장용은 20.83g(4%) 스티렌-부타디엔-스티렌 공중합체를, 방수용은 55.55g(10%) 스티렌-부타디엔-스티렌 공중합체를 가하고 160~170 ℃에서 30분간 고전단 교반기로 교반한 후 시편을 제조하여 하루 뒤에 측정하였다. Asphalt properties were tested for road pavement and waterproofing, and the results are shown in Table 4 and Table 5 for each property measurement. Asphalt used for road pavement is AP-5 made by SK, and AP-3 used for waterproofing. Test specimen was prepared by adding 500.g of asphalt and 20.83g (4%) of styrene-butadiene-styrene copolymer for road pavement, and 55.55g (10%) of styrene-butadiene-styrene copolymer for waterproofing for 30 minutes at 160 ~ 170 ° C. After stirring with a high shear stirrer, a specimen was prepared and measured one day later.

AP-5AP-5 실험예 1-1Experimental Example 1-1 실험예 2-1Experimental Example 2-1 실험예 2-2Experimental Example 2-2 실험예 2-3Experimental Example 2-3 실험예 1-2Experimental Example 1-2 연화점 (℃)Softening Point (℃) 52.452.4 72.472.4 80.580.5 74.174.1 74.574.5 75.075.0 침입도 (dmm)Penetration (dmm) 6767 5252 5353 5353 5454 5151 점도(cps)Viscosity (cps) 80℃80 ℃ 2000020000 169000169000 291000291000 142000142000 142000142000 104000104000 100℃100 ℃ 34703470 1940019400 2880028800 2340023400 2340023400 2110021100 120℃120 ℃ 950950 38903890 51905190 51805180 51805180 45304530 135℃135 ℃ 410410 17601760 21402140 17701770 17701770 16501650 160℃160 ℃ 147147 451451 458458 450450 450450 445445 180℃180 ℃ -- 192192 218218 214214 214214 230230

AP-3AP-3 실험예 1-1Experimental Example 1-1 실험예 2-1Experimental Example 2-1 실험예 2-2Experimental Example 2-2 실험예 2-3Experimental Example 2-3 실험예 1-2Experimental Example 1-2 연화점 (℃)Softening Point (℃) 52.952.9 116.2116.2 115.7115.7 115.2115.2 112.1112.1 112.9112.9 침입도 (dmm)Penetration (dmm) 105105 5252 5050 5151 5353 5252 점도(cps)Viscosity (cps) 120 ℃120 ℃ 910910 181000181000 170000170000 168000168000 120000120000 120000120000 135 ℃135 ℃ 390390 1810018100 1900019000 1920019200 1500015000 1500015000 160 ℃160 ℃ 130130 16901690 18601860 18901890 17401740 17401740 180 ℃180 ℃ -- 770770 830830 800800 820820 820820 200 ℃200 ℃ -- 480480 520520 490490 470470 470470 -10℃ 저온 굴곡 실험 (420초)-10 ℃ low temperature bending test (420 seconds) -- ○○ ○○ ○○ △△ ××

○: 시편에 균열이 일어나지 않음, △: 시편에 균열이 약간 일어남. ×: 시편에 균열이 심하게 남.(Circle): A crack does not generate | occur | produce in a specimen, (triangle | delta): The crack arises a little in a specimen. X: Cracks remain severely in the specimen.

상기 표 4 및 5의 측정결과를 보면 부타디엔의 분할투입에 의한 물성의 저하는 없음을 알 수 있다.
From the measurement results of Tables 4 and 5, it can be seen that there is no deterioration in physical properties due to the divided injection of butadiene.

실험예 3: 부타디엔의 분할 투입 최적 시점에 대한 실험Experimental Example 3: Experiment for Optimal Time of Split Dose of Butadiene

부타디엔 분할 투입법의 중합 시간을 단축시키기 위해서 두번째 부타디엔의 투입 시점을 변경시켜 보았다. 첫번째 부타디엔이 다 반응에 참여할 때까지 기다리지 않고 미리 두번째 부타디엔을 투입하기로 했다. 중합 시간이 가장 짧았던 부타디엔의 투입비율이 80:20인 실험예 2-3의 경우를 선택하여 이와 동일한 방법으로 삼중 블 록 공중합체를 제조하되 두번째 부타디엔을 반응 온도가 각각 95℃ 및 110℃인 때 투입하였다.In order to shorten the polymerization time of the butadiene split dosing method, the input time of the second butadiene was changed. Instead of waiting for the first butadiene to participate in the reaction, the second butadiene was decided in advance. Select the case of Experimental Example 2-3 where the ratio of butadiene having the shortest polymerization time was 80:20 to prepare a triple block copolymer in the same manner, but the second butadiene was reacted at 95 ° C and 110 ° C, respectively. Input.

실험예Experimental Example 중합 시간(분)Polymerization time (minutes) 중합 최고 온도(℃)Polymerization maximum temperature (℃) 실험예 1-2Experimental Example 1-2 1818 118118 실험예 1-1Experimental Example 1-1 1717 122122 실험예 2-3Experimental Example 2-3 20.520.5 116116 실험예 3-1(110℃ 투입)Experimental Example 3-1 (injected at 110 ° C) 18.518.5 119119 실험예 3-2(95℃ 투입)Experimental Example 3-2 (put at 95 ° C) 1818 119119

상기 표 6에서 보면, 두번째 부타디엔을 95 ℃에서 분할 투입했을 경우, 반응 시간과 중합 최고 온도가 실험예 1-2, 즉 TSC를 16.39 중량비로 하여 부타디엔을 일괄 투입하였을 때와 동등한 결과가 나왔다. 따라서, 부타디엔의 분할 투입과 생산성 향상이 동시에 가능함을 확인하였다.
In Table 6, when the second butadiene was separately added at 95 ° C, the reaction time and the highest polymerization temperature were the same as those obtained by collectively adding butadiene with Experimental Example 1-2, that is, 16.39 weight ratio of TSC. Therefore, it was confirmed that butadiene injection and productivity improvement were possible at the same time.

상기에서 기술한 바와 같이, 공액 디엔을 2회 이상 분할 투여하는 것을 특징으로 하는 본 발명에 따른 탄화수소/공액 디엔 블록 공중합체의 제조방법으로 높은 TSC에서 중합이 가능하게 되어 기존 방향족 탄화수소/공액 디엔 블록 공중합체 중합 공정의 중합 생산성이 향상됨을 알 수 있다. As described above, the method for preparing a hydrocarbon / conjugated diene block copolymer according to the present invention, characterized in that the conjugated diene is divided into two or more times, so that polymerization is possible at a high TSC. It can be seen that the polymerization productivity of the copolymer polymerization process is improved.

상기에서 본 발명은 기재된 구체예를 중심으로 상세히 설명되었지만, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 자명하다.While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also obvious.

Claims (4)

비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조방법에 있어서, 사용되는 공액 디엔을 2회 이상 분할하여 투입하되, 첫번째 및 그 나머지 공액 디엔의 투입량이 90~10: 10~90 인 것을 특징으로 하는 비닐 방향족 탄화수소/공액 디엔 블록 공중합체의 제조 방법. In the method for producing a vinyl aromatic hydrocarbon / conjugated diene block copolymer, the conjugated diene to be used is divided into two or more times, and the first and the remaining conjugated dienes have a vinyl content of 90 to 10: 10 to 90. Process for the preparation of aromatic hydrocarbon / conjugated diene block copolymers. 제 1 항에 있어서, 첫번째 이후의 공액 디엔 투입을 60~100 ℃의 중합 온도 및 2.0 ~ 4.0 bar 의 압력 하에서 실행하는 것을 특징으로 하는 제조 방법. The process according to claim 1, wherein the first and subsequent conjugated diene charges are carried out at a polymerization temperature of 60 to 100 ° C and a pressure of 2.0 to 4.0 bar. 제 1 항에 있어서, 제조된 블록 공중합체의 중량 평균 분자량은 5,000 ~ 500,000의 범위를 가지며, 비닐 방향족 탄화수소와 공액 디엔의 비율이 5 : 95 ~ 40 : 60인 것을 특징으로 하는 제조 방법.The method according to claim 1, wherein the weight average molecular weight of the prepared block copolymer has a range of 5,000 to 500,000, and the ratio of vinyl aromatic hydrocarbon and conjugated diene is 5:95 to 40:60. 제 1 항에 있어서, 비닐 방향족 탄화수소는 스티렌, 메틸스티렌 또는 이들의 혼합물에서 선택되며, 공액 디엔은 부타디엔, 이소프렌 또는 이들의 혼합물에서 선택되는 것을 특징으로 하는 제조 방법.The process of claim 1 wherein the vinyl aromatic hydrocarbon is selected from styrene, methylstyrene or mixtures thereof and the conjugated diene is selected from butadiene, isoprene or mixtures thereof.
KR1020040087259A 2004-10-29 2004-10-29 Process for increased productivity of aromatic vinyl-block-conjugated diene block copolymer KR20060038100A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190036186A (en) 2017-09-27 2019-04-04 주식회사 엘지화학 Vinyl chloride polymer, preparation method thereof and interior material comprising the same
KR20190046326A (en) 2017-10-26 2019-05-07 주식회사 엘지화학 preparation method for Vinyl chloride polymer
WO2019124967A1 (en) 2017-12-19 2019-06-27 주식회사 엘지화학 Method for producing vinyl chloride polymer and vinyl chloride polymer produced therefrom

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190036186A (en) 2017-09-27 2019-04-04 주식회사 엘지화학 Vinyl chloride polymer, preparation method thereof and interior material comprising the same
KR20190046326A (en) 2017-10-26 2019-05-07 주식회사 엘지화학 preparation method for Vinyl chloride polymer
WO2019124967A1 (en) 2017-12-19 2019-06-27 주식회사 엘지화학 Method for producing vinyl chloride polymer and vinyl chloride polymer produced therefrom
KR20190073996A (en) 2017-12-19 2019-06-27 주식회사 엘지화학 preparation method for Vinyl chloride polymer and vinyl chloride polymer by the method
US11325998B2 (en) 2017-12-19 2022-05-10 Lg Chem, Ltd. Method for preparing vinyl chloride-based polymer and vinyl chloride-based polymer prepared therefrom

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