KR20230063677A - Manufacturing method of epdm with polar group amd epdm with polar group using the same - Google Patents
Manufacturing method of epdm with polar group amd epdm with polar group using the same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 78
- 239000003999 initiator Substances 0.000 claims abstract description 50
- 230000002378 acidificating effect Effects 0.000 claims abstract description 39
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 15
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- HQLWSPAOVXYSSG-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C.CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C HQLWSPAOVXYSSG-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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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
- C08F8/10—Acylation
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
Abstract
본 발명은 극성기를 가지는 EPDM의 제조 방법 및 이 방법에 의해 제조된 극성기를 가지는 EPDM에 관한 것으로, 보다 구체적으로는 용융 중합(Melt grafting)을 통해 EDPM(Ethylene propylene diene monomer) 고무에 산성기를 도입하되, 중합 전에 산성기와 개시제를 미리 혼합한 마스터배치(Master batch)를 제조한 후 용융 중합에 도입함으로써, 치환율을 극히 향상시킨 개질 EPDM을 제조할 수 있도록 하는, 극성기를 가지는 EPDM의 제조 방법 및 이 방법에 의해 제조된 극성기를 가지는 EPDM에 관한 것이다.The present invention relates to a method for producing EPDM having a polar group and an EPDM having a polar group prepared by the method, and more specifically, to introduce an acidic group into EDPM (Ethylene propylene diene monomer) rubber through melt grafting, A method for producing EPDM having a polar group by preparing a master batch in which an acidic group and an initiator are mixed in advance before polymerization and then introducing it into melt polymerization to produce a modified EPDM with an extremely improved substitution rate, and this method It relates to EPDM having a polar group prepared by.
Description
본 발명은 용융 중합(Melt grafting)을 통해 EDPM(Ethylene propylene diene monomer) 고무에 산성기를 도입하되, 중합 전에 산성기와 개시제를 미리 혼합한 마스터배치(Master batch)를 제조한 후 용융 중합에 도입함으로써 치환율을 극히 향상시킬 수 있도록 하는, 극성기를 가지는 EPDM의 제조 방법 및 이 방법에 의해 제조된 극성기를 가지는 EPDM에 관한 것이다.The present invention introduces an acidic group into EDPM (Ethylene propylene diene monomer) rubber through melt grafting, but prepares a master batch in which the acidic group and an initiator are mixed in advance before polymerization, and then introduces it into melt polymerization, thereby reducing the substitution rate. It relates to a method for producing EPDM having a polar group, and an EPDM having a polar group produced by the method, which can greatly improve the
일반적으로 극성기를 가지는 EPDM(Ethylene propylene diene monomer) 고무는 상용화제나 열가역적인 가교결합을 가지는 탄성체 제조를 위해 사용이 점점 증가되고 있다.In general, EPDM (Ethylene propylene diene monomer) rubber having a polar group is increasingly used as a compatibilizer or for preparing an elastomer having thermoreversible crosslinking.
한편, 극성기를 가지는 EPDM 고무를 제조하는 방법으로 용액 중합과 용융 중합이 있다.On the other hand, there are solution polymerization and melt polymerization as a method for producing EPDM rubber having a polar group.
보다 구체적으로 용액 중합은 치환율을 높일 수 있지만 유기 용매 사용에 따른 환경 문제와 안전 문제, 복잡한 공정 및 용매 회수 등의 문제로 상업화에는 적용이 되지 못하고 있다.More specifically, solution polymerization can increase the substitution rate, but it has not been applied to commercialization due to problems such as environmental problems, safety problems, complicated processes and solvent recovery due to the use of organic solvents.
이를 해결하기 위하여 특허문헌 1 및 2에서는 이타코닉산(Itaconic acid) 등의 카르복실산(carboxylic acid)을 반응개시제의 존재하에서 용융 중합을 통한 반응 압출에 의해 EPDM 또는 폴리프로필렌 공중합체에 그라프트(graft)시키는 기술을 제안하였다.In order to solve this problem, in Patent Documents 1 and 2, a carboxylic acid such as itaconic acid is grafted onto EPDM or a polypropylene copolymer by reaction extrusion through melt polymerization in the presence of a reaction initiator ( grafting technique was proposed.
하지만, 상기와 같은 종래의 용융 중합은 유기 용매를 사용하지 않고 공정이 비교적 간단하지만 치환율이 낮은(현재 상업화되어 있는 제품의 치환율은 2% 미만임) 문제점이 있었다.However, the conventional melt polymerization as described above has a problem of a relatively simple process without using an organic solvent, but a low substitution rate (currently commercialized products have a substitution rate of less than 2%).
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 용융 중합(Melt grafting)을 통해 EDPM(Ethylene propylene diene monomer) 고무에 산성기를 도입하되, 중합 전에 산성기와 개시제를 미리 혼합한 마스터배치(Master batch)를 제조한 후 용융 중합에 도입함으로써, 치환율을 극히 향상시킨 개질 EPDM을 제조할 수 있도록 함을 과제로 한다.The present invention is to solve the above problems, introducing an acidic group into EDPM (Ethylene propylene diene monomer) rubber through melt grafting, but mixing the acidic group and an initiator in advance before polymerization Master batch It is an object to be able to manufacture a modified EPDM with an extremely improved substitution rate by introducing it into melt polymerization after manufacturing.
본 발명은 극성기를 가지는 EPDM의 제조 방법에 있어서, 산성기 기재에 개시제를 혼합하는 단계(S100); 상기 혼합물에 실리콘 오일(Silicon oil)을 투입하여 산성기-개시제 마스터배치(Master batch)를 제조하는 단계(S200); 및 EPDM(Ethylene propylene diene monomer)에 상기 제조된 산성기-개시제 마스터배치를 혼합하여 산성기로 치환된 EPDM을 제조하는 단계(S300);를 포함하는 것을 특징으로 하는, 극성기를 가지는 EPDM의 제조 방법 및 이 방법에 의해 제조된 극성기를 가지는 EPDM을 과제의 해결 수단으로 한다.The present invention is a method for producing EPDM having a polar group, comprising the steps of mixing an initiator with an acidic base material (S100); preparing an acid group-initiator master batch by adding silicon oil to the mixture (S200); and preparing an EPDM substituted with an acidic group by mixing the above-prepared acidic group-initiator masterbatch with EPDM (Ethylene propylene diene monomer) (S300); a method for producing EPDM having a polar group and EPDM having a polar group manufactured by this method is used as a solution to the problem.
보다 구체적으로, 상기 S100 단계는 산성기 기재 100 중량부에 대하여, 개시제 1 ~ 5 중량부를 슈퍼믹서(Super mixer)에서 500 ~ 1000rpm으로 10 ~ 20분간 혼합하여 산성기에 개시제를 흡착시키는 것이 바람직하다.More specifically, in step S100, 1 to 5 parts by weight of an initiator is mixed in a super mixer at 500 to 1000 rpm for 10 to 20 minutes with respect to 100 parts by weight of the acid group base material to adsorb the initiator to the acid group.
그리고, 상기 S200 단계는 산성기 기재 100 중량부를 기준으로, 실리콘 오일 1 ~ 5 중량부를 슈퍼믹서에 추가 투입한 후, 500 ~ 1000rpm으로 5 ~ 10분간 혼합하여 표면 코팅된 산성기-개시제 마스터배치를 제조하는 것이 바람직하다.In the step S200, 1 to 5 parts by weight of silicone oil based on 100 parts by weight of the acid group substrate is additionally added to the super mixer, and then mixed at 500 to 1000 rpm for 5 to 10 minutes to obtain a surface-coated acid group-initiator masterbatch. It is desirable to manufacture
또한, 상기 S300 단계는 EPDM 100 중량부에 대하여 산성기-개시제 마스터배치 3 ~ 5.35 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조하는 것이 바람직하다.In addition, in the step S300, 3 to 5.35 parts by weight of the acid group-initiator masterbatch based on 100 parts by weight of EPDM is introduced into a twin screw extruder set at a temperature of 150 to 220 ° C, and then the EPDM substituted with an acid group is prepared through reaction extrusion. desirable.
한편, 상기 산성기 기재는 용융 온도가 162 ~ 164℃인 이타코닉산(Itaconic acid)을 사용하고, 상기 개시제는 1분 반감기 온도가 170 ~ 180℃인 액상형 퍼옥사이드계 개시제를 사용하는 것이 바람직하다.On the other hand, itaconic acid having a melting temperature of 162 to 164° C. is used as the acidic base material, and a liquid peroxide-based initiator having a 1-minute half-life temperature of 170 to 180° C. is preferably used as the initiator. .
본 발명은 용융 중합(Melt grafting)을 통해 EDPM(Ethylene propylene diene monomer) 고무에 산성기를 도입하되, 중합 전에 산성기와 개시제를 미리 혼합한 마스터배치(Master batch)를 제조한 후 용융 중합에 도입함으로써, 치환율을 극히 향상시킬 수 있는 효과가 있다.The present invention introduces an acidic group into EDPM (Ethylene propylene diene monomer) rubber through melt grafting, prepares a master batch in which the acidic group and an initiator are mixed in advance before polymerization, and then introduces it into melt polymerization, There is an effect that can greatly improve the substitution rate.
도 1은 본 발명에 따른 극성기를 가지는 EPDM의 제조 방법을 나타낸 공정흐름도1 is a process flow chart showing a method of manufacturing EPDM having a polar group according to the present invention
상기의 효과를 달성하기 위한 본 발명은 극성기를 가지는 EPDM의 제조 방법 및 이 방법에 의해 제조된 극성기를 가지는 EPDM에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.The present invention for achieving the above effects relates to a method for producing EPDM having a polar group and an EPDM having a polar group produced by this method, and only parts necessary for understanding the technical configuration of the present invention are described, and other parts are described. It should be noted that descriptions will be omitted so as not to obscure the subject matter of the present invention.
이하, 본 발명에 따른 극성기를 가지는 EPDM의 제조 방법 및 이 방법에 의해 제조된 극성기를 가지는 EPDM을 상세히 설명하면 다음과 같다.Hereinafter, a method for producing EPDM having a polar group according to the present invention and an EPDM having a polar group prepared by this method will be described in detail.
본 발명은 도 1에 도시된 바와 같이, 산성기 기재 및 개시제 혼합단계(S100), 산성기-개시제 마스터배치 제조단계(S200) 및 산성기로 치환된 EPDM 제조단계(S300)를 포함하여 구성된다.As shown in FIG. 1, the present invention includes acidic group substrate and initiator mixing step (S100), acidic group-initiator masterbatch preparation step (S200), and acidic group substituted EPDM preparation step (S300).
상기 S100 단계는 산성기 기재에 개시제를 혼합하는 단계로써, 산성기 기재 100 중량부에 대하여, 개시제 1 ~ 5 중량부를 슈퍼믹서에서 500 ~ 1000rpm으로 10 ~ 20분간 혼합하여 산성기에 개시제를 흡착시킨다.The step S100 is a step of mixing an initiator with an acidic base material, and 1 to 5 parts by weight of the initiator based on 100 parts by weight of the acidic base material are mixed in a supermixer at 500 to 1000rpm for 10 to 20 minutes to adsorb the initiator to the acidic base.
여기서, 상기 산성기 기재는 용융 온도가 162 ~ 164℃인 이타코닉산(Itaconic acid)을 사용한다. Here, itaconic acid having a melting temperature of 162 to 164° C. is used as the acidic base material.
한편, S100 단계의 혼합조건이 상기 범위를 벗어나거나 또는 용융 온도가 상기 범위를 벗어나는 산성기 기재의 사용 시, 치환율이 낮아질 우려가 있다.On the other hand, when the mixing conditions of the step S100 are out of the above range or the melting temperature is out of the above range, when using an acidic base material, there is a concern that the substitution rate is lowered.
아울러, 상기 개시제는 산성기와의 혼합을 위해 액상이 필요하며, 이에 따라 개시제로는 1분 반감기 온도가 170 ~ 180℃인 액상형 퍼옥사이드계 개시제(예를 들면, 2,5-디메틸-2,5-디(터트-부틸퍼옥시)헥산(2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane), 터트-부틸 큐밀 퍼옥사이드(tert-Butyl cumyl peroxide), 디-터트-부틸 퍼옥사이드(Di-tert-butyl peroxide) 등)를 사용한다.In addition, the initiator requires a liquid phase for mixing with the acidic group, and accordingly, a liquid peroxide-based initiator having a 1-minute half-life temperature of 170 to 180 ° C. (eg, 2,5-dimethyl-2,5 -Di(tert-butylperoxy)hexane (2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane), tert-Butyl cumyl peroxide, di-tert-butyl peroxide oxide (Di-tert-butyl peroxide, etc.) is used.
한편, 산성기 용융 온도 보다 반감기 온도가 낮은 개시제 사용시 치환 반응보다 EPDM의 가교 반응이 빠르게 일어나 겔 발생이 증가되며 180℃를 초과하는 경우 미반응 산성기가 많이 잔류하게 될 우려가 있다.On the other hand, when an initiator whose half-life temperature is lower than the melting temperature of the acidic group is used, the crosslinking reaction of EPDM occurs faster than the substitution reaction, resulting in increased gel formation. When the temperature exceeds 180° C., there is a concern that many unreacted acidic groups may remain.
상기 S200 단계는 상기 혼합물에 실리콘 오일을 투입하여 산성기-개시제 마스터배치를 제조하는 단계로써, 산성기 기재 100 중량부를 기준으로, 실리콘 오일 1 ~ 5 중량부를 슈퍼믹서에 추가 투입한 후, 500 ~ 1000rpm으로 5 ~ 10분간 혼합하여 표면 코팅된 산성기-개시제 마스터배치를 제조한다.The step S200 is a step of preparing an acid group-initiator masterbatch by adding silicone oil to the mixture, and based on 100 parts by weight of the acid group substrate, 1 to 5 parts by weight of silicone oil are additionally added to the super mixer, and then 500 to 5 parts by weight are added. A surface-coated acid group-initiator masterbatch is prepared by mixing at 1000 rpm for 5 to 10 minutes.
여기서, 상기 S200 단계의 혼합 조건 및 실리콘 오일의 함량이 상기 범위를 벗어날 경우 마스터배치가 제대로 제조되지 못할 우려가 있다.Here, if the mixing conditions and the content of the silicone oil in step S200 are out of the range, there is a risk that the masterbatch may not be properly prepared.
상기 S300 단계는 EPDM에 상기 제조된 산성기-개시제 마스터배치를 혼합하여 산성기로 치환된 EPDM을 제조하는 단계로써, EPDM 100 중량부에 대하여 산성기-개시제 마스터배치 3 ~ 5.35 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조한다.The step S300 is a step of preparing an EPDM substituted with an acidic group by mixing the prepared acid group-initiator masterbatch with EPDM, and 3 to 5.35 parts by weight of the acidic group-initiator masterbatch based on 100 parts by weight of EPDM is heated at a temperature of 150 to 220 °C. After putting it into a twin-screw extruder set at °C, EPDM substituted with an acidic group is prepared through reaction extrusion.
즉, 코팅된 마스터배치에서 개시제 분해 및 라디칼의 산성기 공격이 먼저 시작된 후 EPDM에 치환 반응이 일어나 EPDM의 개시제에 의한 겔화 현상이 작게 발생되며 미반응 산성기도 적은 치환율이 높은, 산성기로 치환된 EPDM(IA-g-EPDM)의 제조가 가능한 것이다.That is, in the coated masterbatch, decomposition of the initiator and attack of acidic groups by radicals begin first, and then a substitution reaction occurs in EPDM, resulting in a small gelation phenomenon by the initiator of EPDM, and EPDM substituted with acidic groups with a small number of unreacted acidic groups and a high substitution rate. (IA-g-EPDM) is possible.
한편, 상기 S300 단계의 혼합 조건 및 마스터배치의 함량이 상기 범위를 벗어날 경우 치환율이 낮아질 우려가 있다.On the other hand, if the mixing conditions and the content of the masterbatch in step S300 are out of the above ranges, there is a concern that the substitution rate may be lowered.
이하, 본 발명을 아래 실시예에 의거하여 더욱 상세히 설명하지만, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the examples below, but the present invention is not limited by the examples.
1. 산성기-개시제 마스터배치의 제조1. Preparation of acid group-initiator masterbatch
(제조예 1)(Production Example 1)
산성기 기재(용융 온도가 162 ~ 164℃인 이타코닉산) 100 중량부에 대하여, 개시제(1분 반감기 온도가 170 ~ 180℃인 2,5-디메틸-2,5-디(터트-부틸퍼옥시)헥산) 2 중량부를 슈퍼믹서에서 500rpm으로 10분간 혼합하여 산성기에 개시제를 흡착시킨 후(S100), 실리콘 오일 5 중량부를 슈퍼믹서에 추가 투입하고 500rpm으로 5분간 혼합하여 표면 코팅된 산성기-개시제 마스터배치를 제조(S200)하였다.Based on 100 parts by weight of the acidic base material (itaconic acid with a melting temperature of 162 to 164 ° C), an initiator (2,5-dimethyl-2,5-di (tert-butylfer with a 1-minute half-life temperature of 170 to 180 ° C) 2 parts by weight of oxy)hexane) were mixed in a super mixer at 500 rpm for 10 minutes to adsorb the initiator to the acid group (S100), and then 5 parts by weight of silicone oil were added to the super mixer and mixed at 500 rpm for 5 minutes to obtain a surface coated acid group- An initiator masterbatch was prepared (S200).
(제조예 2)(Production Example 2)
산성기 기재(용융 온도가 162 ~ 164℃인 이타코닉산) 100 중량부에 대하여, 개시제(1분 반감기 온도가 170 ~ 180℃인 2,5-디메틸-2,5-디(터트-부틸퍼옥시)헥산) 1 중량부를 슈퍼믹서에서 500rpm으로 10분간 혼합하여 산성기에 개시제를 흡착시킨 후(S100), 실리콘 오일 5 중량부를 슈퍼믹서에 추가 투입하고 500rpm으로 5분간 혼합하여 표면 코팅된 산성기-개시제 마스터배치를 제조(S200)하였다.Based on 100 parts by weight of the acidic base material (itaconic acid with a melting temperature of 162 to 164 ° C), an initiator (2,5-dimethyl-2,5-di (tert-butylfer with a 1-minute half-life temperature of 170 to 180 ° C) After 1 part by weight of oxy)hexane) was mixed in a super mixer at 500 rpm for 10 minutes to adsorb the initiator to the acid group (S100), 5 parts by weight of silicone oil was added to the super mixer and mixed at 500 rpm for 5 minutes to obtain a surface coated acid group- An initiator masterbatch was prepared (S200).
(제조예 3)(Production Example 3)
산성기 기재(용융 온도가 162 ~ 164℃인 이타코닉산) 100 중량부에 대하여, 개시제(1분 반감기 온도가 170 ~ 180℃인 디-터트-부틸 퍼옥사이드) 5 중량부를 슈퍼믹서에서 1000rpm으로 20분간 혼합하여 산성기에 개시제를 흡착시킨 후(S100), 실리콘 오일 1 중량부를 슈퍼믹서에 추가 투입하고 1000rpm으로 10분간 혼합하여 표면 코팅된 산성기-개시제 마스터배치를 제조(S200)하였다.5 parts by weight of an initiator (di-tert-butyl peroxide with a 1-minute half-life temperature of 170 to 180 °C) at 1000 rpm in a supermixer based on 100 parts by weight of the acidic base material (itaconic acid with a melting temperature of 162 to 164 ° C). After mixing for 20 minutes to adsorb the initiator to the acid group (S100), 1 part by weight of silicone oil was added to the supermixer and mixed at 1000 rpm for 10 minutes to prepare a surface-coated acid group-initiator masterbatch (S200).
2. 극성기를 가지는 EPDM의 제조2. Preparation of EPDM having a polar group
(실시예 1)(Example 1)
EPDM 100 중량부에 대하여 상기 제조예 1에 따라 제조된 산성기-개시제 마스터배치 3.21 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조(S300)하였다.3.21 parts by weight of the acid group-initiator masterbatch prepared according to Preparation Example 1 with respect to 100 parts by weight of EPDM was put into a twin-screw extruder set at a temperature of 150 to 220 ° C, and then EPDM substituted with an acid group was prepared through reaction extrusion (S300 ) was done.
(실시예 2)(Example 2)
EPDM 100 중량부에 대하여 상기 제조예 2에 따라 제조된 산성기-개시제 마스터배치 5.35 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조(S300)하였다.After putting 5.35 parts by weight of the acid group-initiator masterbatch prepared according to Preparation Example 2 with respect to 100 parts by weight of EPDM into a twin-screw extruder set at a temperature of 150 to 220 ° C, EPDM substituted with an acid group is prepared through reaction extrusion (S300 ) was done.
(실시예 3)(Example 3)
EPDM 100 중량부에 대하여 상기 제조예 3에 따라 제조된 산성기-개시제 마스터배치 3 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조(S300)하였다.After putting 3 parts by weight of the acid group-initiator masterbatch prepared according to Preparation Example 3 with respect to 100 parts by weight of EPDM into a twin screw extruder set at a temperature of 150 to 220 ° C, EPDM substituted with an acid group is prepared through reaction extrusion (S300 ) was done.
(비교예 1)(Comparative Example 1)
EPDM 100 중량부에 대하여 이타코닉산 3 중량부 및 2,5-디메틸-2,5-디(터트-부틸퍼옥시)헥산 0.06 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조하였다.Based on 100 parts by weight of EPDM, 3 parts by weight of itaconic acid and 0.06 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane were introduced into a twin-screw extruder set at a temperature of 150 to 220 °C, followed by reaction. EPDM substituted with an acidic group was prepared through extrusion.
(비교예 2)(Comparative Example 2)
EPDM 100 중량부에 대하여 이타코닉산 5 중량부 및 2,5-디메틸-2,5-디(터트-부틸퍼옥시)헥산 0.1 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조하였다.Based on 100 parts by weight of EPDM, 5 parts by weight of itaconic acid and 0.1 part by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane were introduced into a twin-screw extruder set at a temperature of 150 to 220 °C, followed by reaction. EPDM substituted with an acidic group was prepared through extrusion.
(비교예 3)(Comparative Example 3)
EPDM 100 중량부에 대하여 이타코닉산 5 중량부 및 디-터트-부틸 퍼옥사이드 0.08 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조하였다.Based on 100 parts by weight of EPDM, 5 parts by weight of itaconic acid and 0.08 parts by weight of di-tert-butyl peroxide were introduced into a twin-screw extruder set at a temperature of 150 to 220° C., and EPDM substituted with an acidic group was prepared through reaction extrusion.
3. 극성기를 가지는 EPDM의 평가3. Evaluation of EPDM with polar groups
상기 실시예 및 비교예에 따라 제조된 극성기를 가지는 EPDM의 치환율 등을 평가하였으며, 그 평가 방법 및 결과는 아래 [표 1]에 나타내었다.The substitution rate of EPDM having a polar group prepared according to the above Examples and Comparative Examples was evaluated, and the evaluation method and results are shown in [Table 1] below.
- 치환율(Grafting ratio) = (Wg-Wo)/Wo×100
- 치환효율(Grafting efficiency) = (Wg-Wo)/WA×100
- 겔 함량(Gel content) = Winsoluble/Wg×100
Wg: 압출된 산성기로 치환된 EPDM(IA-g-EPDM)을 아세톤에 담근 후 40℃에서 48시간 방치 후 추출/건조된 중량
Wo: 순수한 EPDM 중량
WA: 첨가된 산(Acid) 중량
Winsoluble: 압출된 IA-g-EPDM을 자일렌(Xylene)에 담근 후 24시간 끊인 후 추출/건조된 중량
- Grafting ratio = (Wg-Wo)/Wo×100
- Grafting efficiency = (Wg-Wo)/W A × 100
- Gel content = Winsoluble/Wg×100
Wg: Weight of extracted/dried EPDM (IA-g-EPDM) substituted with extruded acidic groups after being immersed in acetone and left at 40° C. for 48 hours
Wo: pure EPDM weight
W A : weight of acid added
Winsoluble: After immersing the extruded IA-g-EPDM in xylene and then boiling it for 24 hours, the extracted/dried weight
상기 [표 1]에서와 같이, 본 발명의 실시예에 따른 극성기를 가지는 EPDM은 비교예에 비하여 치환율이 향상되었을 뿐만 아니라 가교된 EPDM의 비율도 작아 효율적인 방법임을 알 수 있다.As shown in [Table 1], it can be seen that the EPDM having a polar group according to the embodiment of the present invention not only has an improved substitution rate compared to the comparative example, but also has a small ratio of crosslinked EPDM, which is an efficient method.
상술한 바와 같은, 본 발명의 바람직한 실시예에 따른 극성기를 가지는 EPDM의 제조 방법 및 이 방법에 의해 제조된 극성기를 가지는 EPDM을 상기한 설명 및 도면에 따라 설명하였지만 이는 예를 들어 설명한 것에 불과하며 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 변화 및 변경이 가능하다는 것을 이 분야의 통상적인 기술자들은 잘 이해할 수 있을 것이다.As described above, the manufacturing method of EPDM having a polar group according to a preferred embodiment of the present invention and the EPDM having a polar group manufactured by this method have been described according to the above description and drawings, but this is only an example and the present Those skilled in the art will understand that various changes and modifications are possible within the scope of the technical spirit of the invention.
Claims (6)
산성기 기재에 개시제를 혼합하는 단계(S100);
상기 혼합물에 실리콘 오일(Silicon oil)을 투입하여 산성기-개시제 마스터배치(Master batch)를 제조하는 단계(S200); 및
EPDM(Ethylene propylene diene monomer)에 상기 제조된 산성기-개시제 마스터배치를 혼합하여 산성기로 치환된 EPDM을 제조하는 단계(S300);를 포함하는 것을 특징으로 하는, 극성기를 가지는 EPDM의 제조 방법.
In the method for producing EPDM having a polar group,
mixing an initiator with an acidic base material (S100);
Preparing an acid group-initiator master batch by adding silicone oil to the mixture (S200); and
Ethylene propylene diene monomer (EPDM) is mixed with the prepared acid group-initiator masterbatch to prepare EPDM substituted with an acid group (S300); characterized in that it comprises a, a method for producing EPDM having a polar group.
상기 S100 단계는,
산성기 기재 100 중량부에 대하여, 개시제 1 ~ 5 중량부를 슈퍼믹서(Super mixer)에서 500 ~ 1000rpm으로 10 ~ 20분간 혼합하여 산성기에 개시제를 흡착시키는 것을 특징으로 하는, 극성기를 가지는 EPDM의 제조 방법.
According to claim 1,
In step S100,
A method for producing EPDM having a polar group, characterized in that 1 to 5 parts by weight of an initiator are mixed in a super mixer at 500 to 1000 rpm for 10 to 20 minutes with respect to 100 parts by weight of the acidic base material to adsorb the initiator to the acidic group. .
상기 S200 단계는,
산성기 기재 100 중량부를 기준으로, 실리콘 오일 1 ~ 5 중량부를 슈퍼믹서에 추가 투입한 후, 500 ~ 1000rpm으로 5 ~ 10분간 혼합하여 표면 코팅된 산성기-개시제 마스터배치를 제조하는 것을 특징으로 하는, 극성기를 가지는 EPDM의 제조 방법.
According to claim 1,
In the step S200,
Based on 100 parts by weight of the acid group substrate, 1 to 5 parts by weight of silicone oil are additionally added to the supermixer, and then mixed at 500 to 1000 rpm for 5 to 10 minutes to prepare a surface-coated acid group-initiator masterbatch , Method for producing EPDM having a polar group.
상기 S300 단계는,
EPDM 100 중량부에 대하여 산성기-개시제 마스터배치 3 ~ 5.35 중량부를 온도 150 ~ 220℃로 설정된 이축압출기에 투입한 후, 반응압출을 통해 산성기로 치환된 EPDM을 제조하는 것을 특징으로 하는, 극성기를 가지는 EPDM의 제조 방법.
According to claim 1,
In the step S300,
3 to 5.35 parts by weight of the acid group-initiator masterbatch based on 100 parts by weight of EPDM is put into a twin screw extruder set at a temperature of 150 to 220 ° C, and then EPDM substituted with an acid group is prepared through reaction extrusion, with a polar group A method for manufacturing EPDM.
상기 산성기 기재는 용융 온도가 162 ~ 164℃인 이타코닉산(Itaconic acid)을 사용하고,
상기 개시제는 1분 반감기 온도가 170 ~ 180℃인 액상형 퍼옥사이드계 개시제를 사용하는 것을 특징으로 하는, 극성기를 가지는 EPDM의 제조 방법.
According to claim 1,
The acid group substrate uses itaconic acid having a melting temperature of 162 to 164 ° C,
The method for producing EPDM having a polar group, characterized in that the initiator uses a liquid peroxide-based initiator having a 1-minute half-life temperature of 170 to 180 ° C.
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| KR1020210148994A KR102644448B1 (en) | 2021-11-02 | 2021-11-02 | Manufacturing method of epdm with polar group amd epdm with polar group using the same |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100379223B1 (en) | 2000-12-22 | 2003-04-08 | 삼성종합화학주식회사 | Thermoplastic Olefin Elastomer Resin Composition Having Good Adhesive Property And Method Of Preparing The Same |
| KR101644524B1 (en) | 2014-08-21 | 2016-08-02 | 한국생산기술연구원 | Compatibilizer comprising itaconic acid-grafted polyproylene copolymer and PP/EVOH blend using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100379223B1 (en) | 2000-12-22 | 2003-04-08 | 삼성종합화학주식회사 | Thermoplastic Olefin Elastomer Resin Composition Having Good Adhesive Property And Method Of Preparing The Same |
| KR101644524B1 (en) | 2014-08-21 | 2016-08-02 | 한국생산기술연구원 | Compatibilizer comprising itaconic acid-grafted polyproylene copolymer and PP/EVOH blend using the same |
Non-Patent Citations (1)
| Title |
|---|
| Elastomers and Composites, 2014, 49, 181-190. (2014.09.)* * |
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| KR102644448B1 (en) | 2024-03-07 |
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