KR102583331B1 - Ionic copolymer having antistatic properties and method for preparing antistatic composition using the same - Google Patents
Ionic copolymer having antistatic properties and method for preparing antistatic composition using the same Download PDFInfo
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- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
Abstract
본 발명은 이온성 공중합체 및 대전방지 조성물의 제조방법에 관한 것으로서, 폴리올레핀의 보란화 단계, 폴리올레핀의 관능화 단계, 고분자 개시제 제조단계, 공중합체 제조단계, 이온성 공중합체 제조단계, 대전방지제 조성물 제조단계를 거쳐 투명성을 손상시키지 않으며 이행(migration)이 적고 장기간 대전 방지성을 유지하면서 기계적 물성, 가공성 및 내후성이 우수한 이온성 공중합체 및 이를 이용한 대전방지 조성물의 제조방법에 관한 것이다.The present invention relates to a method for producing an ionic copolymer and an antistatic composition, including a boranization step of polyolefin, a functionalization step of polyolefin, a polymer initiator preparation step, a copolymer preparation step, an ionic copolymer preparation step, and an antistatic agent composition. It relates to an ionic copolymer that does not lose transparency through the manufacturing process, has little migration, maintains antistatic properties for a long period of time, and has excellent mechanical properties, processability, and weather resistance, and a method of manufacturing an antistatic composition using the same.
Description
본 발명은 이온성 공중합체 및 대전방지 조성물의 제조방법에 관한 것으로서, 더욱 상세하게는 투명성을 손상시키지 않으며 이행(migration)이 적고 장기간 대전 방지성을 유지하면서 기계적 물성, 가공성 및 내후성이 우수한 대전방지 특성을 갖는 이온성 공중합체 및 이를 이용한 대전방지 조성물의 제조방법에 관한 것이다.The present invention relates to a method for producing an ionic copolymer and an antistatic composition, and more specifically, to an antistatic composition that does not impair transparency, has little migration, maintains antistatic properties for a long period of time, and has excellent mechanical properties, processability, and weather resistance. It relates to an ionic copolymer having properties and a method for producing an antistatic composition using the same.
고분자 수지(polymer resin)는 값이 저렴하면서도 다른 재료에 비하여 가볍고 부식이 안되며, 성형이 비교적 자유로운 특징을 가지고 있어 기존의 목재, 금속 및 석재 등과 같은 고전적인 재료를 대체하여 최근에는 첨단 전자 재료로서도 널리 사용되고 있다. Polymer resin is inexpensive, lightweight compared to other materials, does not corrode, and has the characteristics of being relatively free to form, so it has recently been widely used as an advanced electronic material, replacing traditional materials such as wood, metal, and stone. It is being used.
이와 같은 고분자 관련 산업은 1950년대 석유화학공업 발전과 더불어 빠르게 발달되어 현재는 우리 일상 생활은 물론 모든 분야의 산업 발전에 없어서는 안 되는 위치를 차지하고 있다.This polymer-related industry developed rapidly along with the development of the petrochemical industry in the 1950s, and now occupies an indispensable position in industrial development in all fields as well as our daily lives.
대부분의 고분자 재료는 전기의 흐름이 어렵기 때문에 전기 절연체(insulation)로서 널리 사용되고 있다. 이러한 특성으로 인하여 정전기를 띠기 쉬운데, 이것은 물체들 간에 서로 접촉하거나 마찰 또는 분리하였을 때 양쪽에 극성이 다른 동일한 양의 전하가 대전되면서 일어나는 현상이다. Most polymer materials have difficulty in the flow of electricity, so they are widely used as electrical insulators. Due to this characteristic, it is easy to develop static electricity, which is a phenomenon that occurs when objects with different polarities are charged with the same amount of charge on both sides when they come in contact with each other, rub against each other, or separate.
즉, 두 물질의 사이에 전자의 이동이 일어나 한쪽 표면은 전자가 부족하게 되고, 다른 쪽 표면은 전자가 과잉이 된 상태로 전하의 분리가 일어나는 대전 현상에 의하여 발생하며, 고분자 수지에서 이와 같은 대전 현상이 발생하게 되면 전하의 이동이 일어나지 않아 정전기가 발생하게 되는 데 이러한 현상은 우리주변에서 늘 접할 수 있다. In other words, the movement of electrons between two materials occurs, causing one surface to lack electrons and the other surface to have an excess of electrons, resulting in a charging phenomenon in which charge separation occurs. Such charging occurs in polymer resins. When this phenomenon occurs, the movement of electric charges does not occur and static electricity is generated. This phenomenon can be seen all around us.
이런 대전 현상에 영향을 미치는 요인으로는 고분자 물질의 화학적 구조나 유전율에 따른 대전서열 및 크기 그리고, 접촉 면적, 접촉 시간, 마찰 속도, 접촉 물질 사이의 압력 등이 있다. Factors that affect this charging phenomenon include the chemical structure of the polymer material, charging sequence and size depending on the dielectric constant, contact area, contact time, friction speed, and pressure between contact materials.
하지만 이와 같은 정전기는 모든 산업 분야에서 문제를 발생시키기는 요인 중의 하나로 작용할 수 있다.However, such static electricity can act as one of the factors causing problems in all industrial fields.
일예로 고분자의 성형 과정에서 생산성을 저하시키는 요인으로 작용하기도 하고, 섬유 산업에서는 정전기에 의하여 섬유끼리 서로 달라붙거나, 반발하여 사용 또는 처리가 곤란하게 하며, 인화성 도료나, 용제 및 미분체의 이송 또는 분무시에 정전기가 발생하게 되면 방전된 불꽃에 의하여 화재 또는 폭발을 일으키기도 한다. For example, it acts as a factor that reduces productivity during the polymer molding process, and in the textile industry, static electricity causes fibers to stick to each other or repel each other, making use or processing difficult, and the transport of flammable paints, solvents, and fine powder. Alternatively, if static electricity is generated during spraying, a discharged spark may cause a fire or explosion.
이외에도 반도체 제조 공정에서 정전기의 방전에 의하여 회로를 망가뜨리며, 통신 기기 및 주요 계측기와 같은 정밀한 전자 제품 등의 오작동을 일으켜 대형 사고를 발생시킬 수 있고, 특히, 전자 통신 기술의 발달과 함께 그에 사용되는 부품들도 점차 소형화되어 소자 내부의 미세한 구조가 정전기에 의하여 파손되어 제품의 가동을 멈추게 하는 일이 자주 발생하여 왔다. In addition, in the semiconductor manufacturing process, electrostatic discharge can damage circuits and cause malfunctions in precision electronic products such as communication devices and major measuring instruments, which can cause major accidents. In particular, with the development of electronic communication technology, the devices used therein can be damaged. As parts have become increasingly smaller, it has often occurred that the fine structure inside the device is damaged by static electricity, stopping the operation of the product.
따라서 고분자 수지의 성형과정이나 합성섬유 가공의 경우에는 접지시키는 방법이 가장 널리 쓰이지만, 전기부 폴라(polar) 도체의 접지에 의한 방법으로는 대전방지가 되지 않기 때문에 마찰이 일어나는 부위를 대전량이 적은 재료를 쓰는 것 등으로 대전방지 효과를 얻을 수 있다. 그리고 고주파나 고전압을 발생시켜 전극사이에서 코로나 방전으로 대전되어 고분자 재료 주변의 공기를 이온화 함으로서 반대 극성의 전하를 부착시켜 중화하는 것으로 정전기를 제거하는 방법이 있으나 생산 공정 중에는 쓰일 수 있지만, 사용중인 제품에는 이용 하지 못하는 사용상의 제약이 있다. Therefore, in the case of polymer resin molding or synthetic fiber processing, the grounding method is most widely used, but since the method of grounding the polar conductor in the electrical part does not prevent charging, the area where friction occurs must be moved to a place where there is less charge. An anti-static effect can be achieved by using materials, etc. There is also a method of removing static electricity by generating a high frequency or high voltage to ionize the air around the polymer material by generating a corona discharge between the electrodes, thereby attaching and neutralizing charges of the opposite polarity. This can be used during the production process, but the product in use There are usage restrictions that prevent it from being used.
다음으로 흑연이나 도전성이 있는 금속 분말을 합성수지 등과 함께 성형하여 도전성을 부여하여 대전방지 효과를 나타내는 방법이 있으나, 가격이 비싸면서도 첨가량이 많아 원가가 높아지며, 최종 제품의 물성에도 영향을 주기 쉽다. 또한, 투명한 용도로는 사용하지 못하는 등 색상에도 여러 가지 제한을 받는다. 그러나 도전성 재료가 꼭 필요한 반도체의 포장재 등에 일부 사용되고 있다. Next, there is a method to exhibit an antistatic effect by molding graphite or conductive metal powder with synthetic resin to give conductivity, but it is expensive and has a large amount of addition, which increases the cost and tends to affect the physical properties of the final product. In addition, there are various restrictions on color, such as not being able to be used for transparent purposes. However, it is partially used in semiconductor packaging materials that require conductive materials.
그밖에 폴리아세틸렌(polyacetylene) 필름에 할로겐 원소를 도핑하였을 때, 전기전도도가 급격히 증가하는 현상이 알려진 이후 특수한 대전방지 효과 즉, 도전성이 필요한 경우에는 공액 이중결합을 갖는 폴리아세틸렌, 폴리아닐린(polyaniline), 폴리피롤(polypyrrole), 폴리사이오펜(polythiophene) 등과 같은 전도성 고분자들이 주목을 받고 있고 또한, 개발되어 일부 사용되고 있으나 안정성이 좋지 않고, 용해성이 낮은 것은 물론 가공이 어려운 것이 문제로 되어있다.In addition, since it was known that the phenomenon of a rapid increase in electrical conductivity when polyacetylene film was doped with a halogen element, when special antistatic effect, that is, conductivity, was required, polyacetylene, polyaniline, and polypyrrole with conjugated double bonds were used. Conductive polymers such as polypyrrole and polythiophene are attracting attention and have been developed and are partially used, but problems include poor stability, low solubility, and difficulty in processing.
현재로서는 저분자형 대전방지제를 고분자 수지 내부에 혼입시키거나, 표면에 얇게 도포함으로서 표면의 흡습성이나 이온성을 높여 전하의 누설이 쉽게 되도록 하여 대전방지 효과를 나타내게 함으로써 용도에 맞도록 여러 가지 대전방지제를 사용하여 정전기를 제어하는 방법이 널리 사용되고 있다.Currently, various antistatic agents are available to suit different purposes by incorporating low-molecular-type antistatic agents into the polymer resin or applying them thinly on the surface to increase the hygroscopicity or ionicity of the surface to facilitate leakage of electric charges and to exhibit antistatic effects. Methods for controlling static electricity are widely used.
하지만 종래의 대전방지제는 세척이나 마찰 등 어떤 이유에서 표면으로부터 제거되면 대전방지 효과는 없어지게 된다. 또한, 대전방지제가 표면으로 너무 많이 표출되었을 경우 피접촉 물체를 오염시키거나 인쇄적성 및 끈적임 등을 나타내어 물성을 저하시키고, 대전방지제를 첨가하였어도 고분자 재료 표면으로 나오지 못하거나 그 양이 적으면 대전방지 효과를 발휘하지 못하게 되는 점 등이 단점을 갖는다.However, if the conventional antistatic agent is removed from the surface for any reason such as washing or friction, the antistatic effect is lost. In addition, if too much of the antistatic agent is expressed on the surface, it contaminates the object in contact or reduces physical properties by showing printability and stickiness, and even if the antistatic agent is added, it does not come out to the surface of the polymer material or if the amount is small, the antistatic agent is prevented. It has disadvantages such as the fact that it is not effective.
이런 특성을 개선하기 위하여 지금까지 개발되어 특허 출원된 선행기술과 특허문헌을 살펴보면 다음과 같다. In order to improve these characteristics, the prior art and patent documents that have been developed and patented so far are examined as follows.
따라서 본 발명이 이루고자 하는 기술적 과제는 전술한 필요성을 해결하고자 안출된 것으로서 이온성 공중합체를 대전방지 조성물에 배합함으로써 투명성을 손상시키지 않으며 이행이 적고 장기간 대전 방지성을 유지하면서 기계적 물성, 가공성 및 내후성이 우수한 대전방지 특성을 갖는 이온성 공중합체 및 이를 이용한 대전방지 조성물의 제조방법을 제공함에 본 발명의 목적이 있다. Therefore, the technical problem to be achieved by the present invention was created to solve the above-mentioned need. By mixing an ionic copolymer into an antistatic composition, transparency is not impaired, migration is small, and antistatic properties are maintained for a long period of time, while maintaining mechanical properties, processability, and weather resistance. The purpose of the present invention is to provide an ionic copolymer with excellent antistatic properties and a method for producing an antistatic composition using the same.
상기한 목적을 달성하기 위한 본 발명은, 가스 퍼징(gas purging) 장비, 교반기(stirrer), 온도조절기(thermostat)가 장착된 반응기(reactor)에 불활성 기체(inert gas)를 퍼징시키면서 중합용매(polymerization solvent) 10,000중량부와, 체인 트랜스퍼제(chain transfer agent) 10~300중량부를 투여한 다음, 단량체(monomer)를 공급하여 1~2기압으로 유지시키고 반응기 온도를 20~100℃로 상승시킨다. 상기 반응기에 지르코늄 화합물(zirconium compound)인 촉매(catalyst) 5~40중량부와 알킬알루미녹산(alkylaluminoxane)에서 선택되어지는 조촉매(co-catalyst) 10~60중량부를 투입하여 50~500RPM의 속도로 교반하면서 중합을 개시하고, 반응기 압력은 단량체(monomer)를 연속적으로 공급하여 1~2기압으로 온도는 20~100℃를 유지하면서 1~24시간 동안 중합반응을 진행한다. 반응이 완료된 후, 상기 반응기 하부에서 추출한 중합반응액에 알코올(alcohol) 10~100중량부를 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑(steam stripping) 처리하여 공중합체를 용매에서 분리한 다음, 50~100℃에서 12~48시간 감압 하에 건조시켜 보란-말단 폴리올레핀(borane-terminated polyolefin)을 제조하는 폴리올레핀의 보란화 단계와;In order to achieve the above object, the present invention purges an inert gas into a reactor equipped with gas purging equipment, a stirrer, and a thermostat, thereby purging the polymerization solvent. After administering 10,000 parts by weight of solvent and 10 to 300 parts by weight of chain transfer agent, monomer is supplied to maintain the pressure at 1 to 2 atm and the reactor temperature is raised to 20 to 100°C. 5 to 40 parts by weight of a catalyst, which is a zirconium compound, and 10 to 60 parts by weight of a co-catalyst selected from alkylaluminoxane were added to the reactor and the reactor was reacted at a speed of 50 to 500 RPM. Polymerization is initiated while stirring, and the polymerization reaction proceeds for 1 to 24 hours while maintaining the reactor pressure at 1 to 2 atmospheres and the temperature at 20 to 100°C by continuously supplying monomers. After the reaction was completed, 10 to 100 parts by weight of alcohol was added to the polymerization reaction liquid extracted from the bottom of the reactor to terminate the reaction, and the reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then A boranization step of polyolefin to produce borane-terminated polyolefin by drying under reduced pressure at ~100°C for 12 to 48 hours;
가스 퍼징장비, 적가장치, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 반응용매(reaction solvent) 100,000중량부와, 폴리올레핀의 보란화 단계에서 제조된 보란-말단 폴리올레핀 20,000~40,000중량부를 순차적으로 투여한 다음, 50~500RPM의 속도로 교반하면서 증류수 20,000~40,000중량부, 소디움 하이드록사이드(sodium hydroxide)나 포타슘 하이드록사이드(potassium hydroxide) 등의 염기(base) 2,000~8,000중량부, 알코올 2,000~8,000중량부를 첨가한 후, 반응온도를 -10~0℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 10~30중량% : 물함량 90~70중량%) 15,000~40,000중량부를 30~60분간 적가한 다음, 반응 온도를 30~60℃로 상승시켜 50~500RPM의 속도로 교반하면서 4~12시간 동안 더 반응을 진행한 후, 생성된 반응물을 여과/세척하여 50~100℃에서 12~48시간 감압 하에 건조시켜 하이드록시-말단 폴리올레핀(hydroxy-terminated polyolefin)을 제조하는 폴리올레핀의 관능화 단계와;While purging an inert gas in a reactor equipped with gas purging equipment, a dropper, a stirrer, and a temperature controller, 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the borane-terminated polyolefin prepared in the boranization step of polyolefin were sequentially added. After administration, while stirring at a speed of 50 to 500 RPM, add 20,000 to 40,000 parts by weight of distilled water, 2,000 to 8,000 parts by weight of a base such as sodium hydroxide or potassium hydroxide, and alcohol. After adding 2,000 to 8,000 parts by weight, the reaction temperature was lowered to -10 to 0°C, and 15,000 to 40,000 parts by weight of hydrogen peroxide aqueous solution (10 to 30 wt% of hydrogen peroxide: 90 to 70 wt% of water content) was added to 30%. After adding dropwise for ~60 minutes, the reaction temperature was raised to 30~60℃ and the reaction proceeded for a further 4~12 hours while stirring at a speed of 50~500RPM. Then, the resulting reactant was filtered/washed and stored at 50~100℃. A functionalization step of polyolefin to produce hydroxy-terminated polyolefin by drying under reduced pressure for 12 to 48 hours;
가스 퍼징장비, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서, 반응용매 100,000중량부와 폴리올레핀의 관능화 단계에서 제조된 하이드록시-말단 폴리올레핀 20,000~40,000 중량부를 투여한 다음, 반응기 온도를 30~60℃로 상승시키고 50~500RPM의 속도로 6~24시간 동안 교반시킨 다음, 상기 반응기에 소디움 나프탈라이드(sodium naphthalenide)나 리튬 나프탈라이드(lithium naphthalenide), 칼륨 나프탈라이드(potassium naphthalenide) 등에서 선택 되어지는 환원제 1,000~10,000중량부를 투여하여 반응온도를 30~60℃로 유지시키고 50~500RPM의 속도로 3~12시간 동안 교반한 후 생성된 혼합물을 여과/세척하여 50~100℃에서 12~48시간 동안 감압 하에 건조시켜 고분자 개시제(initiator)를 제조하는 고분자 개시제 제조단계와;While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of the reaction solvent and 20,000 to 40,000 parts by weight of the hydroxy-terminated polyolefin prepared in the functionalization step of the polyolefin were added, and then the reactor temperature was adjusted. Raise the temperature to 30~60℃ and stir at a speed of 50~500RPM for 6~24 hours, then add sodium naphthalenide, lithium naphthalenide, or potassium naphthalenide to the reactor. ), maintain the reaction temperature at 30~60℃ by administering 1,000~10,000 parts by weight of reducing agent selected from ), stir at a speed of 50~500RPM for 3~12 hours, filter/wash the resulting mixture, and store at 50~100℃. A polymer initiator preparation step of preparing a polymer initiator by drying under reduced pressure for 12 to 48 hours;
가스 퍼징장비, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 반응용매 100,000중량부와 고분자 개시제 제조단계에서 제조된 고분자 개시제 20,000~40,000중량부, 알켄 옥사이드(alkene oxide) 10,000~90,000중량부, 금속 하이드라이드(metal hydride) 100~1,000중량부를 가한 후, 반응기 온도를 60~100℃로 상승시켜 50~500RPM의 속도로 24~60시간 동안 반응시킨 다음, 알코올 1,000~2,000중량부를 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척한 다음, 50~100℃에서 12~60시간 동안 감압 하에 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하는 공중합체 제조단계와;While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of the reaction solvent, 20,000 to 40,000 parts by weight of the polymer initiator prepared in the polymer initiator manufacturing step, and 10,000 to 90,000 parts by weight of alkene oxide. After adding 100 to 1,000 parts by weight of metal hydride, the temperature of the reactor was raised to 60 to 100°C and reaction was performed at a rate of 50 to 500 RPM for 24 to 60 hours, and then 1,000 to 2,000 parts by weight of alcohol was added for reaction. A copolymer preparation step of filtering and washing the resulting mixture and then drying it under reduced pressure at 50-100°C for 12-60 hours to produce a polyolefin-polyalkenoxide copolymer;
교반기, 온도조절기가 장착된 반응기에 분산용매 100,000중량부와 상기 공중합체 제조단계에서 제조된 폴리올레핀-폴리알켄옥사이드 공중합체 20,000~40,000중량부를 투여한 다음 반응기 온도를 20~60℃로 상승시키고 50~500RPM의 속도로 1~6시간 동안 교반한 후 상기 반응기에 이온성 액체(ionic liquid) 200~600중량부를 투여하여 반응기 온도를 20~60℃로 유지시키고 50~500RPM의 속도로 1~6시간 동안 교반한 반응물을 여과, 세척 및 50~100℃에서 12~24시간 건조하여 이온성 공중합체를 제조하는 이온성 공중합체 제조단계와;100,000 parts by weight of the dispersion solvent and 20,000 to 40,000 parts by weight of the polyolefin-polyalkenoxide copolymer prepared in the copolymer production step were added to a reactor equipped with a stirrer and a temperature controller, then the reactor temperature was raised to 20 to 60 ° C. and the temperature of the reactor was raised to 50 to 50 ° C. After stirring for 1 to 6 hours at a speed of 500 RPM, 200 to 600 parts by weight of ionic liquid was added to the reactor to maintain the reactor temperature at 20 to 60 ° C. and stirred at a speed of 50 to 500 RPM for 1 to 6 hours. An ionic copolymer preparation step of preparing an ionic copolymer by filtering, washing, and drying the stirred reactant at 50 to 100° C. for 12 to 24 hours;
니더(Kneader)나 헨셀(Hensel), 밴버리(Banbury) 등의 혼합 믹서(mixer)에 폴리올레핀(polyolefin) 수지나 에틸렌공중합체(ethylene copolymer), 합성고무(synthetic rubber)에서 선택되어지는 고분자 중합체 100,000중량부와, 전기 전도성 충진제 100~500중량부, 이온성 공중합체 제조단계에서 제조된 이온성 공중합체 20,000~40,000중량부, 황화합물 중에서 단독 또는 2종 이상 혼합사용 되는 산화방지제 50~200중량부, 지방산 금속염(fatty acid metal salt)에서 선택되어지는 활제(lubricant) 100~1,400중량부를 순차적으로 투여하고 80~200℃ 온도에서 5~60분간 혼련한 덩어리 반죽을 일축(single screw)이나 이축 압출기(twin screw extruder)로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하는 대전방지제 조성물 제조단계를 거쳐; 대전방지 특성을 갖는 이온성 공중합체 및 이를 이용한 조성물을 용이하게 제조할 수 있다.100,000 weight of polymer selected from polyolefin resin, ethylene copolymer, and synthetic rubber in a mixing mixer such as Kneader, Hensel, Banbury, etc. 100 to 500 parts by weight of electrically conductive filler, 20,000 to 40,000 parts by weight of ionic copolymer prepared in the ionic copolymer manufacturing stage, 50 to 200 parts by weight of antioxidant used alone or in combination of two or more of the sulfur compounds, and fatty acid. 100 to 1,400 parts by weight of a lubricant selected from fatty acid metal salts is sequentially administered and kneaded for 5 to 60 minutes at a temperature of 80 to 200°C. The lump dough is then extruded using a single screw or twin screw extruder. Extruder) and go through the antistatic agent composition manufacturing step of producing antistatic agent composition pellets of 3 to 5mm in size through extrusion molding; Ionic copolymers with antistatic properties and compositions using them can be easily manufactured.
이상에서 설명한 바와 같이 본 발명은 투명성을 손상시키지 않으면서 이행(migration)이 적고 장기간 대전 방지성을 유지하는 기계적 물성, 가공성 및 내후성이 우수한 대전방지 특성을 갖는 이온성 공중합체 및 이를 이용한 대전방지 조성물을 용이하게 제조하는 효과를 가지고 있다.As described above, the present invention relates to an ionic copolymer having antistatic properties with excellent mechanical properties, processability, and weather resistance that exhibits low migration and long-term antistatic properties without compromising transparency, and an antistatic composition using the same. It has the effect of making it easy to manufacture.
도1은 본 발명의 실시 방법을 예시한 공정흐름도.1 is a process flow diagram illustrating a method of implementing the present invention.
본 발명은, 가스 퍼징(gas purging) 장비, 교반기(stirrer), 온도조절기(thermostat)가 장착된 반응기(reactor)에 불활성 기체(inert gas)를 퍼징시키면서 중합용매(polymerization solvent) 10,000중량부와 체인 트랜스퍼제(chain transfer agent) 10~300중량부를 투여한 다음 단량체(monomer)를 공급하여 1~2기압으로 유지시키고 반응기 온도를 20~100℃를 상승시킨다. 상기 반응기에 지르코늄 화합물(zirconium compound)에서 선택되어지는 촉매(catalyst) 5~40중량부와 알킬알루미녹산(alkylaluminoxane)에서 선택되어지는 조촉매(co-catalyst) 10~60중량부를 투입하여 50~500RPM의 속도로 교반하면서 중합을 개시하고 반응기 압력은 단량체(monomer)를 연속적으로 공급하여 1~2기압으로, 온도는 20~100℃를 유지하면서 1~24시간 동안 중합반응을 진행한다. 반응이 완료된 후 상기 반응기 하부에서 추출한 중합반응액에 알코올(alcohol) 10~100중량부를 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑(steam stripping) 처리하여 공중합체를 용매에서 분리한 다음, 50~100℃에서 12~48시간 감압 하에 건조시켜 보란-말단 폴리올레핀(borane-terminated polyolefin)을 제조하는 폴리올레핀의 보란화 단계와;The present invention purges an inert gas into a reactor equipped with gas purging equipment, a stirrer, and a thermostat, while purging 10,000 parts by weight of a polymerization solvent and a chain. After administering 10 to 300 parts by weight of a chain transfer agent, monomer is supplied to maintain the pressure at 1 to 2 atm, and the reactor temperature is raised to 20 to 100°C. 5 to 40 parts by weight of a catalyst selected from zirconium compounds and 10 to 60 parts by weight of a co-catalyst selected from alkylaluminoxane were added to the reactor at 50 to 500 RPM. The polymerization is initiated while stirring at a speed of , and the polymerization reaction proceeds for 1 to 24 hours while maintaining the reactor pressure at 1 to 2 atm by continuously supplying monomers and the temperature at 20 to 100°C. After the reaction was completed, 10 to 100 parts by weight of alcohol was added to the polymerization reaction liquid extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then the copolymer was separated from the solvent. A boranization step of polyolefin to produce borane-terminated polyolefin by drying under reduced pressure at 100°C for 12 to 48 hours;
가스 퍼징장비, 적가장치, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 반응용매(reaction solvent) 100,000중량부와, 폴리올레핀의 보란화 단계에서 제조된 보란-말단 폴리올레핀 20,000~40,000중량부를 순차적으로 투여한 다음, 50~500RPM의 속도로 교반하면서 증류수 20,000~40,000중량부, 소디움 하이드록사이드(sodium hydroxide)나 포타슘 하이드록사이드(potassium hydroxide) 등의 염기(base) 2,000~8,000중량부, 알코올 2,000~8,000중량부를 첨가한 후 반응온도를 -10~0℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 10~30중량% : 물함량 90~70중량%) 15,000~40,000중량부를 30~60분간 적가한 다음, 반응 온도를 30~60℃로 상승시켜 50~500RPM의 속도로 교반하면서, 4~12시간 동안 더 반응을 진행한 후 생성된 반응물을 여과, 세척 및 50~100℃에서 12~48시간 감압 하에 건조시켜 하이드록시-말단 폴리올레핀(hydroxy-terminated polyolefin)을 제조하는 폴리올레핀의 관능화 단계와;While purging an inert gas in a reactor equipped with gas purging equipment, a dropper, a stirrer, and a temperature controller, 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the borane-terminated polyolefin prepared in the boranization step of polyolefin were sequentially added. After administration, while stirring at a speed of 50 to 500 RPM, add 20,000 to 40,000 parts by weight of distilled water, 2,000 to 8,000 parts by weight of a base such as sodium hydroxide or potassium hydroxide, and alcohol. After adding 2,000 to 8,000 parts by weight, lower the reaction temperature to -10 to 0℃, and add 15,000 to 40,000 parts by weight of hydrogen peroxide aqueous solution (10 to 30 wt% of hydrogen peroxide: 90 to 70 wt% of water content). After adding dropwise for 60 minutes, the reaction temperature was raised to 30~60℃ and the reaction proceeded for a further 4~12 hours while stirring at a speed of 50~500RPM. The resulting reactant was filtered, washed, and incubated at 50~100℃ for 12 hours. Functionalizing the polyolefin to produce a hydroxy-terminated polyolefin by drying under reduced pressure for ~48 hours;
가스퍼징장비, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 반응용매 100,000중량부와 폴리올레핀의 관능화 단계에서 제조된 하이드록시-말단 폴리올레핀 20,000~40,000중량부를 투여하고, 반응기 온도를 30~60℃로 상승시키고 50~500RPM의 속도 6~24시간 동안 교반시킨 다음, 상기 반응기에 소디움 나프탈라이드(sodium naphthalenide)나 리튬 나프탈라이드(lithium naphthalenide), 칼륨 나프탈라이드(potassium naphthalenide) 등에서 선택 되어지는 환원제 1,000~10,000중량부를 투여하여 반응온도를 30~60℃로 유지시키고 50~500RPM의 속도로 3~12시간 동안 교반한 후 생성된 혼합물을, 여과, 세척하여 50~100℃에서 12~48시간 동안 감압 하에 건조시켜 고분자 개시제(initiator)를 제조하는 고분자 개시제 제조단계와;While purging an inert gas, 100,000 parts by weight of the reaction solvent and 20,000 to 40,000 parts by weight of the hydroxy-terminated polyolefin prepared in the functionalization step of the polyolefin were added to a reactor equipped with gas purging equipment, a stirrer, and a temperature controller, and the reactor temperature was adjusted to 30~40%. Raise the temperature to 60℃ and stir at a speed of 50~500RPM for 6~24 hours, then add sodium naphthalenide, lithium naphthalenide, potassium naphthalenide, etc. to the reactor. 1,000 to 10,000 parts by weight of the reducing agent was administered to maintain the reaction temperature at 30 to 60°C and stirred at a speed of 50 to 500 RPM for 3 to 12 hours. The resulting mixture was filtered and washed and stirred at 50 to 100°C for 12 to 12 hours. A polymer initiator preparation step of preparing a polymer initiator by drying under reduced pressure for 48 hours;
가스 퍼징장비, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서By purging inert gas into a reactor equipped with gas purging equipment, stirrer, and temperature controller,
반응용매 100,000중량부와 고분자 개시제 제조단계에서 제조된 고분자 개시제 20,000~40,000중량부, 알켄 옥사이드(alkene oxide) 10,000~90,000중량부, 금속 하이드라이드(metal hydride) 100~1,000중량부를 가한 후, 반응기 온도를 60~100℃로 상승시켜 50~500RPM의 속도로 24~60시간 동안 반응시킨 다음 알코올 1,000~2,000중량부를 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척한 다음, 50~100℃에서 12~60시간 동안 감압 하에 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하는 공중합체 제조단계와;After adding 100,000 parts by weight of the reaction solvent, 20,000 to 40,000 parts by weight of the polymer initiator prepared in the polymer initiator production step, 10,000 to 90,000 parts by weight of alkene oxide, and 100 to 1,000 parts by weight of metal hydride, the reactor temperature Raise the temperature to 60-100℃ and react at a speed of 50-500RPM for 24-60 hours. Then, 1,000-2,000 parts by weight of alcohol is added to complete the reaction. The mixture is filtered and washed, and then reacted at 50-100℃ for 12-60 hours. A copolymer preparation step of preparing a polyolefin-polyalkenoxide copolymer by drying under reduced pressure for a period of time;
교반기, 온도조절기가 장착된 반응기에 분산용매 100,000중량부와 상기 공중합체 제조단계에서 제조된 폴리올레핀-폴리알켄옥사이드 공중합체 20,000~40,000중량부를 투여한 다음, 반응기 온도를 20~60℃로 상승시키고 50~500RPM의 속도로 1~6시간 동안 교반한 후, 상기 반응기에 이온성 액체(ionic liquid) 200~600중량부를 투여하여 반응기 온도를 20~60℃로 유지시키고 50~500RPM의 속도로 1~6시간 동안 교반한 반응물을, 여과, 세척 및 50~100℃에서 12~24시간 건조하여 이온성 공중합체를 제조하는 이온성 공중합체 제조단계와;100,000 parts by weight of the dispersion solvent and 20,000 to 40,000 parts by weight of the polyolefin-polyalkene oxide copolymer prepared in the copolymer production step were added to a reactor equipped with a stirrer and temperature controller, then the reactor temperature was raised to 20 to 60 ° C. and 50 ° C. After stirring for 1 to 6 hours at a speed of ~500 RPM, 200 to 600 parts by weight of ionic liquid was added to the reactor to maintain the reactor temperature at 20 to 60°C and stirred at a speed of 50 to 500 RPM for 1 to 6 hours. An ionic copolymer preparation step of preparing an ionic copolymer by filtering, washing, and drying the reactant stirred for a period of time at 50 to 100° C. for 12 to 24 hours;
니더(Kneader)나 헨셀(Hensel), 밴버리(Banbury) 등의 혼합 믹서(mixer)에 폴리올레핀(polyolefin)수지나 에틸렌공중합체(ethylene copolymer), 합성고무(synthetic rubber)에서 선택되어지는 고분자 중합체 100,000중량부와, 전기 전도성 충진제 100~500중량부, 이온성 공중합체 제조단계에서 제조된 이온성 공중합체 20,000~40,000 중량부, 황화합물 중에서 단독 내지 2종 이상 혼합사용 되는 산화방지제 50~200중량부, 지방산 금속염(fatty acid metal salt)에서 선택되어지는 활제(lubricant) 100~1,400중량부를 순차적으로 투여하고, 80~200℃ 온도에서 5~60분간 혼련한 덩어리 반죽을 일축(single screw)이나 이축 압출기(twin screw extruder)로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하는 대전방지제 조성물 제조단계를 거쳐; 이온성 공중합체 및 대전방지 조성물을 용이하게 제조할 수 있다.100,000 weight of polymer selected from polyolefin resin, ethylene copolymer, and synthetic rubber in a mixing mixer such as Kneader, Hensel, Banbury, etc. 100 to 500 parts by weight of an electrically conductive filler, 20,000 to 40,000 parts by weight of the ionic copolymer prepared in the ionic copolymer manufacturing step, 50 to 200 parts by weight of an antioxidant used alone or in combination of two or more of the sulfur compounds, and fatty acids. 100 to 1,400 parts by weight of a lubricant selected from fatty acid metal salts is sequentially administered, and the lump dough is kneaded for 5 to 60 minutes at a temperature of 80 to 200°C and extruded using a single screw or twin screw extruder. Going through the antistatic agent composition manufacturing step of producing antistatic agent composition pellets of 3 to 5mm in size through extrusion molding by transferring them to a screw extruder; Ionic copolymers and antistatic compositions can be easily prepared.
본 발명을 실시예를 도1에 의거 상세히 설명하면 다음과 같다The present invention will be described in detail with reference to Figure 1 as an embodiment as follows.
가스 퍼징(gas purging) 장비, 교반기(stirrer), 온도조절기(thermostat)가 장착된 반응기(reactor)에 질소(nitrogen)나, 아르곤(argon), 네온(neon) 등에서 선택되어지는 불활성 기체(inert gas)를 퍼징시키면서 펜탄(pentane)이나, 헥산(hexane), 헵탄(heptane), 옥탄(octane), 시클로헥산(cyclohexane), 벤젠(benzene), 톨루엔(toluene), 크실렌(xylene) 등의 유기용매(organic solvent)에서 선택되어지는 중합용매(polymerization solvent) 10,000중량부와 트리에틸보란(triethylborane)이나, 트리프로필보란(tripropylborane), 디메시틸보란(dimesitylborane), 9-보라비실코노난(9-borabicylcononane), 보론 디피로메텐(boron dipyrromethene), 텍실보란(thexylborane), 디시아밀보란 (disiamylborane) 등의 보란 컴파운드에서 선택되어지는 체인 트랜스퍼제(chain transfer agent) 10~300중량부를 투여한 다음 에틸렌(ethylene)이나, 프로필렌(propylene), 부텐(butene), 시클로펜탄(cyclopentene), 4-메틸-1-펜텐(4-methyl-1-pentene) 등의 알켄(alkene) 단독 또는 2종 이상 선택되어지는 단량체(monomer)를 공급하여, 1~2기압으로 유지시키고 반응기 온도를 20~100℃로 상승시킨다. An inert gas selected from nitrogen, argon, neon, etc. is supplied to a reactor equipped with gas purging equipment, stirrer, and thermostat. ) while purging organic solvents such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene ( 10,000 parts by weight of polymerization solvent selected from organic solvent and triethylborane, tripropylborane, dimesitylborane, or 9-borabicylcononane ), 10 to 300 parts by weight of a chain transfer agent selected from borane compounds such as boron dipyromethene, thexylborane, and disiamylborane, and then added with ethylene. ) or monomers selected from monomers such as propylene, butene, cyclopentene, 4-methyl-1-pentene, etc. (monomer) is supplied, the pressure is maintained at 1 to 2 atm, and the reactor temperature is raised to 20 to 100°C.
상기 반응기에 라세미-디메틸실릴비스(1-인데닐)지르코늄 디클로라이드[rac-dimethylsilylbis(1-indenyl)zirconium dichloride], 라세미-디메틸실릴비스[1-(2-메틸-4,5-벤조인데닐)]지르코늄 디클로라이드{rac-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride}, 라세미-디메틸실릴비스(2-에틸-4-페닐인데닐)지르코늄 디클로라이[rac-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride], 라세미-디메틸실릴비스[1-(2-n-프로필-4-(1-나프틸)인데닐)]지르코늄 디클로라이드 {rac-dimethylsilyl-bis[l-(2-n-propyl-4-(1-naphthyl)indenyl)]zirconium dichloride}, 라세미-디메틸실릴비스[1-(2-에틸-4-(9-페난트릴)인데닐)]지르코늄 디클로라이드{rac-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride}, 라세미-디메틸실릴비스[1-(2-n-프로필-4-(9-페난트릴)인데닐)]지르코늄 디클로라이드{rac-dimethylsilylbis[l-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride} 등의 지르코늄 화합물에서 선택되어지는 촉매(catalyst) 5~40중량부와 메틸알루미녹산(methylaluminoxane)이나, 2,6-디-터트-부틸-4-메틸페놀 변성 메틸알루미녹산(2,6-di-tert-butyl-4-methylphenol modified methylaluminoxane), 폴리메틸알루미녹산(polymethylaluminoxane) 등의 알루미녹산에서 선택되어지는 조촉매(co-catalyst) 10~60중량부를 투입하여 50~500RPM의 속도로 교반하면서 중합을 개시하고, 반응기 압력은 단량체(monomer)를 연속적으로 공급하여 1~2기압으로, 온도는 20~100℃를 유지하면서 1~24시간 동안 중합반응을 진행한다. In the reactor, racemic-dimethylsilylbis(1-indenyl)zirconium dichloride [rac-dimethylsilylbis(1-indenyl)zirconium dichloride], racemic-dimethylsilylbis[1-(2-methyl-4,5-benzo) indenyl)] zirconium dichloride Ly[rac-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride], racemic-dimethylsilylbis[1-(2-n-propyl-4-(1-naphthyl)indenyl)]zirconium dichloride { rac-dimethylsilyl-bis[l-(2-n-propyl-4-(1-naphthyl)indenyl)]zirconium dichloride}, racemic-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl) ) indenyl)] zirconium dichloride {rac-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride}, racemic-dimethylsilylbis[1-(2-n-propyl- 4-(9-phenanthryl)indenyl)]zirconium dichloride {rac-dimethylsilylbis[l-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride}, which is selected from zirconium compounds such as 5 to 40 parts by weight of catalyst and methylaluminoxane or 2,6-di-tert-butyl-4-methylphenol modified methylaluminoxane Polymerization is initiated by adding 10 to 60 parts by weight of a co-catalyst selected from aluminoxane such as modified methylaluminoxane and polymethylaluminoxane and stirring at a speed of 50 to 500 RPM. The reactor pressure is adjusted to the monomer pressure. (monomer) is continuously supplied and the polymerization reaction proceeds for 1 to 24 hours while maintaining the pressure at 1 to 2 atmospheres and the temperature at 20 to 100°C.
반응이 완료된 후 상기 반응기 하부에서 추출한 중합반응액에 메탄올(methanol)이나 에탄올(ethanol), 프로판올(propanol), 이소프로필 알코올(isopropyl alcohol) 등에서 선택되어지는 알코올(alcohol) 10~100중량부를 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑(steam stripping) 처리하여 공중합체를 용매에서 분리한 다음 50~100℃에서 12~48시간 감압 하에 건조시켜 보란-말단 폴리올레핀(borane-terminated polyolefin)을 제조하는 폴리올레핀의 보란화 단계와;After the reaction is completed, 10 to 100 parts by weight of alcohol selected from methanol, ethanol, propanol, isopropyl alcohol, etc. is added to the polymerization reaction solution extracted from the bottom of the reactor. After the reaction is completed, the reaction mixture is subjected to steam stripping to separate the copolymer from the solvent, and then dried under reduced pressure at 50 to 100°C for 12 to 48 hours to produce borane-terminated polyolefin. The boranization step of;
가스 퍼징장비, 적가장치, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 디에틸 에테르(diethyl ether)나 에틸아세테이트(ethyl acetate), 테트라하이드로퓨란(tetrahydrofuran), 메틸에틸케톤(methyl ethyl ketone) 등에서 선택되어지는 반응용매(reaction solvent) 100,000중량부와, 폴리올레핀의 보란화 단계에서 제조된 보란-말단 폴리올레핀 20,000~40,000중량부를 순차적으로 투여한 다음, 50~500RPM의 속도로 교반하면서 증류수 20,000~40,000중량부, 소디움 하이드록사이드(sodium hydroxide)나 포타슘 하이드록사이드(potassium hydroxide) 등의 염기(base) 2,000~8,000중량부, 알코올 2,000~8,000중량부를 첨가한 후 반응온도를 -10~0℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 10~30중량% : 물함량 90~70중량%) 15,000~40,000중량부를 30~60분간 적가한 다음, 반응 온도를 30~60℃로 상승시켜 50~500RPM의 속도로 교반하면서 4~12시간 동안 더 반응을 진행한 후, 생성된 반응물을 여과, 세척 및 50~100℃에서 12~48시간 감압 하에 건조시켜 하이드록시-말단 폴리올레핀(hydroxy-terminated polyolefin)을 제조하는 폴리올레핀의 관능화 단계와;While purging an inert gas in a reactor equipped with gas purging equipment, dropper, stirrer, and temperature controller, diethyl ether, ethyl acetate, tetrahydrofuran, or methyl ethyl ketone ), 100,000 parts by weight of a reaction solvent selected from the group consisting of etc., and 20,000 to 40,000 parts by weight of borane-terminated polyolefin prepared in the boranization step of polyolefin were sequentially added, followed by adding 20,000 to 20,000 parts of distilled water while stirring at a speed of 50 to 500 RPM. After adding 40,000 parts by weight, 2,000 to 8,000 parts by weight of base such as sodium hydroxide or potassium hydroxide, and 2,000 to 8,000 parts by weight of alcohol, the reaction temperature was -10 to 0°C. , add 15,000 to 40,000 parts by weight of hydrogen peroxide aqueous solution (10 to 30% by weight of hydrogen peroxide: 90 to 70% by weight of water) dropwise for 30 to 60 minutes, then raise the reaction temperature to 30 to 60°C. After the reaction proceeded for an additional 4 to 12 hours while stirring at a speed of 50 to 500 RPM, the resulting reactant was filtered, washed, and dried under reduced pressure at 50 to 100°C for 12 to 48 hours to produce hydroxy-terminated polyolefin. a functionalization step of polyolefin to produce polyolefin;
가스 퍼징장비, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 디에틸 에테르(diethyl ether)나 에칠아세테이트(ethyl acetate), 테트라하이드로퓨란(tetrahydrofuran), 메틸에틸케톤(methyl ethyl ketone) 등에서 선택되어지는 반응용매(reaction solvent) 100,000중량부와 폴리올레핀의 관능화 단계에서 제조된 하이드록시-말단 폴리올레핀 20,000~40,000중량부를 투여한 다음, 반응기 온도를 30~60℃로 상승시키고 50~500RPM의 속도로 6~24시간 동안 교반시킨 다음, 상기 반응기에 소디움 나프탈라이드(sodium naphthalenide)나 리튬 나프탈라이드(lithium naphthalenide), 칼륨 나프탈라이드(potassium naphthalenide) 등에서 선택 되어지는 환원제 1,000~10,000중량부를 투여하여 반응온도를 30~60℃로 유지시키고 50~500RPM의 속도로 3~12시간 동안 교반한 후, 생성된 혼합물을 여과, 세척 하여 50~100℃에서 12~48시간 동안 감압 하에 건조시켜 고분자 개시제(initiator)를 제조하는 고분자 개시제 제조단계와;Select from diethyl ether, ethyl acetate, tetrahydrofuran, or methyl ethyl ketone while purging an inert gas in a reactor equipped with gas purging equipment, stirrer, and temperature controller. After adding 100,000 parts by weight of the reaction solvent and 20,000 to 40,000 parts by weight of the hydroxy-terminated polyolefin prepared in the functionalization step of the polyolefin, the temperature of the reactor was raised to 30 to 60 ° C. and the reactor was heated at a speed of 50 to 500 RPM. After stirring for 6 to 24 hours, 1,000 to 10,000 parts by weight of a reducing agent selected from sodium naphthalenide, lithium naphthalenide, potassium naphthalenide, etc. is added to the reactor. The reaction temperature was maintained at 30-60℃ and stirred at a speed of 50-500RPM for 3-12 hours. The resulting mixture was filtered, washed, and dried under reduced pressure at 50-100℃ for 12-48 hours to add a polymer initiator ( A polymer initiator manufacturing step of producing an initiator);
가스 퍼징장비, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 반응용매 100,000중량부와, 고분자 개시제 제조단계에서 제조된 고분자 개시제 20,000~40,000중량부, 에틸렌 옥사이드(ethylene oxide)나, 프로필렌 옥사이드(propylene oxide), 부틸렌 옥사이드(butylene oxide), 옥텐 옥사이드(octene oxide) 등의 알켄 옥사이드(alkene oxide) 10,000~90,000중량부, 베릴륨 하이드라이드(beryllium hydride)나 칼슘 하이드라이드(calcium hydride), 티타늄 하이드라이드(titanium hydride) 등에서 선택되어지는 금속 하이드라이드(metal hydride) 100~1,000중량부를 가한 후, 반응기 온도를 60~100℃로 상승시켜 50~500RPM의 속도로 24~60시간 동안 반응시킨 다음, 알코올 1,000~2,000중량부를 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척한 다음, 50~100℃에서 12~60시간 동안 감압 하에 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하는 공중합체 제조단계와;While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of the reaction solvent, 20,000 to 40,000 parts by weight of the polymer initiator prepared in the polymer initiator production step, ethylene oxide, or propylene oxide. 10,000 to 90,000 parts by weight of alkene oxide such as propylene oxide, butylene oxide, octene oxide, beryllium hydride, calcium hydride, titanium After adding 100 to 1,000 parts by weight of a metal hydride selected from titanium hydride, etc., the temperature of the reactor was raised to 60 to 100°C and reacted at a speed of 50 to 500 RPM for 24 to 60 hours. A copolymer preparation step of preparing a polyolefin-polyalkenoxide copolymer by filtering and washing the mixture in which 1,000 to 2,000 parts by weight of alcohol was added to terminate the reaction, and then drying it under reduced pressure at 50 to 100°C for 12 to 60 hours;
교반기, 온도조절기가 장착된 반응기에 에테르(ether)나 케톤(ketone), 알코올(alcohol) 등에서 선택 되어지는 분산용매 100,000중량부와 상기 공중합체 제조단계에서 제조된 폴리올레핀-폴리알켄옥사이드 공중합체 20,000~40,000중량부를 투여한 다음 반응기 온도를 20~60℃로 상승시키고 50~500RPM의 속도로 1~6시간 동안 교반한 후, 상기 반응기에 소디움 티오시아네이트(sodium thiocyanate)나 포타슘 티오시아네이트(potassium thiocyanate), 1-에틸-3-메틸이미다졸륨 티오시아네이트(1-ethyl 3-methylimidazolium, thiocyanate), 1-부틸-3-메틸이미다졸륨 티오시아네이트(1-butyl-3-methylimidazolium thiocyanate), 1-부틸-1-메틸피롤리디늄 티오시아네이트(1-butyl-1-methylpyrrolidinium thiocyanate), 1-에틸-1-메틸피페리디늄 티오시아네이트(1-ethyl-1-methylpiperidinium thiocyanate) 등에서 선택되어지는 이온성 액체(ionic liquid) 200~600중량부를 투여하여 반응기 온도를 20~60℃로 유지시키고 50~500RPM의 속도로 1~6시간 동안 교반한 반응물을 여과, 세척 및 50~100℃에서 12~24시간 건조하여 이온성 공중합체를 제조하는 이온성 공중합체 제조단계와;In a reactor equipped with a stirrer and temperature controller, 100,000 parts by weight of a dispersion solvent selected from ether, ketone, alcohol, etc. and 20,000 ~ 20,000 parts by weight of the polyolefin-polyalkene oxide copolymer prepared in the copolymer production step. After administering 40,000 parts by weight, raising the temperature of the reactor to 20-60°C and stirring for 1-6 hours at a speed of 50-500 RPM, sodium thiocyanate or potassium thiocyanate is added to the reactor. ), 1-ethyl 3-methylimidazolium, thiocyanate, 1-butyl-3-methylimidazolium thiocyanate, It is selected from 1-butyl-1-methylpyrrolidinium thiocyanate, 1-ethyl-1-methylpiperidinium thiocyanate, etc. 200 to 600 parts by weight of ionic liquid was administered to maintain the reactor temperature at 20 to 60°C, and the reactant was stirred at a speed of 50 to 500 RPM for 1 to 6 hours, filtered, washed, and stirred for 12 hours at 50 to 100°C. An ionic copolymer preparation step of preparing an ionic copolymer by drying for ~24 hours;
니더(Kneader)나 헨셀(Hensel), 밴버리(Banbury) 등의 혼합 믹서(mixer)에 폴리에틸렌(polyethylene)이나, 폴리프로필렌(polypropylene), 폴리메틸펜텐(polymethylpentene) 등의 폴리올레핀(polyolefin) 수지나 에틸렌-비닐아세테이트 공중합체(ethylene-vinyl acetate copolymer)나, 에틸렌-프로필렌 공중합체(ethylene-propylene copolymer), 에틸렌-프로필렌-디엔 공중합체(ethylene-propylene-diene copolymer), 에틸렌-에틸아크릴레이트 공중합체(ethylene-ethylacrylate copolymer) 등의 에틸렌공중합체(ethylene copolymer), 부타디엔 고무(butadiene rubber)나, 니드릴부타디엔 고무(nitrile butadiene rubber), 클로로프렌 고무(chloroprene rubber), 이소부틸렌 고무(isobutylene rubber), 스티렌부타디엔 고무(styrene butadiene rubber) 등의 합성고무(synthetic rubber)에서 선택되어지는 고분자 중합체 100,000중량부와, 그래핀(graphene)이나, 카본 블랙(carbon black), 그래파이트(graphite), 전기 전도성 마이카(electro-conductive mica), 인듐 틴 옥사이드(indium tin oxide), 틴 옥사이드(tin dioxide), 징크 옥사이드(zinc oxide), 안티모니 틴 옥사이드 (antimony-doped tin oxide) 등에서 선택되어지는 전기 전도성 충진제 100~500중량부, 이온성 공중합체 제조단계에서 제조된 이온성 공중합체 20,000~40,000중량부, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트][thiodiethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]나, 티오디프로피오닉 액시드 디옥타데실에스테르(thiodipropionic acid dioctadecylester), 디스테아릴 티오디프로피오네이트(distearyl thiodipropionate), 3-메르캅토프로피오닉 액시드(3-mercaptopropionic acid) 등의 황화합물 중에서 단독 또는 2종 이상 혼합사용 되는 산화방지제 50~200중량부, 칼슘 스테아레이트(calcium stearate), 마그네슘 스테아레이트(magnesium stearate), 알루미늄 스테아레이트(aluminum stearate), 리튬 스테아레이트 (lithium stearate) 등의 지방산 금속염(fatty acid metal salt)에서 선택되어지는 활제(lubricant) 100~1,400중량부를 순차적으로 투여하고 80~200℃ 온도에서 5~60분간 혼련한 덩어리 반죽을 일축(single screw)이나 이축 압출기(twin screw extruder)로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하는 대전방지제 조성물 제조단계를 거쳐; 이온성 공중합체 및 대전방지 조성물을 제조하였다.Add polyolefin resin such as polyethylene, polypropylene, or polymethylpentene to a mixing mixer such as Kneader, Hensel, or Banbury, or ethylene- Vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-ethyl acrylate copolymer (ethylene) -ethylene copolymer such as ethylacrylate copolymer, butadiene rubber, nitrile butadiene rubber, chloroprene rubber, isobutylene rubber, styrene butadiene 100,000 parts by weight of a polymer selected from synthetic rubber such as styrene butadiene rubber, graphene, carbon black, graphite, and electrically conductive mica. 100 to 500 parts by weight of an electrically conductive filler selected from conductive mica, indium tin oxide, tin dioxide, zinc oxide, antimony-doped tin oxide, etc. , 20,000 to 40,000 parts by weight of the ionic copolymer prepared in the ionic copolymer production step, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][thiodiethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodipropionic acid dioctadecylester, distearyl thiodipropionate ), 50 to 200 parts by weight of antioxidants used alone or in combination of two or more sulfur compounds such as 3-mercaptopropionic acid, calcium stearate, and magnesium stearate. ), 100 to 1,400 parts by weight of a lubricant selected from fatty acid metal salts such as aluminum stearate and lithium stearate are sequentially administered and treated at a temperature of 80 to 200°C. The antistatic agent composition manufacturing step is to transfer the lump dough kneaded for 5 to 60 minutes to a single screw or twin screw extruder and produce antistatic agent composition pellets of 3 to 5 mm in size through extrusion molding; An ionic copolymer and antistatic composition were prepared.
상기 폴리올레핀의 보란화 단계에서 체인 트랜스퍼제는 중합체 말단에 보란기를 도입시키며 트리에틸보란이나, 트리프로필보란, 디메시틸보란, 9-보라비실코노난, 보론 디피로메텐, 텍실보란, 디시아밀보란 등이 바람직하며 10~300중량부가 사용된다.In the boranization step of the polyolefin, the chain transfer agent introduces a borane group at the end of the polymer and adds triethylborane, tripropylborane, dimethylborane, 9-boravisylcononane, boron dipyrromethene, thexylborane, and disiamylborane. etc. are preferable and 10 to 300 parts by weight are used.
이때 체인 트랜스퍼제가 10중량부 미만인 경우 반응성이 떨어지고 300중량부 이상인 경우 경제성이 떨어진다.At this time, if the chain transfer agent is less than 10 parts by weight, reactivity is low, and if it is more than 300 parts by weight, economic feasibility is low.
상기 폴리올레핀의 보란화 단계에서 단량체는 중합체를 형성하며 에틸렌이나, 프로필렌, 부텐, 시클로펜탄, 4-메틸-1-펜텐 등의 알켄 화합물이 단독 또는 2종 이상 선택되어 사용되나 본 발명은 이에 제한 되는게 아니다.In the boranization step of the polyolefin, the monomer forms a polymer, and alkene compounds such as ethylene, propylene, butene, cyclopentane, and 4-methyl-1-pentene are used singly or in combination of two or more, but the present invention is not limited thereto. no.
이때 단량체의 압력이 1기압 미만인 경우 수율이 떨어지고 2기압 이상인 경우 분자량이 증가된다.At this time, if the pressure of the monomer is less than 1 atm, the yield decreases, and if the pressure is more than 2 atm, the molecular weight increases.
상기 폴리올레핀의 보란화 단계에서 촉매는 중합반응 촉매로 라세미-디메틸실릴비스(1-인데닐)지르코늄 디클로라이드, 라세미-디메틸실릴비스[1-(2-메틸-4,5-벤조인데닐)]지르코늄 디클로라이드, 라세미-디메틸실릴비스(2-에틸-4-페닐인데닐)지르코늄 디클로라이, 라세미-디메틸실릴비스[1-(2-n-프로필-4-(1-나프틸)인데닐)]지르코늄 디클로라이드, 라세미-디메틸실릴비스[1-(2-에틸-4-(9-페난트릴)인데닐)]지르코늄 디클로라이드, 라세미-디메틸실릴비스[1-(2-n-프로필-4-(9-페난트릴)인데닐)]지르코늄 디클로라이드 등의 지르코늄 화합물이 5 내지 40 중량부 사용되나 본 발명은 이에 제한 되는게 아니다.In the boranization step of the polyolefin, the catalyst used as a polymerization reaction catalyst is racemic-dimethylsilylbis(1-indenyl)zirconium dichloride, racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl) )] zirconium dichloride, racemic-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride, racemic-dimethylsilylbis[1-(2-n-propyl-4-(1-naph) Tyl)indenyl)]zirconium dichloride, racemic-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride, racemic-dimethylsilylbis[1-( 5 to 40 parts by weight of zirconium compounds such as 2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride are used, but the present invention is not limited thereto.
이때 촉매가 5중량부 미만인 경우 반응수율이 떨어지고 40중량부 이상인 경우 경제성이 떨어진다.At this time, if the catalyst is less than 5 parts by weight, the reaction yield decreases, and if it is more than 40 parts by weight, economic feasibility decreases.
상기 폴리올레핀의 보란화 단계에서 조촉매는 촉매의 반응 활성을 향상시키며 메틸알루미녹산이나, 2,6-디-터트-부틸-4-메틸페놀 변성 메틸알루미녹산, 폴리메틸알루미녹산 등의 알킬알루미녹산 10~60중량부가 사용된다.In the boranization step of the polyolefin, the cocatalyst improves the reaction activity of the catalyst and is an alkyl aluminoxane such as methylaluminoxane, 2,6-di-tert-butyl-4-methylphenol-modified methylaluminoxane, and polymethylaluminoxane. 10 to 60 parts by weight are used.
이때 조촉매가 10중량부 미만인 경우 반응수율이 떨어지고 60중량부 이상인 경우 촉매잔사가 증가된다.At this time, if the cocatalyst is less than 10 parts by weight, the reaction yield decreases, and if it is more than 60 parts by weight, catalyst residue increases.
상기 폴리올레핀의 보란화 단계에서 알코올은 중한반응 종결제로 메탄올이나 에탄올, 프로판올, 이소프로필 알코올 등이 10~100중량부가 사용되나 본 발명은 이에 제한되는게 아니다.In the boranization step of the polyolefin, 10 to 100 parts by weight of alcohol, such as methanol, ethanol, propanol, or isopropyl alcohol, is used as a heavy reaction terminating agent, but the present invention is not limited thereto.
상기 고분자 개시제 제조단계에서 메탈 나프탈라이드는 환원제로 소디움 나프탈라이드나 리튬 나프탈라이드, 칼륨 나프탈라이드 등이 1,000~10,000중량부가 사용되나 본 발명은 이에 제한 되는게 아니다.In the polymer initiator manufacturing step, 1,000 to 10,000 parts by weight of metal naphthalide, such as sodium naphthalide, lithium naphthalide, or potassium naphthalide, is used as a reducing agent, but the present invention is not limited thereto.
이때 메탈 나프탈라이드가 1,000중량부 미만인 경우 중합 반응성이 떨어지고 10,000중량부 이상인 경우 경제성이 떨어진다.At this time, if the metal naphthalide is less than 1,000 parts by weight, polymerization reactivity is low, and if it is more than 10,000 parts by weight, economic feasibility is poor.
본 발명에 따른 이온성 공중합체 및 대전방지 조성물의 제조방법을 보다 상세하게 살펴보고, 그에 따른 실시예를 서술하면 다음과 같다.The manufacturing method of the ionic copolymer and antistatic composition according to the present invention will be examined in more detail, and examples thereof will be described as follows.
이하 실시예를 통하여 본 발명을 더욱 상세히 설명한다. The present invention will be described in more detail through examples below.
단 본 발명의 범위가 예시한 실시예만으로 한정되는 것은 아니다.However, the scope of the present invention is not limited to the illustrative examples.
실시예1Example 1
반응기에 아르곤을 퍼징시키면서 헥산 10,000g, 9-보라비실코노난 200g을 투여한 다음, 에틸렌을 공급하여 1기압으로 유지시키고 반응기 온도를 60℃로 상승시킨다. 상기 반응기에 라세미-디메틸실릴비스[1-(2-메틸-4,5-벤조인데닐)]지르코늄 디클로라이드 20g, 2,6-디-터트-부틸-4-메틸페놀 변성 메틸알루미녹산 30g을 투입하여 100RPM의 속도로 교반하면서 중합을 개시하고 반응기 압력은 단량체를 연속적으로 공급하여 1기압으로, 온도는 60℃를 유지하면서 2시간 동안 중합반응을 진행한다. 반응이 완료된 후, 상기 반응기 하부에서 추출한 중합반응물에 메탄올 50g을 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑 처리하여 공중합체를 용매에서 분리한 다음, 50~60℃ 진공오븐에서 24시간 건조시켜 보란-말단 폴리올레핀을 제조하였다.While purging argon into the reactor, 10,000 g of hexane and 200 g of 9-boravisilcononane were added, and then ethylene was supplied to maintain the pressure at 1 atm and raise the reactor temperature to 60°C. In the reactor, 20 g of racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride and 30 g of 2,6-di-tert-butyl-4-methylphenol-modified methylaluminoxane were added to the reactor. is added and the polymerization is initiated while stirring at a speed of 100 RPM. The reactor pressure is set to 1 atm by continuously supplying monomers, and the polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C. After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then dried in a vacuum oven at 50-60°C for 24 hours to obtain borane. -Terminated polyolefin was prepared.
반응기에 아르곤을 퍼징시키면서 테트라하이드로퓨란 100,000g, 보란-말단 폴리올레핀 25,000g을 순차적으로 투여한 다음, 50RPM의 속도로 교반하면서 증류수 25,000g, 소디움 하이드록사이드 2,500g, 메탄올 3,000g을 첨가한 후, 반응기 온도를 -5℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 30중량%) 20,000g을 60분간 적가한 다음, 반응 온도를 40℃로 상승시켜 100RPM의 속도로 교반하면서 8시간 동안 더 반응을 진행한 후, 생성된 반응물을 여과, 세척 및 60℃ 진공오븐에서 24시간 건조시켜 하이드록시-말단 폴리올레핀을 제조하였다.While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM. The reactor temperature was lowered to -5°C, and 20,000 g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide) was added dropwise over 60 minutes. Then, the reaction temperature was raised to 40°C and stirred at a speed of 100 RPM for an additional 8 hours. After the reaction proceeded, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.
반응기에 질소를 퍼징시키면서 테트라하이드로퓨란 100,000g와 하이드록시-말단 폴리올레핀 25,000g을 투여한 다음, 반응기 온도를 50℃로 상승시켜서 100RPM의 속도로 10시간 동안 교반시키고, 상기 반응기에 칼륨 나프탈라이드 4,000g을 투여하여 반응온도를 50℃로 유지하면서 100RPM의 속도로 8시간 동안 교반한 후, 생성된 혼합물을 여과, 세척 및 60℃ 진공오븐에서 24시간 동안 건조시켜 고분자 개시제를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C and stirred at a speed of 100 RPM for 10 hours, and 4,000 g of potassium naphthalide was added to the reactor. g was administered and stirred for 8 hours at a speed of 100 RPM while maintaining the reaction temperature at 50°C, and then the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer initiator.
반응기에 질소를 퍼징시키면서 테트라하이드로 퓨란 100,000g과 고분자 개시제 25,000g, 에틸렌 옥사이드 50,000g, 칼슘 하이드라이드 200g을 가한 후, 반응기 온도를 80℃로 상승시켜 100RPM의 속도로 50시간 동안 반응시킨 다음, 메탄올 1,500g을 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척한 다음, 60℃ 진공오븐에서 24시간 동안 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added. The reactor temperature was raised to 80°C and reacted at a rate of 100 RPM for 50 hours, followed by methanol. The reaction was terminated by adding 1,500 g, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.
반응기에 에탄올 100,000g, 폴리올레핀-폴리알켄옥사이드 공중합체 25,000g 투여하여 반응기 온도를 40℃로 상승시켜서 100RPM의 속도로 1시간 동안 교반한 후, 1-부틸-1-메틸피롤리디늄 티오시아네이트 500g을 투여하여 40℃로 유지하면서 100RPM의 속도로 2시간 동안 교반한 반응물을 여과, 세척 하여 60℃ 진공오븐에서 12시간 건조하여 이온성 공중합체를 제조하였다.100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer were added to the reactor, the temperature of the reactor was raised to 40°C and stirred for 1 hour at a speed of 100 RPM, and then 500 g of 1-butyl-1-methylpyrrolidinium thiocyanate was added. was administered and stirred for 2 hours at a speed of 100 RPM while maintaining the temperature at 40°C. The reaction product was filtered, washed, and dried in a vacuum oven at 60°C for 12 hours to prepare an ionic copolymer.
니더 믹서에 폴리에틸렌 100,000g, 안티모니 틴 옥사이드 300g, 이온성 공중합체 25,000g, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트 150g, 칼슘 스테아레이트 400g를 투여한 후, 120℃ 온도에서 20분간 혼련 한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3 내지 5mm 크기의 대전방지제 조성물 펠렛을 제조하였다.In a kneader mixer, 100,000g of polyethylene, 300g of antimony tin oxide, 25,000g of ionic copolymer, 150g of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, calcium After administering 400 g of stearate, the lump dough kneaded for 20 minutes at a temperature of 120° C. was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets with a size of 3 to 5 mm.
실시예2Example 2
반응기에 아르곤을 퍼징시키면서 헥삭 10,000g 트리프로필보란 200g을 투여한 다음, 에틸렌을 공급하여 1기압으로 유지시키고 반응기 온도를 60℃로 상승시킨다. 상기 반응기에 라세미-디메틸실릴비스(1-인데닐)지르코늄 디클로라이드 20g, 메틸알루미녹산 30g을 투입하여 100RPM의 속도로 교반하면서 중합을 개시하고, 반응기 압력은 단량체를 연속적으로 공급하여 1기압으로, 온도는 60℃를 유지하면서 2시간 동안 중합반응을 진행한다. 반응이 완료된 후, 상기 반응기 하부에서 추출한 중합반응물에 메탄올 50g을 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑 처리하여 공중합체를 용매에서 분리한 다음, 50~60℃ 진공오븐에서 24시간 건조시켜 보란-말단 폴리올레핀을 제조하였다.While purging argon into the reactor, 10,000 g of Hexac and 200 g of tripropylborane were added, and then ethylene was supplied to maintain the pressure at 1 atm and raise the reactor temperature to 60°C. 20 g of racemic-dimethylsilylbis(1-indenyl)zirconium dichloride and 30 g of methylaluminoxane were added to the reactor to initiate polymerization while stirring at a speed of 100 RPM, and the reactor pressure was adjusted to 1 atm by continuously supplying monomers. , the polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C. After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then dried in a vacuum oven at 50-60°C for 24 hours to obtain borane. -Terminated polyolefin was prepared.
반응기에 아르곤을 퍼징시키면서 테트라하이드로퓨란 100,000g, 보란-말단 폴리올레핀 25,000g을 순차적으로 투여한 다음, 50RPM의 속도로 교반하면서 증류수 25,000g, 소디움 하이드록사이드 2,500g, 메탄올 3,000g을 첨가한 후, 반응기 온도를 -5℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 30중량%) 20,000g을 60분간 적가한 다음, 반응 온도를 40℃로 상승시켜 100RPM의 속도로 교반하면서 8시간 동안 더 반응을 진행한 후, 생성된 반응물을 여과, 세척 및 60℃ 진공오븐에서 24시간 건조시켜 하이드록시-말단 폴리올레핀을 제조하였다.While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM. The reactor temperature was lowered to -5°C, and 20,000 g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide) was added dropwise over 60 minutes. Then, the reaction temperature was raised to 40°C and stirred at a speed of 100 RPM for an additional 8 hours. After the reaction proceeded, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.
반응기에 질소를 퍼징시키면서 테트라하이드로퓨란 100,000g과 하이드록시-말단 폴리올레핀 25,000g을 투여한 다음, 반응기 온도를 50℃로 상승시켜서 100RPM의 속도로 10시간 동안 교반시키고, 상기 반응기에 소디움 나프탈라이드 4,000g을 투여하여 반응온도를 50℃로 유지하여 100RPM의 속도로 8시간 동안 교반한 후, 생성된 혼합물을 여과, 세척 및 60℃ 진공오븐에서 24시간 동안 건조시켜 고분자 개시제를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C, the reactor was stirred at a speed of 100 RPM for 10 hours, and 4,000 g of sodium naphthalide was added to the reactor. g was administered to maintain the reaction temperature at 50°C and stir at a speed of 100 RPM for 8 hours. Then, the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer initiator.
반응기에 질소를 퍼징시키면서 테트라하이드로 퓨란 100,000g과 고분자 개시제 25,000g, 에틸렌 옥사이드 50,000g, 칼슘 하이드라이드 200g을 가한 후, 반응기 온도를 80℃로 상승시켜 100 RPM의 속도로 50시간 동안 반응시킨 다음, 메탄올 1,500g을 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척한 다음 60℃ 진공오븐에서 24시간 동안 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added, then the reactor temperature was raised to 80°C and reacted at a speed of 100 RPM for 50 hours. The reaction was terminated by adding 1,500 g of methanol, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.
반응기에 에탄올 100,000g 폴리올레핀-폴리알켄옥사이드 공중합체 25,000g 투여하여 반응기 온도를 40℃로 상승시켜서 100RPM의 속도로 1시간 동안 교반한 후, 포타슘 티오시아네이트 500g을 투여하여 40℃로 유지하여 100RPM의 속도로 2시간 동안 교반한 반응물을 여과, 세척 및 60℃ 진공오븐에서 12시간 건조하여 이온성 공중합체를 제조하였다.100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer were added to the reactor to raise the temperature of the reactor to 40°C and stirred for 1 hour at a speed of 100 RPM. Then, 500 g of potassium thiocyanate was added to maintain the temperature at 40°C and the temperature was maintained at 100 RPM. The reaction product was stirred at high speed for 2 hours, filtered, washed, and dried in a vacuum oven at 60°C for 12 hours to prepare an ionic copolymer.
니더 믹서에 폴리에틸렌 100,000g, 그래핀 300g, 이온성 공중합체 25,000g, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트 150g, 칼슘 스테아레이트 400g를 투여한 후 120℃ 온도에서 20분간 혼련 한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하였다.In a kneader mixer, add 100,000g of polyethylene, 300g of graphene, 25,000g of ionic copolymer, 150g of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and calcium stearate. After administering 400 g, the kneaded dough for 20 minutes at a temperature of 120°C was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets of 3 to 5 mm in size.
실시예3Example 3
반응기에 아르곤을 퍼징시키면서 헵탄 10,000g 디메시틸보란 200g을 투여한 다음 프로필렌을 공급하여 1기압으로 유지시키고, 반응기 온도를 60℃로 상승시킨다. While purging argon into the reactor, 10,000 g of heptane and 200 g of dimethylborane were added, propylene was supplied to maintain the pressure at 1 atm, and the temperature of the reactor was raised to 60°C.
상기 반응기에 라세미-디메틸실릴비스[1-(2-메틸-4,5-벤조인데닐)]지르코늄 디클로라이드 20g, 2,6-디-터트-부틸-4-메틸페놀 변성 메틸알루미녹산 30g을 투입하여 100RPM의 속도로 교반하면서 중합을 개시하고, 반응기 압력은 단량체를 연속적으로 공급하여 1기압으로, 온도는 60℃를 유지하면서 2시간 동안 중합반응을 진행한다. In the reactor, 20 g of racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride and 30 g of 2,6-di-tert-butyl-4-methylphenol-modified methylaluminoxane were added to the reactor. The polymerization is initiated while stirring at a speed of 100 RPM. The reactor pressure is set to 1 atm by continuously supplying monomers, and the polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C.
반응이 완료된 후 상기 반응기 하부에서 추출한 중합반응물에 메탄올 50g을 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑 처리하여 공중합체를 용매에서 분리한 다음, 50~60℃ 진공오븐에서 24시간 건조시켜 보란-말단 폴리올레핀을 제조하였다.After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then dried in a vacuum oven at 50-60°C for 24 hours to produce borane- A terminal polyolefin was prepared.
반응기에 아르곤을 퍼징시키면서 테트라하이드로퓨란 100,000g, 보란-말단 폴리올레핀 25,000g을 순차적으로 투여한 다음, 50RPM의 속도로 교반하면서 증류수 25,000g 소디움 하이드록사이드 2,500g, 메탄올 3,000g을 첨가한 후, 반응기 온도를 -5℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 30중량%) 20,000g을 60분간 적가한 다음, 반응 온도를 40℃로 상승시켜 100RPM의 속도로 교반하면서 8시간 동안 더 반응을 진행한 후 생성된 반응물을 여과, 세척 및 60℃ 진공오븐에서 24시간 건조시켜 하이드록시-말단 폴리올레핀을 제조하였다.While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM, and then added to the reactor. Lower the temperature to -5℃, add 20,000g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide) dropwise over 60 minutes, then raise the reaction temperature to 40℃ and react for another 8 hours while stirring at a speed of 100RPM. After proceeding, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.
반응기에 질소를 퍼징시키면서 테트라하이드로퓨란 100,000g와 하이드록시-말단 폴리올레핀 25,000g을 투여한 다음 반응기 온도를 50℃로 상승시키고, 100RPM의 속도로 10시간 동안 교반시키고 상기 반응기에 리튬 나프탈라이드 4,000g을 투여하여 반응온도를 50℃로 유지시키고 100RPM의 속도로 8시간 동안 교반한 후, 생성된 혼합물을 여과, 세척 및 60℃ 진공오븐에서 24시간 동안 건조시켜 고분자 개시제를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C, stirred at a speed of 100 RPM for 10 hours, and 4,000 g of lithium naphthalide was added to the reactor. was administered to maintain the reaction temperature at 50°C and stirred at a speed of 100 RPM for 8 hours. Then, the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer initiator.
반응기에 질소를 퍼징시키면서 테트라하이드로 퓨란 100,000g과 고분자 개시제 25,000g, 프로필렌 옥사이드 50,000g, 칼슘 하이드라이드 200g을 가한 후, 반응기 온도를 80℃로 상승시켜 100 RPM의 속도로 50시간 동안 반응시킨 다음, 메탄올 1,500g을 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척하여서 60℃ 진공오븐에서 24시간 동안 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of propylene oxide, and 200 g of calcium hydride were added, the temperature of the reactor was raised to 80°C, and reaction was performed at a speed of 100 RPM for 50 hours. The reaction was terminated by adding 1,500 g of methanol, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.
반응기에 에탄올 100,000g 폴리올레핀-폴리알켄옥사이드 공중합체 25,000g 투여하여 반응기 온도를 40℃로 상승시키고, 100RPM의 속도로 1시간 동안 교반한 후 1-에틸-3-메틸이미다졸륨 티오시아네이트 500g을 투여하여 40℃로 유지하여 100RPM의 속도로 2시간 동안 교반한 반응물을 여과, 세척 및 60℃ 진공오븐에서 12시간 건조하여 이온성 공중합체를 제조하였다.100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer were added to the reactor to raise the temperature of the reactor to 40°C. After stirring for 1 hour at a speed of 100 RPM, 500 g of 1-ethyl-3-methylimidazolium thiocyanate was added. The reactant was administered, maintained at 40°C, and stirred at a speed of 100 RPM for 2 hours, then filtered, washed, and dried in a 60°C vacuum oven for 12 hours to prepare an ionic copolymer.
니더 믹서에 폴리프로필렌, 100,000g, 틴 옥사이드 300g, 이온성 공중합체 25,000g, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트 150g, 칼슘 스테아레이트 400g를 투여한 후 160℃ 온도에서 20분간 혼련 한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하였다.In a kneader mixer, add 100,000g of polypropylene, 300g of tin oxide, 25,000g of ionic copolymer, 150g of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and calcium. After administering 400 g of stearate, the dough was kneaded at 160°C for 20 minutes and transferred to a twin-screw extruder to produce antistatic agent composition pellets of 3 to 5 mm in size through extrusion molding.
실시예4Example 4
반응기에 아르곤을 퍼징시키면서 톨루엔 10,000g, 9-보라비실코노난 200g을 투여한 다음, 4-메틸-1-펜텐을 공급하여 1기압으로 유지시키고, 반응기 온도를 60℃로 상승시킨다. While purging argon into the reactor, 10,000 g of toluene and 200 g of 9-boravisilcononane were added, then 4-methyl-1-pentene was supplied to maintain the pressure at 1 atm, and the reactor temperature was raised to 60°C.
상기 반응기에 라세미-디메틸실릴비스(2-에틸-4-페닐인데닐)지르코늄 디클로라이드 20g, 폴리메틸알루미녹산 30g을 투입하여 100RPM의 속도로 교반하면서 중합을 개시하고, 반응기 압력은 단량체를 연속적으로 공급하여 1기압으로, 온도는 60℃를 유지하면서 2시간 동안 중합반응을 진행한다. Polymerization was initiated by adding 20 g of racemic-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride and 30 g of polymethylaluminoxane to the reactor and stirring at a speed of 100 RPM, and the reactor pressure was used to continuously separate the monomers. The polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C at 1 atm.
반응이 완료된 후 상기 반응기 하부에서 추출한 중합반응물에 메탄올 50g을 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑 처리하여 공중합체를 용매에서 분리한 다음 50~60℃ 진공오븐에서 24시간 건조시켜 보란-말단 폴리올레핀을 제조하였다.After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent and then dried in a vacuum oven at 50-60°C for 24 hours to remove borane-terminated residues. Polyolefin was prepared.
반응기에 아르곤을 퍼징시키면서 테트라하이드로퓨란 100,000g, 보란-말단 폴리올레핀 25,000g을 순차적으로 투여한 다음, 50RPM의 속도로 교반하면서 증류수 25,000g 소디움 하이드록사이드 2,500g, 메탄올 3,000g을 첨가한 후 반응기 온도를 -5℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 30중량%, 물 70중량%) 20,000g을 60분간 적가한 다음, 반응 온도를 40℃로 상승시켜 100RPM의 속도로 교반하면서 8시간 동안 더 반응을 진행한 후, 생성된 반응물을 여과, 세척 및 60℃ 진공오븐에서 24시간 건조시켜 하이드록시-말단 폴리올레핀을 제조하였다.While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM, and the reactor temperature was adjusted to Lowered to -5℃, added 20,000g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide, 70% by weight of water) dropwise over 60 minutes, then raised the reaction temperature to 40℃ and stirred at 100RPM for 8 minutes. After the reaction proceeded for an additional time, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.
반응기에 질소를 퍼징시키면서 테트라하이드로퓨란 100,000g와 하이드록시-말단 폴리올레핀 25,000g을 투여한 다음, 반응기 온도를 50℃로 상승시켜서 100RPM의 속도로 10시간 동안 교반시키고, 상기 반응기에 칼륨 나프탈라이드 4,000g을 투여하여 반응온도를 50℃로 유지시키고 100RPM의 속도로 8시간 동안 교반한 후, 생성된 혼합물을 여과, 세척 및 60℃ 진공오븐에서 24시간 동안 건조시켜 고분자 개시를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C and stirred at a speed of 100 RPM for 10 hours, and 4,000 g of potassium naphthalide was added to the reactor. g was administered to maintain the reaction temperature at 50°C and stirred at a speed of 100 RPM for 8 hours, and then the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer starter.
반응기에 질소를 퍼징시키면서 테트라하이드로 퓨란 100,000g과 고분자 개시제 25,000g, 에틸렌 옥사이드 50,000g, 칼슘 하이드라이드 200g을 가한 후, 반응기 온도를 80℃로 상승시켜 100RPM의 속도로 50시간 동안 반응시킨 다음, 메탄올 1,500g을 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척하여서 60℃ 진공오븐에서 24시간 동안 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added. The reactor temperature was raised to 80°C and reacted at a rate of 100 RPM for 50 hours, followed by methanol. The reaction was terminated by adding 1,500 g, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.
반응기에 에탄올 100,000g 폴리올레핀-폴리알켄옥사이드 공중합체 25,000g 투여하여 반응기 온도를 40℃로 상승시키고 100RPM의 속도로 1시간 동안 교반한 후, 1-부틸-1-메틸피롤리디늄 티오시아네이트 500g을 투여하여 40℃로 유지시키고, 100RPM의 속도로 2시간 동안 교반한 반응물을 여과, 세척 및 60℃ 진공오븐에서 12시간 건조하여 이온성 공중합체를 제조하였다.Add 100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer to the reactor to raise the temperature of the reactor to 40°C. After stirring for 1 hour at a speed of 100 RPM, 500 g of 1-butyl-1-methylpyrrolidinium thiocyanate was added. The reactant was administered, maintained at 40°C, and stirred at a speed of 100 RPM for 2 hours, then filtered, washed, and dried in a 60°C vacuum oven for 12 hours to prepare an ionic copolymer.
니더 믹서에 폴리메틸펜텐 100,000g, 징크 옥사이드 300g, 이온성 공중합체 25,000g, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트 150g, 칼슘 스테아레이트 400g를 투여한 후, 80~200℃ 온도에서 20분간 혼련한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하였다.In a kneader mixer, 100,000g of polymethylpentene, 300g of zinc oxide, 25,000g of ionic copolymer, 150g of thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, calcium After administering 400 g of stearate, the lump dough kneaded for 20 minutes at a temperature of 80 to 200° C. was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets of 3 to 5 mm in size.
실시예5Example 5
반응기에 아르곤을 퍼징시키면서 톨루엔 10,000g 9-보라비실코노난 200g을 투여한 다음, 에틸렌과 프로필렌을 공급하여 1기압으로 유지시키고 반응기 온도를 60℃로 상승시킨다. While purging argon into the reactor, 10,000 g of toluene and 200 g of 9-boravisylcononane were added, and then ethylene and propylene were supplied to maintain the pressure at 1 atm and raise the reactor temperature to 60°C.
상기 반응기라세미-디메틸실릴비스[1-(2-메틸-4,5-벤조인데닐)]지르코늄 디클로라이드 20g, 메틸알루미녹산 30g을 투입하여 100RPM의 속도로 교반하면서 중합을 개시하고, 반응기 압력은 단량체를 연속적으로 공급하여 1기압으로, 온도는 60℃를 유지하면서 2시간 동안 중합반응을 진행한다. In the reactor, 20 g of racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride and 30 g of methylaluminoxane were added and polymerization was initiated while stirring at a speed of 100 RPM, and the reactor pressure was increased. The silver monomer is continuously supplied and the polymerization reaction proceeds for 2 hours while maintaining a pressure of 1 atm and a temperature of 60°C.
반응이 완료된 후 상기 반응기 하부에서 추출한 중합반응물에 메탄올 50g을 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑 처리하여 공중합체를 용매에서 분리한 다음, 50~60℃ 진공오븐에서 24시간 건조시켜 보란-말단 폴리올레핀을 제조하였다.After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent, and then dried in a vacuum oven at 50-60°C for 24 hours to produce borane- A terminal polyolefin was prepared.
반응기에 아르곤을 퍼징시키면서 테트라하이드로퓨란 100,000g, 보란-말단 폴리올레핀 25,000g을 순차적으로 투여한 다음 50RPM의 속도로 교반하면서 증류수 25,000g 소디움 하이드록사이드 2,500g, 메탄올 3,000g을 첨가한 후 반응기 온도를 -5℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 30중량% : 물함량 70중량%) 20,000g을 60분간 적가한 다음, 반응 온도를 40℃로 상승시켜 100RPM의 속도로 교반하면서 8시간 동안 더 반응을 진행한 후, 생성된 반응물을 여과, 세척 및 60℃ 진공오븐에서 24시간 건조시켜 하이드록시-말단 폴리올레핀을 제조하였다.While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM, and the temperature of the reactor was adjusted to Lower the temperature to -5℃, add 20,000g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide: 70% by weight of water) dropwise over 60 minutes, then raise the reaction temperature to 40℃ and stir at 100RPM for 8 minutes. After the reaction proceeded for an additional time, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.
반응기에 질소를 퍼징시키면서 테트라하이드로퓨란 100,000g와 하이드록시-말단 폴리올레핀 25,000g을 투여한 다음, 반응기 온도를 50℃로 상승시켜서 100RPM의 속도로 10시간 동안 교반시키고, 상기 반응기에 칼륨 나프탈라이드 4,000g을 투여하여 반응온도를 50℃로 유지시키고 100RPM의 속도로 8시간 동안 교반한 후 생성된 혼합물을 여과, 세척 및 60℃ 진공오븐에서 24시간 동안 건조시켜 고분자 개시제를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C and stirred at a speed of 100 RPM for 10 hours, and 4,000 g of potassium naphthalide was added to the reactor. g was administered to maintain the reaction temperature at 50°C and stirred at a speed of 100 RPM for 8 hours. The resulting mixture was filtered, washed, and dried in a 60°C vacuum oven for 24 hours to prepare a polymer initiator.
반응기에 질소를 퍼징시키면서 테트라하이드로 퓨란 100,000g과 고분자 개시제 25,000g, 에틸렌 옥사이드 50,000g, 칼슘 하이드라이드 200g을 가한 후 반응기 온도를 80℃로 상승시켜 100RPM의 속도로 50시간 동안 반응시킨 다음, 메탄올 1,500g을 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척한 다음, 60℃ 진공오븐에서 24시간 동안 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added, the temperature of the reactor was raised to 80°C, reaction was performed at a rate of 100 RPM for 50 hours, and then 1,500 g of methanol was added. The mixture where the reaction was terminated by adding g was filtered and washed, and then dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkenoxide copolymer.
반응기에 에탄올 100,000g 폴리올레핀-폴리알켄옥사이드 공중합체 25,000g 투여하여 반응기 온도를 40℃로 상승시켜서 100RPM의 속도로 1시간 동안 교반한 후, 1-부틸-1-메틸피롤리디늄 티오시아네이트 500g을 투여하여 40℃로 유지시키고, 100RPM의 속도로 2시간 동안 교반한 반응물을 여과, 세척 및 60℃ 진공오븐에서 12시간 건조하여 이온성 공중합체를 제조하였다.100,000 g of ethanol and 25,000 g of polyolefin-polyalkenoxide copolymer were added to the reactor, the temperature of the reactor was raised to 40°C and stirred for 1 hour at a speed of 100 RPM, and then 500 g of 1-butyl-1-methylpyrrolidinium thiocyanate was added. The reactant was administered, maintained at 40°C, and stirred at a speed of 100 RPM for 2 hours, then filtered, washed, and dried in a 60°C vacuum oven for 12 hours to prepare an ionic copolymer.
니더 믹서에 에틸렌-프로필렌 공중합체 100,000g, 안티모니 틴 옥사이드 300g, 이온성 공중합체 25,000g, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트 150g, 칼슘 스테아레이트 400g를 투여한 후, 100℃ 온도에서 20분간 혼련 한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하였다.In a kneader mixer, 100,000 g of ethylene-propylene copolymer, 300 g of antimony tin oxide, 25,000 g of ionic copolymer, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propio. After administering 150 g of nate and 400 g of calcium stearate, the dough was kneaded at 100°C for 20 minutes and transferred to a twin-screw extruder to produce antistatic agent composition pellets of 3 to 5 mm in size through extrusion molding.
실시예6Example 6
상기 실시예5의 대전방지제 조성물 제조를 하기와 같이 바꾸는 것 외에는 상기 실시예5와 동일한 방법으로 대전방지제 조성물을 제조하였다.An antistatic agent composition was prepared in the same manner as in Example 5 except that the preparation of the antistatic agent composition in Example 5 was changed as follows.
니더 믹서에 에틸렌-비닐아세테이트 공중합체 100,000g, 카본 블랙 300g, 이온성 공중합체 25,000g, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트 150g, 칼슘 스테아레이트 400g를 투여한 후, 100℃ 온도에서 20분간 혼련한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하였다.In a kneader mixer, 100,000 g of ethylene-vinylacetate copolymer, 300 g of carbon black, 25,000 g of ionic copolymer, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. After administering 150 g of calcium stearate and 400 g of calcium stearate, the lump dough kneaded at 100°C for 20 minutes was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets of 3 to 5 mm in size.
실시예7Example 7
상기 실시예5의 대전방지제 조성물 제조를 하기와 같이 바꾸는 것 외에는 상기 실시예5와 동일한 방법으로 대전방지제 조성물을 제조하였다.An antistatic agent composition was prepared in the same manner as in Example 5 except that the preparation of the antistatic agent composition in Example 5 was changed as follows.
니더 믹서에 폴리에틸렌 에틸렌-비닐아세테이트 공중합체 100,000g, 그래파이트 300g, 이온성 공중합체 25,000g, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트 150g, 칼슘 스테아레이트 400g를 투여한 후, 80~200℃ 온도에서 20분간 혼련한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하였다.In a kneader mixer, 100,000 g of polyethylene ethylene-vinylacetate copolymer, 300 g of graphite, 25,000 g of ionic copolymer, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. After administering 150 g of calcium stearate and 400 g of calcium stearate, the lump dough kneaded for 20 minutes at a temperature of 80 to 200 ° C was transferred to a twin-screw extruder and extruded to produce antistatic composition pellets of 3 to 5 mm in size.
비교예1-1Comparative Example 1-1
상기 실시예1의 대전방지제 조성물 제조에서 이온성 공중합체를 사용하지 않는 것 외에는 실시예1과 동일한 방법으로 대전방지제 제조를 완료하였다.The preparation of the antistatic agent was completed in the same manner as in Example 1, except that the ionic copolymer was not used in the preparation of the antistatic agent composition of Example 1.
비교예1-2Comparative Example 1-2
반응기에 아르곤을 퍼징시키면서 헥산 10,000g, 9-보라비실코노난 200g을 투여한 다음, 에틸렌을 공급하여 1기압으로 유지시키고 반응기 온도를 60℃로 상승시킨다. While purging argon into the reactor, 10,000 g of hexane and 200 g of 9-boravisilcononane were added, and then ethylene was supplied to maintain the pressure at 1 atm and raise the reactor temperature to 60°C.
상기 반응기에 라세미-디메틸실릴비스[1-(2-메틸-4,5-벤조인데닐)]지르코늄 디클로라이드 20g, 2,6-디-터트-부틸-4-메틸페놀 변성 메틸알루미녹산 30g을 투입하여 100RPM의 속도로 교반하면서 중합을 개시하고, 반응기 압력은 단량체를 연속적으로 공급하여 1기압으로, 온도는 60℃를 유지하면서 2시간 동안 중합반응을 진행한다. In the reactor, 20 g of racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride and 30 g of 2,6-di-tert-butyl-4-methylphenol-modified methylaluminoxane were added to the reactor. The polymerization is initiated while stirring at a speed of 100 RPM. The reactor pressure is set to 1 atm by continuously supplying monomers, and the polymerization reaction proceeds for 2 hours while maintaining the temperature at 60°C.
반응이 완료된 후 상기 반응기 하부에서 추출한 중합반응물에 메탄올 50g을 첨가하여 반응을 종료시킨 반응혼합물을 스팀 스트리핑 처리하여 공중합체를 용매에서 분리한 다음 50~60℃ 진공오븐에서 24시간 건조시켜 보란-말단 폴리올레핀을 제조하였다.After the reaction was completed, 50 g of methanol was added to the polymerization product extracted from the bottom of the reactor to terminate the reaction. The reaction mixture was subjected to steam stripping to separate the copolymer from the solvent and then dried in a vacuum oven at 50-60°C for 24 hours to remove borane-terminated residues. Polyolefin was prepared.
반응기에 아르곤을 퍼징시키면서 테트라하이드로퓨란 100,000g, 보란-말단 폴리올레핀 25,000g을 순차적으로 투여한 다음 50RPM의 속도로 교반하면서 증류수 25,000g 소디움 하이드록사이드 2,500g, 메탄올 3,000g을 첨가한 후, 반응기 온도를 -5℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 30중량% : 물함량 70중량%) 20,000g을 60분간 적가한 다음, 반응 온도를 40℃로 상승시켜 100RPM의 속도로 교반하면서 8시간 동안 더 반응을 진행한 후, 생성된 반응물을 여과, 세척 및 60℃ 진공오븐에서 24시간 건조시켜 하이드록시-말단 폴리올레핀을 제조하였다.While purging argon into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of borane-terminated polyolefin were sequentially added, and then 25,000 g of distilled water, 2,500 g of sodium hydroxide, and 3,000 g of methanol were added while stirring at a speed of 50 RPM, and the reactor temperature was adjusted to Lowered to -5℃, added 20,000g of hydrogen peroxide aqueous solution (30% by weight of hydrogen peroxide: 70% by weight of water) dropwise over 60 minutes, then raised the reaction temperature to 40℃ and stirred at a speed of 100RPM. After the reaction proceeded for another 8 hours, the resulting reactant was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare hydroxy-terminated polyolefin.
반응기에 질소를 퍼징시키면서 테트라하이드로퓨란 100,000g와 하이드록시-말단 폴리올레핀 25,000g을 투여한 다음 반응기 온도를 50℃로 상승시키고 100RPM의 속도로 10시간 동안 교반시키고, 상기 반응기에 칼륨 나프탈라이드 4,000g을 투여하여 반응온도를 50℃로 유지시키고 100RPM의 속도로 8시간 동안 교반한 후, 생성된 혼합물을 여과, 세척 및 60℃ 진공오븐에서 24시간 동안 건조시켜 고분자 개시제를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran and 25,000 g of hydroxy-terminated polyolefin were added, the temperature of the reactor was raised to 50°C, stirred at a speed of 100 RPM for 10 hours, and 4,000 g of potassium naphthalide was added to the reactor. was administered to maintain the reaction temperature at 50°C and stirred at a speed of 100 RPM for 8 hours, and then the resulting mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polymer initiator.
반응기에 질소를 퍼징시키면서 테트라하이드로 퓨란 100,000g과 고분자 개시제 25,000g, 에틸렌 옥사이드 50,000g, 칼슘 하이드라이드 200g을 가한 후 반응기 온도를 80℃로 상승시켜 100 RPM의 속도로 50시간 동안 반응시킨 다음, 메탄올 1,500g을 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척하여 60℃ 진공오븐에서 24시간 동안 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하였다.While purging nitrogen into the reactor, 100,000 g of tetrahydrofuran, 25,000 g of polymer initiator, 50,000 g of ethylene oxide, and 200 g of calcium hydride were added, the temperature of the reactor was raised to 80°C, reaction was performed at a speed of 100 RPM for 50 hours, and methanol was added. The reaction was terminated by adding 1,500 g, and the mixture was filtered, washed, and dried in a vacuum oven at 60°C for 24 hours to prepare a polyolefin-polyalkene oxide copolymer.
니더 믹서에 폴리에틸렌 100,000g, 안티모니 틴 옥사이드 300g, 폴리올레핀-폴리알켄옥사이드 공중합체 25,000g, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트 150g, 칼슘 스테아레이트 400g를 투여한 후, 120℃ 온도에서 20분간 혼련한 덩어리 반죽을 이축 압출기로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하였다.In a kneader mixer, add 100,000 g of polyethylene, 300 g of antimony tin oxide, 25,000 g of polyolefin-polyalkenoxide copolymer, and thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. After administering 150 g of calcium stearate and 400 g of calcium stearate, the lump dough kneaded at 120°C for 20 minutes was transferred to a twin-screw extruder and extruded to produce antistatic agent composition pellets of 3 to 5 mm in size.
비교예1-3Comparative Example 1-3
상기 비교예1-2 대전방지제 조성물 제조에서 안티모니 틴 옥사이드를 사용하지 않는 것 외에는 비교예1-2과 동일한 방법으로 대전방지제 제조를 완료하였다.The preparation of the antistatic agent was completed in the same manner as Comparative Example 1-2, except that antimony tin oxide was not used in the preparation of the antistatic agent composition of Comparative Example 1-2.
이렇게 제조된 열가소성탄성체 조성물은 핫프레스(hot-press)를 이용하여 170~220℃에서 1.5mm 두께의 시편을 제작하고 표면저항과 종이조각 부착시험을 시행하여 그 결과를 표 1에 나타내었다. The thermoplastic elastomer composition prepared in this way was manufactured into a 1.5 mm thick specimen at 170~220°C using a hot press, and surface resistance and paper piece adhesion tests were performed. The results are shown in Table 1.
시편의 표면저항은 25℃로 유지되는 건조오븐에서 1일 방치한 후, 동일 조건하에서 초절연계를 사용하여 측정하였다. 세척후의 표면저항은 시험편을 80℃의 더운 물에 30분 침지하여, 깨끗한 옷감으로 표면을 닦아낸 후 측정하였다. The surface resistance of the specimen was left in a drying oven maintained at 25°C for 1 day and then measured using a super dielectric meter under the same conditions. Surface resistance after washing was measured by immersing the test piece in hot water at 80°C for 30 minutes and wiping the surface with a clean cloth.
표 1에서와같이 본 발명에 따른 실시예의 표면저항이 낮고, 세척후 변화가 없으며 종이조각 부착성이 없어 대전방지 효과가 비교예 보다 뛰어남을 확인 할 수 있다.As shown in Table 1, the surface resistance of the example according to the present invention is low, there is no change after washing, and there is no adhesion to paper pieces, so it can be confirmed that the antistatic effect is superior to the comparative example.
본 발명의 이온성 공중합체 및 대전방지 조성물의 제조방법은 투명성을 손상시키지 않으며 이행이 적고 장기간 대전 방지성을 유지하면서 기계적 물성, 가공성 및 내후성이 우수한 이온성 공중합체 및 이를 이용한 대전방지 조성물을 용이하게 제조 할 수 있는 효과를 가지고 있어 산업상 이용가치가 대단하다 할 것이다.The manufacturing method of the ionic copolymer and antistatic composition of the present invention facilitates the production of an ionic copolymer and an antistatic composition using the same that do not impair transparency, have little migration, and maintain antistatic properties for a long period of time while maintaining excellent mechanical properties, processability, and weather resistance. It has great industrial value as it has the effect of being easily manufactured.
Claims (4)
가스 퍼징장비, 적가장치, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 반응용매(reaction solvent) 100,000중량부와 상기 보란-말단 폴리올레핀 제조단계에서 제조된 보란-말단 폴리올레핀 20,000~40,000중량부를 순차적으로 투여하고, 50~500RPM의 속도로 교반하면서 증류수 20,000~40,000중량부, 염기(base) 2,000~8,000중량부, 알코올 2,000~8,000중량부를 첨가한 후, 반응온도를 -10~0℃로 낮추고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 10~30중량% : 물함량 90~70중량%) 15,000~40,000중량부를 30~60분간 적가한 다음, 반응 온도를 30~60℃로 상승시켜 50~500RPM의 속도로 교반하면서 4~12시간 동안 더 반응을 진행한 후, 생성된 반응물을 여과/세척하여 50~100℃에서 12~48시간 건조시켜서 관능화된 하이드록시-말단 폴리올레핀(hydroxy-terminated polyolefin)을 제조하는 하이드록시-말단 폴리올레핀 제조단계와;
가스 퍼징장비, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 반응용매(reaction solvent) 100,000중량부와 상기 하이드록시-말단 폴리올레핀 제조단계에서 제조된 하이드록시-말단 폴리올레핀 20,000~40,000중량부를 투여한 다음, 반응기 온도를 30~60℃로 상승시키고 50~500RPM의 속도로 6~24시간 동안 교반시킨 후, 상기 반응기에 환원제 1,000~10,000중량부를 투여하여 반응온도를 30~60℃로 유지시키고 50~500RPM의 속도로 3~12시간 동안 교반하여 생성된 혼합물을 여과/세척후, 50~100℃에서 12~48시간 동안 건조시켜 고분자 개시제(initiator)를 제조하는 고분자 개시제 제조단계와;
가스퍼징장비, 교반기, 온도조절기가 장착된 반응기에 불활성 기체를 퍼징시키면서 반응용매 100,000중량부와 고분자 개시제 제조단계에서 제조된 고분자 개시제 20,000~40,000중량부, 알켄 옥사이드(alkene oxide) 10,000~90,000중량부, 금속 하이드라이드(metal hydride) 100~1,000중량부를 투여하고, 반응기 온도를 60~100℃로 상승시켜 50~500RPM의 속도로 24~60시간 동안 반응시킨 다음, 알코올 1,000~2,000중량부를 첨가하여 반응을 종료시킨 혼합물을 여과 및 세척 후, 50~100℃에서 12~60시간 동안 건조시켜 폴리올레핀-폴리알켄옥사이드 공중합체를 제조하는 공중합체 제조단계와;
교반기, 온도조절기가 장착된 반응기에 분산용매 100,000중량부와 상기 공중합체 제조단계에서 제조된 폴리올레핀-폴리알켄옥사이드 공중합체 20,000~40,000중량부를 투여하고, 반응기 온도를 20~60℃로 상승시켜서 100~500RPM의 속도로 1~6시간 동안 교반한 후, 이온성 액체(ionic liquid) 200~600중량부를 투여하여 반응기 온도를 20~60℃로 유지시키고 50~500RPM의 속도로 1~6시간 동안 교반한 반응물을 여과/세척하여 5~100℃에서 12~24시간 건조하여서 이온성 공중합체를 제조하는 이온성 공중합체 제조단계와;
니더(Kneader)나 헨셀(Hensel), 밴버리(Banbury) 중 하나의 혼합 믹서(mixer)에 에틸렌공중합체(ethylene copolymer), 합성고무(synthetic rubber)에서 선택되어지는 고분자 중합체 100,000중량부와, 전기 전도성 충진제 100~500중량부, 이온성 공중합체 제조단계에서 제조된 이온성 공중합체 20,000~40,000중량부, 산화방지제 50~200중량부, 활제(lubricant) 100~1,400 중량부를 순차적으로 투여하고, 80~200℃ 온도에서 5~60분간 혼련한 덩어리 반죽을 일축(single screw)이나 이축 압출기(twin screw extruder)로 이송시켜 압출성형을 통해 3~5mm 크기의 대전방지제 조성물 펠렛을 제조하는 대전방지제 조성물 제조단계로 이루어짐을 특징으로 하는 대전방지 특성을 갖는 이온성 공중합체를 이용한 대전방지 조성물의 제조방법.While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and a thermostat, 10,000 parts by weight of a polymerization solvent and a chain transfer agent are added. (chain transfer agent) was administered at 10 to 300 parts by weight, monomer was supplied to maintain the pressure at 1 to 2 atm, the reactor temperature was raised to 20 to 100°C, a catalyst (5 to 40 parts by weight) and crude Polymerization is initiated by adding 10 to 60 parts by weight of a co-catalyst and stirring at a speed of 50 to 500 RPM. Monomers are continuously supplied so that the reactor pressure is 1 to 2 atmospheres and the temperature is 20 to 100°C. After the polymerization reaction was completed for 1 to 24 hours while maintaining , 10 to 100 parts by weight of alcohol was added to the polymerization reaction liquid extracted from the bottom of the reactor to terminate the reaction, and the reaction mixture was steam stripped. ) treatment to separate the copolymer from the solvent, followed by drying at 50 to 100°C for 12 to 48 hours to produce borane-terminated polyolefin;
While purging an inert gas in a reactor equipped with gas purging equipment, a dropper, a stirrer, and a temperature controller, 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the borane-terminated polyolefin prepared in the borane-terminated polyolefin production step are added. Dosing sequentially, adding 20,000 to 40,000 parts by weight of distilled water, 2,000 to 8,000 parts by weight of base, and 2,000 to 8,000 parts by weight of alcohol while stirring at a speed of 50 to 500 RPM, then lowering the reaction temperature to -10 to 0°C. , Add 15,000 to 40,000 parts by weight of hydrogen peroxide aqueous solution (10 to 30% by weight of hydrogen peroxide: 90 to 70% by weight of water) dropwise over 30 to 60 minutes, then raise the reaction temperature to 30 to 60°C to 50 to 500 RPM. After the reaction proceeded for a further 4 to 12 hours while stirring at a speed of A hydroxy-terminated polyolefin production step for producing;
While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of reaction solvent and 20,000 to 40,000 parts by weight of hydroxy-terminated polyolefin prepared in the hydroxy-terminated polyolefin production step were administered. Then, the reactor temperature was raised to 30-60°C and stirred at a speed of 50-500RPM for 6-24 hours, and then 1,000-10,000 parts by weight of reducing agent was added to the reactor to maintain the reaction temperature at 30-60°C and 50°C. A polymer initiator preparation step of preparing a polymer initiator by filtering/washing the resulting mixture by stirring for 3 to 12 hours at a speed of ~500 RPM and drying it at 50 to 100°C for 12 to 48 hours;
While purging an inert gas in a reactor equipped with gas purging equipment, a stirrer, and temperature controller, 100,000 parts by weight of reaction solvent, 20,000 to 40,000 parts by weight of polymer initiator prepared in the polymer initiator manufacturing step, and 10,000 to 90,000 parts by weight of alkene oxide. , 100 to 1,000 parts by weight of metal hydride was administered, the reactor temperature was raised to 60 to 100°C and reaction was performed at a rate of 50 to 500 RPM for 24 to 60 hours, and then 1,000 to 2,000 parts by weight of alcohol was added for reaction. A copolymer production step of filtering and washing the resulting mixture and drying it at 50 to 100°C for 12 to 60 hours to produce a polyolefin-polyalkenoxide copolymer;
100,000 parts by weight of the dispersion solvent and 20,000 to 40,000 parts by weight of the polyolefin-polyalkenoxide copolymer prepared in the copolymer production step were added to a reactor equipped with a stirrer and a temperature controller, and the temperature of the reactor was raised to 20 to 60 ° C. After stirring for 1 to 6 hours at a speed of 500 RPM, 200 to 600 parts by weight of ionic liquid was added to maintain the reactor temperature at 20 to 60°C and stirred for 1 to 6 hours at a speed of 50 to 500 RPM. An ionic copolymer preparation step of preparing an ionic copolymer by filtering/washing the reactant and drying it at 5-100°C for 12-24 hours;
100,000 parts by weight of a polymer selected from ethylene copolymer and synthetic rubber in a mixing mixer made by Kneader, Hensel, or Banbury, and an electrically conductive 100 to 500 parts by weight of filler, 20,000 to 40,000 parts by weight of ionic copolymer prepared in the ionic copolymer manufacturing step, 50 to 200 parts by weight of antioxidant, and 100 to 1,400 parts by weight of lubricant are sequentially administered, and Antistatic agent composition manufacturing step in which the lump dough kneaded at 200°C for 5 to 60 minutes is transferred to a single screw or twin screw extruder to produce antistatic agent composition pellets of 3 to 5 mm in size through extrusion molding. A method for producing an antistatic composition using an ionic copolymer with antistatic properties, characterized in that it consists of.
상기 폴리올레핀의 보란화 단계에서 불활성 기체(inert gas)는, 질소(nitrogen)나, 아르곤(argon), 네온(neon) 중에서 선택되며, 상기 중합용매(polymerization solvent)는 펜탄(pentane)이나, 헥산(hexane), 헵탄(heptane), 옥탄(octane), 시클로헥산(cyclohexane), 벤젠(benzene), 톨루엔(toluene), 크실렌(xylene) 중 하나의 유기용매(organic solvent)에서 선택되며, 상기 체인 트랜스퍼제(chain transfer agent)는, 트리에틸보란(triethylborane)이나, 트리프로필보란(tripropylborane), 디메시틸보란(dimesitylborane), 9-보라비실코노난(9-borabicylcononane), 보론 디피로메텐(boron dipyrromethene), 텍실보란(thexylborane), 디시아밀보란 (disiamylborane) 중 하나의 보란 컴파운드에서 선택되며, 상기 단량체(monomer)는, 에틸렌(ethylene)이나, 프로필렌(propylene), 부텐(butene), 시클로펜탄(cyclopentene), 4-메틸-1-펜텐(4-methyl-1-pentene) 중 하나의 알켄(alkene)을 단독 또는 2종 이상 선택되며, 상기 촉매(catalyst)는, 라세미-디메틸실릴비스(1-인데닐)지르코늄 디클로라이드[rac-dimethylsilylbis(1-indenyl)zirconium dichloride], 라세미-디메틸실릴비스[1-(2-메틸-4,5-벤조인데닐)]지르코늄 디클로라이드{rac-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride}, 라세미-디메틸실릴비스(2-에틸-4-페닐인데닐)지르코늄 디클로라이[rac-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride], 라세미-디메틸실릴비스[1-(2-n-프로필-4-(1-나프틸)인데닐)]지르코늄 디클로라이드 {rac-dimethylsilyl-bis[l-(2-n-propyl-4-(1-naphthyl)indenyl)]zirconium dichloride}, 라세미-디메틸실릴비스[1-(2-에틸-4-(9-페난트릴)인데닐)]지르코늄 디클로라이드{rac-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride}, 라세미-디메틸실릴비스[1-(2-n-프로필-4-(9-페난트릴)인데닐)]지르코늄 디클로라이드{rac-dimethylsilylbis[l-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride} 중 하나의 지르코늄 화합물에서 선택되며, 상기 조촉매(co-catalyst)는, 메틸알루미녹산(methylaluminoxane)이나, 2,6-디-터트-부틸-4-메틸페놀 변성 메틸알루미녹산(2,6-di-tert-butyl-4-methylphenol modified methylaluminoxane), 폴리메틸알루미녹산(polymethylaluminoxane) 중 하나의 알루미녹산에서 선택되며, 상기 알코올(alcohol)은, 메탄올(methanol)이나 에탄올(ethanol), 프로판올(propanol), 이소프로필 알코올(isopropyl alcohol) 중 하나에서 선택되며;
상기 폴리올레핀의 관능화 단계에서 반응용매(reaction solvent)는, 디에틸 에테르(diethyl ether)나 에틸아세테이트(ethyl acetate), 테트라하이드로퓨란(tetrahydrofuran), 메틸에틸케톤(methyl ethyl ketone) 중 하나에서 선택되며, 상기 염기(base)는, 소디움 하이드록사이드(sodium hydroxide)나 포타슘 하이드록사이드(potassium hydroxide) 중 하나이며;
상기 고분자 개시제 제조단계에서 반응용매(reaction solvent)는, 디에틸 에테르(diethyl ether)나 에칠아세테이트(ethyl acetate), 테트라하이드로퓨란(tetrahydrofuran), 메틸에틸케톤(methyl ethyl ketone) 중 하나에서 선택되며, 상기 환원제는, 소디움 나프탈라이드(sodium naphthalenide)나 리튬 나프탈라이드(lithium naphthalenide), 칼륨 나프탈라이드(potassium naphthalenide) 중 하나에서 선택되며;
상기 공중합체 제조단계에서 알켄 옥사이드(alkene oxide)는, 에틸렌 옥사이드(ethylene oxide)나, 프로필렌 옥사이드(propylene oxide), 부틸렌 옥사이드(butylene oxide), 옥텐 옥사이드(octene oxide) 중 하나이며, 상기 금속 하이드라이드(metal hydride)는, 베릴륨 하이드라이드(beryllium hydride)나 칼슘 하이드라이드(calcium hydride), 티타늄 하이드라이드(titanium hydride) 중 하나에서 선택되며;
상기 이온성 공중합체 제조단계에서 분산용매는, 에테르(ether)나 케톤(ketone), 알코올(alcohol) 중 하나에서 선택되며, 상기 이온성 액체(ionic liquid)는, 소디움 티오시아네이트(sodium thiocyanate)나 포타슘 티오시아네이트(potassium thiocyanate), 1-에틸-3-메틸이미다졸륨 티오시아네이트(1-ethyl 3-methylimidazolium, thiocyanate), 1-부틸-3-메틸이미다졸륨 티오시아네이트(1-butyl-3-methylimidazolium thiocyanate), 1-부틸-1-메틸피롤리디늄 티오시아네이트(1-butyl-1-methylpyrrolidinium thiocyanate), 1-에틸-1-메틸피페리디늄 티오시아네이트(1-ethyl-1-methylpiperidinium thiocyanate) 중 하나에서 선택되며;
대전방지제 조성물 제조단계에서 고분자 중합체는, 폴리에틸렌(polyethylene)이나, 폴리프로필렌(polypropylene), 폴리메틸펜텐(polymethylpentene) 중 하나의 폴리올레핀(polyolefin) 수지나, 에틸렌-비닐아세테이트 공중합체(ethylene-vinyl acetate copolymer)나, 에틸렌-프로필렌 공중합체(ethylene-propylene copolymer), 에틸렌-프로필렌-디엔 공중합체(ethylene-propylene-diene copolymer), 에틸렌-에틸아크릴레이트 공중합체(ethylene-ethylacrylate copolymer) 중 하나의 에틸렌공중합체(ethylene copolymer), 부타디엔 고무(butadiene rubber)나, 니드릴부타디엔 고무(nitrile butadiene rubber), 클로로프렌 고무(chloroprene rubber), 이소부틸렌 고무(isobutylene rubber), 스티렌부타디엔 고무(styrene butadiene rubber) 중 하나의 합성고무(synthetic rubber)에서 선택되며, 상기 전기 전도성 충진제는, 그래핀(graphene)이나, 카본 블랙(carbon black), 그래파이트(graphite), 전기 전도성 마이카(electro-conductive mica), 인듐 틴 옥사이드(indium tin oxide), 틴 옥사이드(tin dioxide), 징크 옥사이드(zinc oxide), 안티모니 틴 옥사이드 (antimony-doped tin oxide) 중 하나에서 선택되며, 상기 산화방지제는, 티오디에틸렌 비스[3-(3,5-디-터트-부틸-4-히드로옥시페닐)프로피오네이트][thiodiethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]나, 티오디프로피오닉 액시드 디옥타데실에스테르(thiodipropionic acid dioctadecylester), 디스테아릴 티오디프로피오네이트(distearyl thiodipropionate), 3-메르캅토프로피오닉 액시드(3-mercaptopropionic acid) 중 하나의 황화합물 중에서 단독 또는 2종 이상 혼합사용 되며, 상기 활제(lubricant)는, 칼슘 스테아레이트(calcium stearate), 마그네슘 스테아레이트(magnesium stearate), 알루미늄 스테아레이트(aluminum stearate), 리튬 스테아레이트 (lithium stearate) 중 하나의 지방산 금속염(fatty acid metal salt)에서 선택되는 것을 특징으로 하는 대전방지 특성을 갖는 이온성 공중합체를 이용한 대전방지 조성물의 제조방법.According to paragraph 1,
In the boranization step of the polyolefin, the inert gas is selected from nitrogen, argon, and neon, and the polymerization solvent is pentane or hexane ( selected from the group consisting of hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene, and the chain transfer agent (Chain transfer agent) is triethylborane, tripropylborane, dimesitylborane, 9-borabicylcononane, and boron dipyromethene. , thexylborane, and disiamylborane, and the monomer is ethylene, propylene, butene, or cyclopentene. , 4-methyl-1-pentene, one alkene is selected alone or two or more types are selected, and the catalyst is racemic-dimethylsilylbis (1-). Nyl) zirconium dichloride [rac-dimethylsilylbis(1-indenyl)zirconium dichloride], racemic-dimethylsilylbis[1-(2-methyl-4,5-benzoindenyl)]zirconium dichloride {rac-dimethylsilylbis[1 -(2-methyl-4,5-benzoindenyl)]zirconium dichloride}, racemic-dimethylsilylbis(2-ethyl-4-phenylindenyl)zirconium dichloride[rac-dimethylsilylbis(2-ethyl-4-phenylindenyl) )zirconium dichloride], racemic-dimethylsilylbis[1-(2-n-propyl-4-(1-naphthyl)indenyl)]zirconium dichloride {rac-dimethylsilyl-bis[l-(2-n- propyl-4-(1-naphthyl)indenyl)]zirconium dichloride}, racemic-dimethylsilylbis[1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride{rac-dimethylsilylbis[ 1-(2-ethyl-4-(9-phenanthryl)indenyl)]zirconium dichloride}, racemic-dimethylsilylbis[1-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium Dichloride {rac-dimethylsilylbis[l-(2-n-propyl-4-(9-phenanthryl)indenyl)]zirconium dichloride} is selected from one zirconium compound, and the co-catalyst is methylaluminum. Among methylaluminoxane, 2,6-di-tert-butyl-4-methylphenol modified methylaluminoxane, and polymethylaluminoxane One aluminoxane is selected, and the alcohol is selected from methanol, ethanol, propanol, or isopropyl alcohol;
In the functionalization step of the polyolefin, the reaction solvent is selected from diethyl ether, ethyl acetate, tetrahydrofuran, and methyl ethyl ketone. , the base is either sodium hydroxide or potassium hydroxide;
In the polymer initiator preparation step, the reaction solvent is selected from diethyl ether, ethyl acetate, tetrahydrofuran, and methyl ethyl ketone, The reducing agent is selected from sodium naphthalenide, lithium naphthalenide, and potassium naphthalenide;
In the copolymer manufacturing step, the alkene oxide is one of ethylene oxide, propylene oxide, butylene oxide, and octene oxide, and the metal oxide Metal hydride is selected from beryllium hydride, calcium hydride, and titanium hydride;
In the ionic copolymer manufacturing step, the dispersion solvent is selected from ether, ketone, or alcohol, and the ionic liquid is sodium thiocyanate. Na potassium thiocyanate, 1-ethyl 3-methylimidazolium, thiocyanate, 1-butyl-3-methylimidazolium thiocyanate (1- butyl-3-methylimidazolium thiocyanate), 1-butyl-1-methylpyrrolidinium thiocyanate, 1-ethyl-1-methylpiperidinium thiocyanate (1-ethyl- 1-methylpiperidinium thiocyanate);
In the antistatic agent composition manufacturing step, the polymer is a polyolefin resin such as polyethylene, polypropylene, or polymethylpentene, or an ethylene-vinyl acetate copolymer. ) or, one of ethylene-propylene copolymer, ethylene-propylene-diene copolymer, and ethylene-ethylacrylate copolymer. (ethylene copolymer), butadiene rubber, nitrile butadiene rubber, chloroprene rubber, isobutylene rubber, or styrene butadiene rubber. It is selected from synthetic rubber, and the electrically conductive filler is graphene, carbon black, graphite, electro-conductive mica, or indium tin oxide. It is selected from one of tin oxide, tin dioxide, zinc oxide, and antimony-doped tin oxide, and the antioxidant is thiodiethylene bis [3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate] [thiodiethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or thiodipropionic acid di It is used alone or in combination of two or more sulfur compounds among octadecyl ester (thiodipropionic acid dioctadecylester), distearyl thiodipropionate, and 3-mercaptopropionic acid. The lubricant is a fatty acid metal salt of calcium stearate, magnesium stearate, aluminum stearate, or lithium stearate. A method for producing an antistatic composition using an ionic copolymer with antistatic properties, characterized in that the selected.
반응용매(reaction solvent) 100,000중량부와, 상기 보란-말단 폴리올레핀 20,000~40,000중량부를 교반하면서 증류수 20,000~40,000중량부, 염기(base) 2,000~8,000중량부, 알코올 2,000~8,000 중량부를 첨가하고, 하이드로겐 퍼옥사이드수용액(하이드로겐 퍼옥사이드 10~30중량% : 물함량 90~70중량%) 15,000~40,000중량부를 적가하여 얻어진 하이드록시-말단 폴리올레핀(hydroxy-terminated polyolefin)과;
불활성 기체를 퍼징시키면서 반응용매(reaction solvent) 100,000중량부와 상기 하이드록시-말단 폴리올레핀 20,000~40,000중량부를 교반하고, 환원제 1,000~10,000중량부를 투여하여 얻은 고분자 개시제(initiator)와;
반응용매 100,000중량부와 고분자 개시제 20,000~40,000중량부, 알켄 옥사이드(alkene oxide) 10,000~90,000중량부, 금속 하이드라이드(metal hydride) 100~1,000중량부를 교반하여 반응시킨 다음 알코올 1,000~2,000중량부를 첨가하여 반응을 종료시켜서 폴리올레핀-폴리알켄옥사이드 공중합체를 얻고,
분산용매 100,000중량부와 상기 폴리올레핀-폴리알켄옥사이드 공중합체 20,000~40,000중량부를 교반하고, 이온성 액체(ionic liquid) 200~600중량부를 투여하여 얻어진 것을 특징으로 하는 대전방지 특성을 갖는 이온성 공중합체.While purging an inert gas, 10,000 parts by weight of a polymerization solvent selected from an organic solvent and 10 to 300 parts by weight of a chain transfer agent selected from a borane compound. 5 to 40 parts by weight of a catalyst selected from a zirconium compound and 10 to 60 parts by weight of a co-catalyst selected from aluminoxane are stirred, and an alkene is added alone or two or more types. A borane-terminated polyolefin prepared by supplying a selected monomer and adding 10 to 100 parts by weight of alcohol to the polymerization reaction solution in which the polymerization reaction was performed;
While stirring 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the borane-terminated polyolefin, 20,000 to 40,000 parts by weight of distilled water, 2,000 to 8,000 parts by weight of a base, and 2,000 to 8,000 parts by weight of alcohol were added, and hydro A hydroxy-terminated polyolefin obtained by dropwise adding 15,000 to 40,000 parts by weight of an aqueous solution of hydrogen peroxide (10 to 30% by weight of hydrogen peroxide: 90 to 70% by weight of water);
A polymer initiator obtained by stirring 100,000 parts by weight of a reaction solvent and 20,000 to 40,000 parts by weight of the hydroxy-terminated polyolefin while purging an inert gas, and adding 1,000 to 10,000 parts by weight of a reducing agent;
Stir and react 100,000 parts by weight of reaction solvent, 20,000 to 40,000 parts by weight of polymer initiator, 10,000 to 90,000 parts by weight of alkene oxide, and 100 to 1,000 parts by weight of metal hydride, then add 1,000 to 2,000 parts by weight of alcohol. The reaction is terminated to obtain a polyolefin-polyalkenoxide copolymer,
An ionic copolymer with antistatic properties obtained by stirring 100,000 parts by weight of a dispersion solvent and 20,000 to 40,000 parts by weight of the polyolefin-polyalkenoxide copolymer and adding 200 to 600 parts by weight of an ionic liquid. .
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