KR100342668B1 - Crosslinked polymer having a good oil absorbency and method of preparing the same - Google Patents
Crosslinked polymer having a good oil absorbency and method of preparing the same Download PDFInfo
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- KR100342668B1 KR100342668B1 KR1019990032111A KR19990032111A KR100342668B1 KR 100342668 B1 KR100342668 B1 KR 100342668B1 KR 1019990032111 A KR1019990032111 A KR 1019990032111A KR 19990032111 A KR19990032111 A KR 19990032111A KR 100342668 B1 KR100342668 B1 KR 100342668B1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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Abstract
본 발명의 흡유성 가교 고분자는 비닐단량체-무수말레산 공중합체에 친유성 그룹을 갖는 알킬알코올을 반응시킨 후, 그 생성물에 가교제를 가교반응시켜 제조된다. 상기 비닐단량체-무수말레산 공중합체는 용해성이 우수한 폴리(스티렌-무수말레산)공중합체가 바람직하며, 상기 알킬알코올은 메틸렌기의 탄소 수가 긴 n-테트라데칸올, n-헥사데칸올, n-옥타데칸올 및 4-도데실페놀로부터 선택된다. 사용되는 상기 알킬알코올의 양은 비닐단량체-무수말레산 공중합체에 포함된 무수말레산 농도의 20 내지 100%의 범위가 바람직하다. 상기 가교제는 양말단에 작용기를 갖는 것으로, 그 예로는 장쇄 탄화수소디올 또는 디글리시딜에테르가 있으며, 사용되는 가교제의 양은 상기 비닐단량체-무수말레산 공중합체에 포함된 무수말레산 농도의 30 내지 100%의 범위가 바람직하다. 본 발명의 흡유성 가교 고분자는 유기용매를 흡수, 팽윤 및 겔화시킴으로써 외부의 압력을 받아도 흡수된 용매를 배출하지 않는 우수한 가압보지력을 가지며, 사용된 유기용매의 종류에 따라 본 발명의 흡유성 가교 고분자 자체 무게당 5 내지 40 배의 흡유능을 갖는다.The oil-absorbing crosslinked polymer of the present invention is prepared by reacting an alkyl alcohol having a lipophilic group with a vinyl monomer-maleic anhydride copolymer and then crosslinking a crosslinking agent with the product. The vinyl monomer-maleic anhydride copolymer is preferably a poly (styrene-maleic anhydride) copolymer having excellent solubility, and the alkyl alcohol is n-tetradecanol, n-hexadecanol, n having a long carbon number of the methylene group. -Octadecanol and 4-dodecylphenol. The amount of the alkyl alcohol to be used is preferably in the range of 20 to 100% of the maleic anhydride concentration contained in the vinyl monomer-maleic anhydride copolymer. The crosslinking agent has a functional group at the sock end, and examples thereof include long-chain hydrocarbon diol or diglycidyl ether, and the amount of the crosslinking agent used is 30 to 30% of the maleic anhydride concentration contained in the vinyl monomer-maleic anhydride copolymer. The range of 100% is preferable. The oil-absorbing crosslinked polymer of the present invention has excellent pressure holding power which does not discharge the absorbed solvent even under external pressure by absorbing, swelling and gelling the organic solvent, and according to the type of organic solvent used It has an oil absorption of 5 to 40 times per weight of the polymer itself.
Description
발명의 분야Field of invention
본 발명은 물에 혼합되어 있는 할로겐화 유기용매, 톨루엔, 벤젠 또는 탄소 수가 5개 이상인 탄화수소 유기용매들을 선택적으로 흡수, 팽윤시켜 겔화할 수 있는 신규의 흡유성 가교 고분자 및 그 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 유기용매와 반데르발스 인력(van der waals interaction)이 매우 큰 긴 알킬기를 고분자 사슬에 도입한 신규의 흡유성 가교 고분자 및 그의 제조방법에 관한 것이다.The present invention relates to a novel oil-absorbing crosslinked polymer capable of selectively absorbing, swelling and gelating a halogenated organic solvent, toluene, benzene or a hydrocarbon organic solvent having 5 or more carbon atoms mixed in water, and a method for producing the same. More specifically, the present invention relates to a novel oil-absorbing crosslinked polymer in which a long alkyl group having a very large van der waals interaction with an organic solvent is introduced into a polymer chain, and a method for preparing the same.
발명의 배경Background of the Invention
최근 산업의 발달로 유기용제 및 석유의 사용량이 급속히 증가함에 따라 유기용매들이 물과 혼합되어 있는 폐액(廢液)의 방출로 인하여 수질 오염이 심각해지고 있다. 또한, 매년 유조선의 해양사고로 인하여 해양오염은 물론 환경생태계의파괴가 심각하다. 따라서 수질개선 및 지구환경 보호를 위하여 유출된 유기용제나 석유 등을 물로부터 선택적으로 흡수, 분리할 수 있는 흡유성 고분자의 개발이 절실히 요구된다.Recently, as the amount of organic solvent and petroleum is rapidly increased due to the development of the industry, water pollution is serious due to the discharge of the waste liquid in which the organic solvent is mixed with water. In addition, due to the marine accident of the tanker every year, not only marine pollution, but also the destruction of environmental ecosystem. Therefore, there is an urgent need to develop an oil absorbent polymer capable of selectively absorbing and separating organic solvents or petroleum spilled from water to improve water quality and protect the global environment.
해양에 유출된 오일을 제거하는 종래의 방법으로서 첫째, 분말형태의 재(cinder) 또는 점토(clay)를 바다에 분산시킨 후 유출된 오일을 흡착시켜 침전시키는 흡착침전물을 이용하는 방법(미국특허 제3,843,306호)과 둘째, 계면활성제를 오일이 유출된 지역에 뿌린 후 물 제트기(water jet)와 같은 기계로 교반시켜 물과 기름을 에멀젼 상태로 만든 다음 자연분해 되도록 하는 방법(日本水産學會編, 1979, 石油汚染水産生物, p128-145)이 있다.As a conventional method of removing oil spilled into the ocean, first, a method of using an adsorption precipitate which disperses powdered cinder or clay in the sea and then adsorbs the precipitated oil to precipitate (US Patent No. 3,843,306). No. 2) and second, a method of spraying a surfactant into an oil spill area and then stirring it with a machine such as a water jet to make the water and oil an emulsion and then decomposing it naturally (日本 水産 學會 編, 1979,石油 汚染 水産 生物, p128-145).
또한, 미국특허 제3,668,118호 및 제3,812,973호에 의하면 기존의 폴리에틸렌 또는 폴리프로필렌 섬유에 파라핀(paraffin) 등의 친유성 화합물을 코팅시켜 만든 부직포를 이용하여 유출된 오일을 흡착시켜 분리하는 방법이 알려져 있다.In addition, US Pat. Nos. 3,668,118 and 3,812,973 disclose a method of adsorbing and separating oil spilled by using a nonwoven fabric made by coating a lipophilic compound such as paraffin on an existing polyethylene or polypropylene fiber. .
그러나 상기 흡착침전물을 사용할 경우 재나 점토에 흡착된 오일이 시간이 지남에 따라 방출되는 단점이 있으며, 그리고 상기 계면활성제를 이용하는 경우는 흡수한 오일을 다시 회수하기 어렵고 오일 에멀젼에 의해 해양생태계를 파괴시키는 2차 오염을 피할 수 없게 된다. 또한 폴리에틸렌 등의 부직포를 사용하는 경우도 흡유 배율이 매우 낮고 가압보지력이 약하여 흡수된 오일이 방출되기 쉬운 단점이 있다.However, there is a disadvantage in that the adsorbed sediment is released over time as the oil adsorbed on the ash or clay, and when using the surfactant, it is difficult to recover the absorbed oil again and destroy the marine ecosystem by the oil emulsion. Secondary pollution is inevitable. In addition, in the case of using a nonwoven fabric such as polyethylene, there is a disadvantage in that the oil absorption ratio is very low and the pressure holding force is weak so that the absorbed oil is easily released.
이러한 문제점을 극복하기 위하여 미국의 다우 케미컬(Dow Chemical)사는 p-t-부틸스티렌(p-t-butylstyrene) 단량체로부터 유도된 가교 폴리부틸스티렌 및 이들의 공중합체를 개발하였다(일본특허공고 제45-27081호). 일본의 미쓰이 석유화학은 t-부틸메타크릴레이트(t-butylmethacrylate), 1,5-디메틸-6-비시클로[3,2,1]옥틸메타크릴레이트(1,5-dimethyl-6-bicyclo[3,2,1]octylmethacrylate), 메틸아크릴레이트, 또는 아릴메타크릴레이트(arylmethacrylate)와 같은 단량체를 이용하여 아크릴레이트계 가교 고분자 및 이들 단량체와 스티렌 단량체로부터 유도된 공중합체를 개발하였다(일본특허공개 제50-15882호, 제50-59486호, 및 제50-94092호). 또한 장쇄 탄화수소기를 측쇄에 갖는 아크릴레이트계 저가교밀도형 고분자가 일본촉매화학사에 의해 개발되어 발표되었다(일본 기능재료 1990. 11. pp43-49).To overcome this problem, Dow Chemical of the United States has developed crosslinked polybutylstyrene and copolymers thereof derived from pt-butylstyrene monomers (Japanese Patent Publication No. 45-27081). . Japan's Mitsui Petrochemical Co., Ltd. has t-butylmethacrylate, 1,5-dimethyl-6-bicyclo [3,2,1] octyl methacrylate (1,5-dimethyl-6-bicyclo [ Acrylate-based crosslinked polymers and copolymers derived from these monomers and styrene monomers were developed using monomers such as 3,2,1] octylmethacrylate), methylacrylate, or arylmethacrylate (Japanese Patent Laid-Open). 50-15882, 50-59486, and 50-94092). In addition, an acrylate-based low-molecular-weight polymer having a long-chain hydrocarbon group in its side chain was developed and published by Nippon Catalytic Chemicals Co., Ltd. (Japanese functional material 1990. 11. pp43-49).
상기 공지의 기술들은 비닐단량체에 라디칼 개시제를 이용하여 라디칼 중합반응을 일으킴으로써 흡유성 고분자를 얻는 방법이다. 이런 방법은 중합공정상 흡유성 고분자의 제조가 매우 용이하다. 그러나 기본적으로 흡유성 가교 고분자의 분자구조를 조절하기 어려운 단점이 있다. 즉, 라디칼 중합반응을 일으키기 위해서는 비닐단량체와 비닐그룹이 2개 이상 결합된 가교제를 반드시 사용해야 하는데 할로겐 유기용매, 벤젠 또는 석유계 탄화수소와 같은 흡유물질과 친화력이 큰 관능성 그룹(functional group)의 도입이 매우 어려울 뿐만 아니라 단량체와 가교제의 선택이 극히 제한되어 있다.The known techniques are a method of obtaining an oil absorbent polymer by causing a radical polymerization reaction using a radical initiator on a vinyl monomer. This method is very easy to prepare the oil absorbent polymer in the polymerization process. However, there is a disadvantage in that it is difficult to control the molecular structure of the oil absorbing crosslinked polymer. In other words, in order to cause the radical polymerization reaction, a crosslinking agent in which two or more vinyl monomers and vinyl groups are combined must be used. A functional group having a high affinity with an oil absorbent such as a halogen organic solvent, benzene or petroleum hydrocarbon is introduced. Not only is this very difficult, but the choice of monomers and crosslinkers is extremely limited.
이에 본 발명자들은 상기 공지 제조기술들의 단점을 극복할 수 있는 흡수배율이 비교적 높고 흡유속도가 빠르며 가공이 용이한 다공성의 흡유성 가교 고분자를 개발하기에 이른 것이다.Accordingly, the present inventors have led to the development of a porous oil-absorbing crosslinked polymer having a relatively high absorption rate, a high oil absorption rate, and easy processing that can overcome the disadvantages of the known manufacturing techniques.
본 발명의 목적은 유기용매와 친화력이 큰 알킬기를 측쇄에 가지고 있어 상기 유기용매를 물로부터 선택적으로 흡수, 분리할 수 있으며, 흡수배율이 높고, 그리고 흡유속도가 빠른 흡유성 가교 고분자를 제공하기 위한 것이다.An object of the present invention is to provide an oil-absorbing crosslinked polymer having an alkyl group having a high affinity with an organic solvent in the side chain to selectively absorb and separate the organic solvent from water, high absorption ratio, and high oil absorption rate. will be.
본 발명의 다른 목적은 비닐단량체-무수말레산 공중합체에 포함된 무수말레산 농도의 30 내지 100%로 가교제를 사용함으로써 흡유능 및 가압보지력이 우수하여 외부의 압력에도 흡수된 용매를 쉽게 배출하지 않는 흡유성 가교 고분자를 제공하기 위한 것이다.Another object of the present invention is to use a crosslinking agent at a concentration of 30 to 100% of the maleic anhydride concentration contained in the vinyl monomer-maleic anhydride copolymer, so that the solvent absorbed by external pressure can be easily discharged due to its excellent oil absorption and pressure holding ability. To provide an oil-absorbing crosslinked polymer that does not.
본 발명의 또 다른 목적은 폐액으로부터 유기용제나 석유 등을 분리함으로써 수질개선 및 나아가 지구 환경을 보호할 수 있는 흡유성 가교 고분자를 제공하기 위한 것이다.Another object of the present invention is to provide an oil-absorbing crosslinked polymer that can improve the water quality and further protect the global environment by separating organic solvents, petroleum, and the like from the waste liquid.
본 발명의 또 다른 목적은 물과 혼합되어 있는 유기용제를 선택적으로 흡수 및 분리할 수 있고, 흡수배율이 높고 흡유속도가 빠르며 가공이 용이한 흡유성 가교 고분자의 제조방법을 제공하기 위한 것이다.Still another object of the present invention is to provide a method for preparing an oil absorbent crosslinked polymer which can selectively absorb and separate an organic solvent mixed with water, and has a high absorption ratio, a high oil absorption rate, and easy processing.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다. 이하 본 발명의 내용을 하기에 상세히 설명한다.The above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the content of the present invention will be described in detail.
본 발명의 흡유성 가교 고분자는 기질 고분자로서 비닐단량체-무수말레산 공중합체를 사용하고, 상기 비닐단량체-무수말레산 공중합체를 알킬알코올과 반응시켜서 흡유성 고분자를 생성하고, 그리고 생성된 흡유성 고분자에 양말단에 작용기를 갖는 가교제를 가교반응시킴으로써 제조된다.The oil absorbent crosslinked polymer of the present invention uses a vinyl monomer-maleic anhydride copolymer as a substrate polymer, and reacts the vinyl monomer-maleic anhydride copolymer with an alkyl alcohol to produce an oil absorbent polymer, and the resulting oil absorbent It is prepared by crosslinking a crosslinking agent having a functional group on a sock end in a polymer.
비닐단량체-무수말레산 공중합체는 폴리(스티렌-무수말레산), 폴리(에틸렌-무수말레산), 폴리(프로필렌-무수말레산), 폴리(에틸렌-t-부틸아크릴레이트-무수말레산), 및 폴리(에틸렌-에틸아크릴레이트-무수말레산)으로 이루어지는 군으로부터 선택되며, 이 중에서 용해도가 우수한 폴리(스티렌-무수말레산)이 바람직하다. 비닐단량체-무수말레산 공중합체에서 무수말레산의 조성은 5 내지 50%가 바람직하며, 더 바람직하기로는 5 내지 30%의 범위이다.Vinyl monomer-maleic anhydride copolymers include poly (styrene-maleic anhydride), poly (ethylene-maleic anhydride), poly (propylene-maleic anhydride), poly (ethylene-t-butylacrylate-maleic anhydride) And poly (ethylene-ethyl acrylate-maleic anhydride), among which poly (styrene-maleic anhydride) excellent in solubility is preferred. The composition of maleic anhydride in the vinyl monomer-maleic anhydride copolymer is preferably 5 to 50%, more preferably in the range of 5 to 30%.
친유성 그룹을 가지는 알킬알코올은 n-테트라데칸올, n-헥사데칸올, n-옥타데칸올 및 4-도데실페놀로 이루어지는 군으로부터 선택된다. 사용되는 알킬알코올의 양은 상기 비닐단량체-무수말레산 공중합체에 포함된 무수말레산 농도의 20 내지 100%의 범위가 바람직하다. 상기 공중합체와 알킬알코올과의 반응온도 및 반응시간은 적용되는 기질 고분자에 따라 다르나 60 내지 160℃에서 4시간 내지 12시간 반응시키는 것이 바람직하다. 더 바람직하기로는 60 내지 100℃에서 4시간 내지 8시간 반응시키는 것이다.The alkyl alcohol having a lipophilic group is selected from the group consisting of n-tetradecanol, n-hexadecanol, n-octadecanol and 4-dodecylphenol. The amount of alkyl alcohol to be used is preferably in the range of 20 to 100% of the maleic anhydride concentration contained in the vinyl monomer-maleic anhydride copolymer. The reaction temperature and reaction time of the copolymer and alkyl alcohol are different depending on the substrate polymer to be applied, but it is preferable to react at 60 to 160 ℃ for 4 hours to 12 hours. More preferably, it is made to react at 60-100 degreeC for 4 hours-8 hours.
상기 공중합체와 알코올과의 반응으로 생성되는 흡유성 고분자를 가교시키기 위한 가교제로서 장쇄 탄화수소디올 또는 디글리시딜에테르가 바람직하다. 가교반응에 적합한 온도, 압력 및 시간의 가교 조건은 60℃ 내지 100℃, 1 내지 10 ㎜Hg에서 4시간 내지 12시간동안 반응시키는 것이 바람직하며, 더 바람직하기로는 8시간 내지 12시간 반응시키는 것이다.Long-chain hydrocarbondiol or diglycidyl ether is preferred as a crosslinking agent for crosslinking the oil absorbent polymer produced by the reaction of the copolymer with alcohol. The crosslinking conditions of temperature, pressure and time suitable for the crosslinking reaction are preferably reacted at 60 ° C. to 100 ° C. for 1 to 10 mmHg for 4 to 12 hours, and more preferably 8 to 12 hours.
상기 가교제의 양은 상기 비닐단량체-무수말레산 공중합체에 포함된 무수말레산 농도의 30 내지 100%로 사용하는 것이 바람직하다. 가교제의 양이 너무 적은 경우에는 가교 밀도가 낮아져서 흡유성 가교 고분자의 흡유능 및 가압보지력이 떨어지게 된다. 또한 가교제의 양을 과다하게 사용하면 흡유속도 및 가압보지력은 증가하지만, 가교 고분자의 사슬이 유동성을 잃어버리기 때문에 흡유능이 급속히 감소한다.The amount of the crosslinking agent is preferably used at 30 to 100% of the maleic anhydride concentration contained in the vinyl monomer-maleic anhydride copolymer. If the amount of the crosslinking agent is too small, the crosslinking density is lowered, so that the oil absorption ability and the pressure holding force of the oil absorbent crosslinked polymer are lowered. In addition, when the amount of the crosslinking agent is excessively used, the oil absorption rate and the pressure holding force are increased, but the oil absorption capacity is rapidly decreased because the chain of the crosslinked polymer loses fluidity.
따라서 원하는 흡유능, 가압보지력 및 흡유속도를 갖는 흡유성 가교 고분자를 제조하기 위해서는 가교제의 종류, 농도 및 조건을 최적화하는 것이 무엇보다 중요하다.Therefore, it is most important to optimize the type, concentration and conditions of the crosslinking agent in order to prepare the oil absorbent crosslinked polymer having the desired oil absorption capacity, pressure holding force and oil absorption rate.
본 발명의 한 구체예인 흡유성 가교 고분자의 합성은 기질 고분자로서 하기 화학식(1)으로 표시되는 폴리(스티렌-무수말레산)과 친유성 그룹을 가지는 하기 화학식(2)의 알코올을 반응시켜서 하기 화학식(3)의 흡유성 고분자를 제조하고; 그리고 하기 화학식(4)으로 표시되는 가교제를 일정시간동안 반응시킴으로써 이루어진다:Synthesis of the oil-absorbing crosslinked polymer which is one embodiment of the present invention is carried out by reacting a poly (styrene-maleic anhydride) represented by the following formula (1) with an alcohol of the following formula (2) having a lipophilic group as a substrate polymer. Preparing the oil absorbent polymer of (3); And it is made by reacting the crosslinking agent represented by following formula (4) for a predetermined time:
; ;
상기 흡유성 가교 고분자는 유기용매를 흡수, 팽윤 및 겔화시켜 외부의 압력을 받아도 흡수된 용매를 배출하지 않는 우수한 가압보지력을 갖는다. 또한 사용된 유기용매의 종류에 따라 흡유성 가교 고분자 자체 무게당 5 내지 40배의 흡유능을 갖는다.The oil-absorbing crosslinked polymer has excellent pressure holding power that does not discharge the absorbed solvent even when the organic solvent is absorbed, swelled and gelated under external pressure. In addition, depending on the type of organic solvent used, the oil-absorbing crosslinked polymer itself has an oil absorption capacity of 5 to 40 times per weight.
상기 비닐단량체-무수말레산 공중합체에 포함되어 있는 무수말레산 그룹이 반응성 작용기로 사용되어, 유출된 유기용제 또는 석유 등과 친화력이 큰 친유성 그룹을 가지는 알킬알코올과 반응함으로써 흡유성 고분자를 생성한다. 그리고 상기 흡유성 고분자를 가교제와 반응시켜 가교결합을 형성함으로써 본 발명의 흡유성 가교 고분자를 제조한다. 이때 가교제의 알킬기의 탄소 수를 조절함으로써 가교결합의 길이를 제어할 수 있다. 그러므로 종래의 기술에서는 볼 수 없는 다양한 구조의 흡유성 가교 고분자를 제조할 수 있는 장점을 갖는다.The maleic anhydride group included in the vinyl monomer-maleic anhydride copolymer is used as a reactive functional group to generate an oil-repellent polymer by reacting with an alkyl alcohol having a lipophilic group having a high affinity with the spilled organic solvent or petroleum. . The oil-absorbing crosslinked polymer of the present invention is prepared by reacting the oil absorbent polymer with a crosslinking agent to form a crosslink. At this time, the length of the crosslinking can be controlled by adjusting the carbon number of the alkyl group of the crosslinking agent. Therefore, the oil-absorbing crosslinked polymer having various structures, which cannot be seen in the prior art, has the advantage of being able to be produced.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
본 발명의 흡유성 가교 고분자의 흡유능 및 흡유속도를 다음과 같이 측정하였다:The oil absorption capacity and oil absorption rate of the oil absorbent crosslinked polymer of the present invention were measured as follows:
흡유성 가교 고분자 1.0g을 비이커에 넣고 선택된 유기용매 10cc를 넣은 뒤 1시간 동안 흡수, 팽윤시킨 후 팽윤된 겔을 금속망(100메시)에 10분간 여과시킨 뒤 팽윤된 무게를 측정하여 시료의 흡유능(흡수배율)을 계산하였다. 50mL의 다공성 유리필터 깔때기(sintered glass funnel)를 50mL 뷰렛에 실리콘 튜브로 연결하고 튜브 중간은 잠금장치로 개폐할 수 있도록 하였다. 깔때기의 유리필터와 뷰렛의 눈금(0mL)을 수평으로 맞추고 측정할 유기용매를 0mL까지 채운 후 잠금장치를 닫고 합성한 흡유성 가교 고분자 1.0g을 유리필터 표면에 골고루 뿌린 다음 잠금장치를 열고 시간에 따른 뷰렛눈금의 감소를 측정하여 흡유속도(mL/분)를 계산하였다.1.0 g of oil-absorbing crosslinked polymer was placed in a beaker, 10 cc of the selected organic solvent was added, absorbed and swelled for 1 hour, the swelled gel was filtered through a metal mesh (100 mesh) for 10 minutes, and the swelled weight was measured. Competence (absorption magnification) was calculated. A 50 mL porous glass filter funnel was connected to a 50 mL burette with a silicone tube and the middle of the tube could be opened and closed with a locking device. Level the scale of the funnel glass filter and burette (0mL), fill the organic solvent to be measured to 0mL, close the locking device, evenly spray the synthesized oil-absorbing crosslinked polymer 1.0g on the surface of the glass filter, and open the lock The rate of oil absorption (mL / min) was calculated by measuring the decrease in burette scale.
실시예 1Example 1
무수말레산의 조성이 14wt%인 폴리(스티렌-무수말레산) 2.0g을 클로로포름 용매에 녹여 15% 용액으로 만든 후 n-헥사데칸올(n-hexadecanol) 0.69g을 넣고 62℃에서 6시간동안 반응하였다. 반응 후 불투명한 점성있는 액체를 상온으로 냉각한 뒤 가교제인 폴리(프로필렌 글리콜)디글리시딜에테르(PPDE, Mn-380) 0.29mL를 넣고 교반하여 균일한 용액으로 만든 뒤 테프론 몰드(10 x 10cm)안에 넣고 진공오븐에서 80℃로 12시간동안 가교반응을 일으켜 흡유성 가교 고분자를 제조하였다.2.0 g of poly (styrene-maleic anhydride) having a composition of 14 wt% maleic anhydride was dissolved in a chloroform solvent to make a 15% solution, and then 0.69 g of n-hexadecanol was added thereto at 62 ° C. for 6 hours. Reacted. After the reaction, the opaque viscous liquid was cooled to room temperature, and 0.29 mL of poly (propylene glycol) diglycidyl ether (PPDE, Mn-380), a crosslinking agent, was added to the solution and stirred to form a uniform solution. ) Into a crosslinking reaction at 80 ℃ in a vacuum oven for 12 hours to prepare an oil-absorbing crosslinked polymer.
실시예 2Example 2
친유성 알코올로서 n-헥사데칸올 대신 4-도데실페놀 0.75g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 흡유성 가교 고분자를 제조하였다.An oil-absorbing crosslinked polymer was prepared in the same manner as in Example 1 except that 0.75 g of 4-dodecylphenol was used instead of n-hexadecanol as a lipophilic alcohol.
실시예 3.Example 3.
가교제인 PPDE의 농도를 0.58mL 사용한 것을 제외하고는 실시예 2와 동일한 방법으로 흡유성 가교 고분자를 제조하였다.An oil absorbent crosslinked polymer was prepared in the same manner as in Example 2, except that 0.58 mL of PPDE, which was a crosslinking agent, was used.
실시예 4.Example 4.
가교제를 PPDE 대신 1,6-헥사디올 0.35g을 사용한 것을 제외하고는 실시예 2와 동일한 방법으로 흡유성 가교 고분자를 제조하였다.An oil absorbent crosslinked polymer was prepared in the same manner as in Example 2 except that 0.35 g of 1,6-hexadiol was used instead of PPDE.
실시예 1∼4에 의해 제조된 흡유성 가교 고분자의 용매에 대한 흡유능 및 흡유시간은 하기 표 1과 같다. 흡유시간은 상기 흡유속도 측정장치를 이용했을 때 최대 흡유능에 도달하는 시간을 의미한다.Oil absorption ability and oil absorption time for the solvent of the oil-absorbing crosslinked polymer prepared in Examples 1 to 4 are shown in Table 1 below. Oil absorption time means the time to reach the maximum oil absorption capacity using the oil absorption rate measuring device.
본 발명은 물과 혼합되어 있는 할로겐화 유기용매, 톨루엔, 벤젠 또는 탄소 수가 5개 이상인 탄화수소 유기용매들을 선택적으로 흡수, 팽윤시켜 겔화할 수 있고, 흡수배율 및 흡유속도가 빠르며 가압보지력이 우수하여 외부의 압력에도 흡수된 용매를 쉽게 배출하지 않으며 가공이 용이한 다공성의 흡유성 가교 고분자 및 그 제조방법을 제공하는 효과를 갖는다.The present invention can be gelated by selectively absorbing and swelling halogenated organic solvents, toluene, benzene or hydrocarbon organic solvents having 5 or more carbon atoms mixed with water, having a high absorption ratio and oil absorption rate, and excellent pressure holding ability. It does not easily discharge the absorbed solvent even at the pressure of and has the effect of providing a porous oil-absorbing crosslinked polymer and a method for producing the same easily processed.
본 발명의 단순한 변형 또는 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 이해될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or variations of the present invention can be readily understood by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.
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| KR100464846B1 (en) * | 2001-12-14 | 2005-01-05 | 제일모직주식회사 | New Crosslinked Polymer Having a Good Oil Absorbancy and Method of Preparing the Same |
| KR101189197B1 (en) | 2010-10-29 | 2012-10-09 | 한양대학교 산학협력단 | Adsorbent of volatile organic compounds and their adsorption method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH059211A (en) * | 1991-06-28 | 1993-01-19 | Toyo Ink Mfg Co Ltd | Oil-absorptive resin |
| JPH059243A (en) * | 1991-06-28 | 1993-01-19 | Toyo Ink Mfg Co Ltd | Oil-absorbing resin |
| JPH07133383A (en) * | 1993-11-08 | 1995-05-23 | Kuraray Co Ltd | Oil-absorbing resin |
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| JPH059211A (en) * | 1991-06-28 | 1993-01-19 | Toyo Ink Mfg Co Ltd | Oil-absorptive resin |
| JPH059243A (en) * | 1991-06-28 | 1993-01-19 | Toyo Ink Mfg Co Ltd | Oil-absorbing resin |
| JPH07133383A (en) * | 1993-11-08 | 1995-05-23 | Kuraray Co Ltd | Oil-absorbing resin |
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| KR100464846B1 (en) * | 2001-12-14 | 2005-01-05 | 제일모직주식회사 | New Crosslinked Polymer Having a Good Oil Absorbancy and Method of Preparing the Same |
| KR101189197B1 (en) | 2010-10-29 | 2012-10-09 | 한양대학교 산학협력단 | Adsorbent of volatile organic compounds and their adsorption method |
| US8911537B2 (en) | 2010-10-29 | 2014-12-16 | Lg Chem, Ltd. | Adsorbent of volatile organic compounds and adsorption method using thereof |
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