KR100674609B1 - Modification of Chlorinated Polyethylene and Its Preparation Method - Google Patents
Modification of Chlorinated Polyethylene and Its Preparation Method Download PDFInfo
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Abstract
본 발명은 염소화폴리에틸렌의 변성체에 관한 것으로 각종 플라스틱의 성형체나 필름 또는 시트 등에서 잉크의 인쇄, 코팅 시 잉크의 접착력을 증가시켜 인쇄성을 향상시킬 수 있는 신규한 변성 염소화폴리에틸렌을 제공하는 것이다. The present invention relates to a modified body of chlorinated polyethylene, to provide a novel modified chlorinated polyethylene that can improve the printability by increasing the adhesion of the ink during printing and coating of the ink in a molded body, film or sheet of various plastics.
본 발명은 수평균분자량 100 ~ 400,000이고 염소의 함량이 1 ~ 45 중량%의 염소화폴리에틸렌의 염소원소의 1 ~ 99.9몰%를 암모니아 또는 아민화합물로 치환한 염소화폴리에틸렌 변성체에 관한 것이다.The present invention relates to a chlorinated polyethylene modified body in which 1 to 99.9 mol% of chlorine elements of chlorinated polyethylene having a number average molecular weight of 100 to 400,000 and a chlorine content of 1 to 45% by weight are substituted with ammonia or an amine compound.
염소화폴리에틸렌, 아민화, 개질, 변성체, 인쇄성 Chlorinated Polyethylene, Amination, Modified, Modified, Printable
Description
본 발명은 염소화폴리에틸렌의 변성체에 관한 것으로 각종 플라스틱의 성형체나 필름 또는 시트 등에서 잉크의 인쇄, 코팅 시 잉크의 접착력을 증가시켜 인쇄성을 향상시킬 수 있는 신규한 변성 염소화폴리에틸렌을 제공하는 것이다. The present invention relates to a modified body of chlorinated polyethylene, to provide a novel modified chlorinated polyethylene that can improve the printability by increasing the adhesion of the ink during printing and coating of the ink in a molded body, film or sheet of various plastics.
포장 재료로서의 플라스틱 필름은 인쇄성이 요구되는 경우가 많다. 인쇄성은 젖음 지수로서 판단하는데, 알려진 바와 같이 플라스틱의 젖음 지수는 낮다. 특히 폴리에틸렌의 젖음 지수는 아주 낮아 인쇄 등 다양한 표면 가공을 할 수 없다. 이러한 문제점을 해결하고 젖음 지수를 높이기 위하여 코로나 방전처리를 하는 것이 일반적이다. 그러나 강제적으로 높여진 플라스틱 표면의 젖음 지수는 시간이 지나면서 낮아진다.Plastic films as packaging materials are often required to be printable. The printability is judged as the wetness index, which, as is known, is low in plastics. In particular, the wetness index of polyethylene is very low, and various surface processing such as printing cannot be performed. In order to solve this problem and increase the wetness index, it is common to perform a corona discharge treatment. However, the wetness index of the forcibly raised plastic surface decreases over time.
종래 사용되어 오던 염소화폴리에틸렌계 수지로 제조되는 성형체은 인쇄성이 약하고, 코로나 처리를 하여 젖음 지수를 높이는 경우에도 고온에서 장시간 방치하면 젖음 지수가 현저히 저하되어 인쇄 용도에는 사용할 수 없다. 또한, 열 등 외부 환경의 영향으로 특히 여름철에는 시간의 경과에 따라 표면장력이 급격히 저하되어 인쇄, 증착 등의 작업성이 현저히 떨어지게 된다.Molded articles made of chlorinated polyethylene resins, which have been conventionally used, have poor printability, and even when they are subjected to corona treatment to increase the wetness index, when left at a high temperature for a long time, the wetness index is significantly lowered and cannot be used for printing applications. In addition, due to the influence of the external environment such as heat, especially in summer, the surface tension is drastically lowered with time, and workability such as printing and deposition is significantly reduced.
본 발명자들은 상기의 문제점을 해결하고자 다양한 연구를 한 결과 아민계 화합물로 변성된 염소화폴리에틸렌 변성체가 각종 성형체, 필름, 각종 적층체의 가공 등에 첨가하여 사용되는 경우 광범위한 특성을 부여하고 다양한 수지들의 인쇄성과 접착성을 우수하게 하는 특성을 부여하는 것을 알게 되어 본 발명을 완성하게 되었다.The present inventors conducted various studies to solve the above problems, and when the chlorinated polyethylene modified body modified with the amine compound is used in addition to the processing of various molded articles, films, and various laminates, it gives a wide range of properties and printability of various resins. The present invention has been completed to provide a property of excellent adhesion.
따라서, 본 발명은 폴리에틸렌과 잘 혼합되고, 젖음 지수를 향상 시키는 극성기를 도입하는 신규한 변성 염소화폴리에틸렌을 제공하는 것이다.Accordingly, the present invention provides a novel modified chlorinated polyethylene that is well mixed with polyethylene and introduces a polar group that improves the wetness index.
본 발명의 또 다른 목적은 신규한 변성 염소화폴리에틸렌을 간단하고 쉽게 제조할 수 있는 방법을 제공하는 것이다.It is still another object of the present invention to provide a method for producing a simple modified chlorinated polyethylene simply and easily.
본 발명의 또 다른 목적은 상기 신규한 변성 염소화폴리에틸렌을 이용한 인쇄성과 염색성이 개선된 폴리올레핀조성물을 제공하는 것이다.Still another object of the present invention is to provide a polyolefin composition having improved printability and dyeability using the novel modified chlorinated polyethylene.
본 발명의 염소화폴리에틸렌 변성체는 염소화 함량이 1 ~ 45 중량%, 수평균분자량이 100 ~ 400,000의 염소화폴리에틸렌을 용매에 용해한 후 아민화합물을 투입하여 승온 상태에서 반응시켜 염소를 아민화합물로 치환함으로써 변성체를 제조 한다.The chlorinated polyethylene modified body of the present invention is modified by dissolving chlorinated polyethylene having a chlorinated content of 1 to 45% by weight and a number average molecular weight of 100 to 400,000 in a solvent, followed by adding an amine compound to react at elevated temperature to replace chlorine with an amine compound. Manufacture sieve.
본 발명에 따른 제조방법은 염소화폴리에틸렌을 유기용매에 투입 용해하여 반응용액을 제조하는 단계;The production method according to the present invention comprises the steps of dissolving chlorinated polyethylene in an organic solvent to prepare a reaction solution;
상기 반응용액에 아민유도체를 투입하고 승온하여 반응하는 단계;Adding an amine derivative to the reaction solution and reacting by raising the temperature;
원심분리기를 이용하여 상기 반응용액으로부터 미 반응 아민화합물 및 염을 분리하여 제거하는 단계 및 유기용매층의 염소화폴리에틸렌의 변성체를 회수하는 단계;Separating and removing the unreacted amine compound and salt from the reaction solution using a centrifuge and recovering the modified product of chlorinated polyethylene in the organic solvent layer;
를 포함하는 염소화폴리에틸렌의 아민개질 변성체의 제조방법 및 그 제조방법에 따른 변성체를 제공한다.It provides a method for producing an amine-modified modified form of chlorinated polyethylene comprising a and a modified according to the method.
본 발명에 사용하는 염소화폴리에틸렌은 수평균 분자량이 100 ~ 400,000의 것으로서, 염소 함량은 1 ~ 45 중량%의 것이 사용된다. 상기의 염소화폴리에틸렌을 암모니아 또는 최소한 1개의 1차 또는 2차 아민기를 가지는 아민화합물과 반응시킴으로써 염소의 치환반응에 의하여 염소원소의 1 ~ 99.9몰%가 아민기로 치환되는 아민변성 염소화폴리에틸렌이 생성된다.The chlorinated polyethylene used in the present invention has a number average molecular weight of 100 to 400,000 and a chlorine content of 1 to 45% by weight. By reacting the chlorinated polyethylene with an ammonia or an amine compound having at least one primary or secondary amine group, an amine-modified chlorinated polyethylene is produced in which 1 to 99.9 mol% of the chlorine element is replaced by an amine group by the substitution reaction of chlorine.
본 반응에 사용하는 유기용제로는 염소화폴리에틸렌의 용매로 사용가능한 것이라면 크게 제한이 없지만, 좋게는 톨루엔, 자일렌, 클로로벤젠, 테트라하이드로퓨란, 디옥산, 디메틸포름아마이드, 모폴린, 에틸렌글리콜디메틸에테르, 에틸렌글리콜디에틸에테르, 디에틸렌글리콜 디메틸에테르 등의 유기용매를 사용한다.The organic solvent used in this reaction is not particularly limited as long as it can be used as a solvent of chlorinated polyethylene, but preferably toluene, xylene, chlorobenzene, tetrahydrofuran, dioxane, dimethylformamide, morpholine, ethylene glycol dimethyl ether Organic solvents such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether are used.
다음, 본 반응의 개질제로 사용되는 아민화합물은 1차 아민 또는 2차 아민으로서, 치환기를 가지거나 또는 가지지 않는 것 모두 사용가능하다. 그 사용가능한 아민으로서는 1차 아민은 하기식의 화합물과 같다.Next, the amine compound used as the modifying agent of the present reaction may be used as a primary amine or a secondary amine, with or without a substituent. As the usable amine, the primary amine is the same as the compound of the following formula.
[구조식 1] A1-NH2 [Formula 1] A 1 -NH 2
(상기에 있어서, A1은 직쇄형 또는 분기되었거나 사이클릭 또는 아로마틱 링을 포함하는 탄소수 1 ~ 18개의 탄화수소이며, 주쇄 또는 측쇄에 질소나 산소 그리고 황에서 선택되는 1개 이상의 헤테로 작용기를 가지는 것을 포함한다.)(In the above, A 1 is a straight-chain or branched hydrocarbon having 1 to 18 carbon atoms containing a cyclic or aromatic ring, including one having at least one hetero functional group selected from nitrogen, oxygen and sulfur in the main chain or side chain. do.)
상기 구조식의 일차아민으로는 메틸아민, 에틸아민, 프로필아민, 이소프로필아민, 부틸아민, 이소부틸아민, t-부틸아민, 펜틸아민, 헥실아민, 사이크로헥실아민, 헵틸아민, 옥틸아민, 이소옥틸아민, 아닐린, 에틸렌디아민, 프로필렌디아민, 부틸렌디아민, 헥사메틸렌디아민, 에탄올아민, 아미노프로판올, 아미노부탄올, 벤지딘, 4,4’-디아미노벤즈아닐아이드, 아미노벤젠설포닉산, 디아미노벤젠, 아미노프로판올, 페닐렌디아민, 4,4’-디아미노디페닐메탄, 4,4’-디아미노디사이클로헥실메탄, 4,4’-디아미노디페닐옥사이드, 4,4’-디아미노디사이클로헥실에테르, 4,4’-디아미노디페닐-3,3’-디아미노디페닐설폰, 4,4’-디아미노디페닐설파이드, 디메틸아미노프로필아민 등이 있다.Primary amines of the above structural formula include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, iso Octylamine, aniline, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, ethanolamine, aminopropanol, aminobutanol, benzidine, 4,4'-diaminobenzanilide, aminobenzenesulfonic acid, diaminobenzene, Aminopropanol, phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyloxide, 4,4'-diaminodicyclo Hexyl ether, 4,4'-diaminodiphenyl-3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, dimethylaminopropylamine and the like.
본 발명의 2차 아민으로는 다음과 같은 구조식의 화합물을 사용한다.As the secondary amine of the present invention, a compound having the following structural formula is used.
[구조식 2] A2-NH-A3 [Formula 2] A 2 -NH-A 3
(A2 및 A3는 직쇄형 또는 분기되었거나 사이클릭 또는 아로마틱링을 포함하는 탄소수 1~18 사이의 탄화수소이며 주쇄 또는 측쇄에 질소나 산소 그리고 황 등에서 선택되는 어느 하나 이상의 작용기를 가지는 것을 포함한다.) (A 2 and A 3 are linear or branched hydrocarbons having 1 to 18 carbon atoms including cyclic or aromatic rings and include those having at least one functional group selected from nitrogen, oxygen, sulfur, etc. in the main chain or side chain. )
상기 화합물의 대표적인 예로는 디메틸디아민, 디에틸아민, 디프로필아민, 디이소프로필아민, 디부틸아민, 디이소부틸아민, 디-t-부틸아민, 디펜틸아민, 디헥실아민, 디사이클로헥실아민, 디헵틸아민, 디옥틸아민, 디이소옥틸아민, 디페닐아민, N-메틸아닐린, N-에틸아닐린, N-프로필아닐린, N-부틸아닐린, N-하이드록시에틸아닐린, N-하이드록시프로필아닐린, N-메틸에탄올아민, N-에틸에탄올아민, 디에탄올아민, 모폴린, 디프로판올아민 등을 예로 들 수 있다.Representative examples of the compound include dimethyldiamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-t-butylamine, dipentylamine, dihexylamine, dicyclohexylamine , Diheptylamine, dioctylamine, diisooctylamine, diphenylamine, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N-hydroxyethylaniline, N-hydroxypropyl Aniline, N-methylethanolamine, N-ethylethanolamine, diethanolamine, morpholine, dipropanolamine, etc. are mentioned.
본 발명의 2차아민으로는 하기와 같은 아민화합물을 사용하는 것도 가능하다.As the secondary amine of the present invention, it is also possible to use the following amine compounds.
[구조식 3] A4-HN-(A5-NH-A6-NH)n-A7 [Formula 3] A 4 -HN- (A 5 -NH-A 6 -NH) n -A 7
(상기 A4 내지 A7은 직쇄형 또는 분기되었거나 사이클릭 또는 아로마틱링을 포함하는 탄소수 1 ~ 18 사이의 탄화수소이며 주쇄 또는 측쇄에 질소나 산소 그리고 황 등에서 선택되는 어느 하나 이상의 작용기를 가지는 것을 포함하며, n은 1 ~ 10 사이의 정수이고, A4 및 A7은 수소일 수 있다.)(A 4 to A 7 is a linear or branched hydrocarbon having 1 to 18 carbon atoms including cyclic or aromatic ring, and includes one or more functional groups selected from nitrogen, oxygen, sulfur, etc. in the main chain or side chain, , n is an integer between 1 and 10, and A 4 and A 7 may be hydrogen.)
상기, 2차아민의 예로는 디에틸렌트리아민, 트리에틸렌테트라민, 테트라에틸렌펜타아민, 펜타에틸렌헥사아민, 폴리에틸렌이민, 디시안디아미드 등이 있다.Examples of the secondary amines include diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, pentaethylenehexaamine, polyethyleneimine, and dicyandiamide.
본 발명의 변성반응온도는 용매와 반응성에 따라 변경가능한 것으로 크게 제한을 받는 것은 아니지만 통상 30 ~ 150℃의 범위에서 반응시간은 치환되는 아민 화합물에 따라서 변경하여 선택할 수 있는 것이지만 통상적으로 2 ~ 48시간의 범위에서 반응이 이루어지는데, 먼저 염소화폴리에틸렌(CPE)를 용매에 용해한 후, 승온 하고, 아민계 반응물을 투입하여 염소를 아민화합물로 치환함으로써 본 개질반응을 달성하였다.The modification reaction temperature of the present invention is not limited to be changed depending on the solvent and reactivity, but usually in the range of 30 ~ 150 ℃ reaction time can be selected according to the amine compound to be substituted, but usually 2 to 48 hours The reaction was carried out in the range of. First, the chlorinated polyethylene (CPE) was dissolved in a solvent, and then heated up, and an amine-based reactant was added to substitute chlorine with an amine compound to achieve the present reforming reaction.
본 발명에 따른 개질 중합체는 개질되는 아민화합물의 구조에 따라서 자외선 차단제(t-부틸아민 등 개질반응에 의해 CPE의 주쇄에 차폐된 형태의 아민의 구조를 생성시키는 개질제 등), 산화방지제(2-하이드록시아닐린 등), 대전방지제(에탄올아민 등), 난연제(디에틸렌트리아민 등) 및 금속이온봉쇄제에 사용하는 통상의 구조를 채택함으로써 상기의 기능을 가지는 개질제로 사용가능하다.The modified polymer according to the present invention may be a sunscreen (such as t-butylamine, a modifier that produces a structure of an amine shielded in the main chain of the CPE by a modification reaction), an antioxidant (2- Hydroxyaniline and the like), an antistatic agent (ethanolamine and the like), a flame retardant (diethylenetriamine and the like) and a metal ion sequestering agent can be used as a conventional modifier having the above functions.
본 발명에 의해 제조되는 개질 CPE는 그 자체로서 필름, 시트 및 성형체로 가공 가능할 뿐만 아니라 다른 수지성분과 블랜딩 함으로써, 개질CPE가 가지는 성질을 수지조성물 전체에 부여할 수 있다. 이때 사용하는 수지로서는 CPE와 상용성이 우수한 폴리프로필렌, 폴리에틸렌, 폴리프로필렌 공중합체, 폴리에틸렌공중합체 등의 수지가 상용성 등의 면에서 좋다.The modified CPE produced by the present invention can not only be processed into a film, a sheet and a molded body by itself, but also blended with other resin components to impart the properties of the modified CPE to the entire resin composition. As the resin used at this time, resins such as polypropylene, polyethylene, polypropylene copolymer, polyethylene copolymer and the like which are excellent in compatibility with CPE are preferable in view of compatibility.
이하는 본 발명에 따른 CPE의 개질반응의 실시 예를 통하여 본 발명을 더욱 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail through examples of the reforming reaction of CPE according to the present invention.
[실시예 1] 염소화폴리에틸렌(CPE) + 암모니아(NH 3 ) Example 1 Chlorinated Polyethylene (CPE) + Ammonia (NH 3 )
톨루엔 200중량부에 염소화폴리에틸렌((Showa Denko, Elaslen 301A, 염소함량 30%) 20중량부를 80℃에서 용해시킨다. 이 용액을 500mL 고압반응기(Autoclave Engineers社)에 옮긴 후 밀폐한다. 상온에서 교반하면서 암모니아를 압력 5kg/cm2이 되도록 충진한다. 반응기와 통하는 벨브를 모두 잠그고 반응온도 100℃에서 12시간 교반하였다. 반응기를 실온으로 냉각시키고 여분의 기체는 배기시킨다. 반응액을 원심분리기로 옮긴 후 5,000 rpm에서 30분간 처리한 후 상등액을 취하여 회전증발기를 이용하여 용매를 제거하고 진공건조 하여 생성물을 얻었다. 원소분석결과 질소함량 0.96%(염소 8.0mol% 치환)로서 암모니아가 도입되었음을 알 수 있었다. 20 parts by weight of chlorinated polyethylene (Showa Denko, Elaslen 301A, chlorine content 30%) is dissolved in 200 parts by weight of toluene at 80 ° C. The solution is transferred to a 500 mL autoclave engineer (Autoclave Engineers) and sealed. Ammonia was charged to a pressure of 5 kg / cm 2 The valves through the reactor were closed and stirred for 12 hours at a reaction temperature of 100 ° C. The reactor was cooled to room temperature and the excess gas was evacuated. After treatment at 5,000 rpm for 30 minutes, the supernatant was removed, the solvent was removed using a rotary evaporator, and vacuum dried to obtain a product, and elemental analysis showed that ammonia was introduced as 0.96% of nitrogen (substituted by 8.0 mol% of chlorine).
[실시예 2] 염소화폴리에틸렌(CPE) + t-부틸아민(t-Butylamine) Example 2 Chlorinated Polyethylene (CPE) + t-Butylamine
톨루엔 200중량부에 염소화폴리에틸렌((Showa Denko, Elaslen 301A, 염소함량 30%) 20중량부를 80℃에서 용해시킨다. 이 용액에 t-부틸아민(t-Butylamine) 50중량부를 투입한 후 500mL 고압반응기(Autoclave Engineers社)에 옮긴 후 밀폐한다. 반응기와 통하는 벨브를 모두 잠그고 반응온도 100℃에서 12시간 교반하였다. 반응기를 실온으로 냉각시키고 반응액을 원심분리기로 옮긴 후 5,000 rpm에서 30분간 처리한 후 상등액을 취하여 회전증발기를 이용하여 용매를 제거하고 진공건조 하여 생성물을 얻었다. 원소분석결과 질소함량 1.1%로서 아민이 도입되었음을 알 수 있었다. 20 parts by weight of chlorinated polyethylene (Showa Denko, Elaslen 301A, 30% of chlorine) was dissolved in 80 parts by weight of toluene at 80 ° C. 50 parts by weight of t-butylamine were added to the solution, followed by a 500 mL high pressure reactor. After the transfer to Autoclave Engineers, the valves were closed and stirred for 12 hours at a reaction temperature of 100 ° C. The reactor was cooled to room temperature, the reaction solution was transferred to a centrifuge, and treated at 5,000 rpm for 30 minutes. The supernatant was removed, the solvent was removed using a rotary evaporator, and the product was dried in vacuo.The elemental analysis showed that the amine was introduced as 1.1% of nitrogen.
[실시예 3] 염소화폴리에틸렌(CPE) + 디메틸아미노프로필아민(DMAPA) Example 3 Chlorinated Polyethylene (CPE) + Dimethylaminopropylamine (DMAPA)
톨루엔 200중량부에 염소화폴리에틸렌(Showa Denko, Elaslen 301A, 염소함량 30%) 20중량부를 80℃에서 용해시킨다. 이 용액에 디메틸아미노프로필아민(3-Dimethyl- aminopropylamine) 50중량부를 투입한 후 500mL 둥근 플라스크에 옮긴 후 100℃에서 12시간 반응시켰다. 반응기를 실온으로 냉각시키고 반응액을 원심분리기로 옮긴 후 5,000 rpm에서 30분간 처리한 후 상등액을 취하여 회전증발기를 이용하여 용매를 제거하고 진공건조 하여 생성물을 얻었다. 원소분석결과 질소함량 2.0%로서 아민이 도입되었음을 알 수 있었다. 20 parts by weight of chlorinated polyethylene (Showa Denko, Elaslen 301A, chlorine content 30%) is dissolved in 80 parts by weight of toluene at 80 ° C. 50 parts by weight of dimethylaminopropylamine (3-Dimethylaminopropylamine) was added to the solution, which was then transferred to a 500 mL round flask, followed by reaction at 100 ° C for 12 hours. The reactor was cooled to room temperature, the reaction solution was transferred to a centrifuge, treated at 5,000 rpm for 30 minutes, the supernatant was taken out, the solvent was removed using a rotary evaporator, and the product was dried under vacuum. Elemental analysis showed that the amine was introduced as nitrogen content 2.0%.
[실시예 4] 염소화폴리에틸렌(CPE) + 모폴린(Morpholine) Example 4 Chlorinated Polyethylene (CPE) + Morpholine
톨루엔 200중량부에 염소화폴리에틸렌(Showa Denko, Elaslen 301A, 염소함량 30%) 20중량부를 80℃에서 용해시킨다. 이 용액에 모폴린(Morpholine) 50중량부를 투입한 후 500mL 둥근 플라스크에 옮긴 후 100℃에서 12시간 환류시켰다. 반응기를 실온으로 냉각시키고 반응액을 원심분리기로 옮긴 후 5,000 rpm에서 30분간 처리한 후 상등액을 취하여 회전증발기를 이용하여 용매를 제거하고 진공건조 하여 생성물을 얻었다. 원소분석결과 질소함량 0.8%로서 아민이 도입되었음을 알 수 있었다. 20 parts by weight of chlorinated polyethylene (Showa Denko, Elaslen 301A, chlorine content 30%) is dissolved in 80 parts by weight of toluene at 80 ° C. 50 parts by weight of morpholine (Morpholine) was added to the solution, which was transferred to a 500 mL round flask and refluxed at 100 ° C for 12 hours. The reactor was cooled to room temperature, the reaction solution was transferred to a centrifuge, treated at 5,000 rpm for 30 minutes, the supernatant was taken out, the solvent was removed using a rotary evaporator, and the product was dried under vacuum. Elemental analysis showed that the amine was introduced as nitrogen content 0.8%.
[실시예 5] 염소화폴리에틸렌(CPE) + 모폴린(Morpholine) Example 5 Chlorinated Polyethylene (CPE) + Morpholine
모폴린(Morpholine) 200중량부에 염소화폴리에틸렌(Showa Denko, Elaslen 301A, 염소함량 30%) 20중량부를 투입하고 110℃에서 24시간 반응시킨다. 온도를 실온으로 내린 후 가성소다 20중량부를 물 40중량부에 녹인 용액을 투입하고 100℃에서 1시간 교반 후 소석회(CaO) 40중량부를 투입하고 1시간 추가 교반하였다. 반 응액을 원심분리기로 옮긴 후 5,000 rpm에서 30분간 처리한 후 상등액을 취하여 회전증발기를 이용하여 용매를 제거하고 진공건조 하여 생성물을 얻었다. 원소분석결과 질소함량 7.6%(염소 90.0mol% 치환)로서 아민이 도입되었음을 알 수 있었다. 20 parts by weight of chlorinated polyethylene (Showa Denko, Elaslen 301A, chlorine content 30%) is added to 200 parts by weight of morpholine (Morpholine) and reacted at 110 ° C for 24 hours. After the temperature was lowered to room temperature, a solution obtained by dissolving 20 parts by weight of caustic soda in 40 parts by weight of water was added. After stirring for 1 hour at 100 ° C., 40 parts by weight of hydrated lime (CaO) was added and stirred for 1 hour. The reaction solution was transferred to a centrifuge, treated at 5,000 rpm for 30 minutes, the supernatant was collected, the solvent was removed using a rotary evaporator, and vacuum dried to obtain a product. Elemental analysis showed that the amine was introduced as nitrogen content 7.6% (90.0 mol% chlorine substitution).
또한 인쇄성 테스트를 위해서 실시예 5에서 제조한 CPE 변성 수지를 메틸렌크로라이드 용매에 녹인 후 유리판위에 코팅을 하고 용매를 휘발시켜 시트를 제조한 후, 표면에 수성펜으로 사선을 그었을 때 균일하게 필기가 되었으나, 본 발명의 CPE 변성 수지가 아닌 일반 CPE 경우는 동일한 방법으로 테트라하이드로퓨란에 녹여 시트를 제조한 후 수성펜으로 필기한 결과 균일한 필기형상을 나타내지 않았다.In addition, for the printability test, the CPE modified resin prepared in Example 5 was dissolved in a methylene chromide solvent, coated on a glass plate, and the solvent was volatilized to prepare a sheet. However, in the case of general CPE other than the CPE modified resin of the present invention, a sheet was prepared by dissolving in tetrahydrofuran in the same manner and writing with an aqueous pen.
따라서, 본 실시예에 따른 CPE 변성 수지 조성물의 시트는, CPE로부터 제조한 시트에 비하여 친수성이 매우 우수하여 염색성이 우수한 효과를 가지는 것을 알 수 있었는 바, 본 발명에 따른 개질 CPE 수지는 CPE 수지의 염색성을 개선하면서 상용성이 우수한 효과를 부여하는 것을 알 수 있었다.Therefore, it was found that the sheet of the CPE modified resin composition according to the present embodiment has an excellent hydrophilic property and excellent dyeability compared to the sheet prepared from the CPE. It was found that the effect of excellent compatibility was given while improving the dyeability.
본 발명의 CPE의 개질방법은 간단하면서도 효과적으로 아민화합물에 의해 염소가 치환된 개질 CPE를 제조할 수 있음을 알 수 있었고, 개질 변성체는 염색성 및 인쇄성이 매우 증대되었음을 알 수 있었다. 또한 개질 아민화합물의 구조를 디자인함으로써, 그 아민화합물의 기능기에 따라서 자외선방지기능기, 대전방지기능기 및 산화방지 기능 등의 다양한 기능을 가지는 아민화합물을 이용함으로써 고분자의 자 외선방지제, 산화방지제, 난연제, 대전방지제 및 금속이온봉쇄제등의 다용한 용도의 첨가제로 사용가능함을 알 수 있었다.It was found that the modification method of the CPE of the present invention was simple and effective to prepare a modified CPE substituted with chlorine by the amine compound, and the modified modified body was found to have greatly increased dyeability and printability. In addition, by designing the structure of the modified amine compound, by using the amine compound having various functions such as UV protection function, antistatic function and antioxidant function according to the functional group of the amine compound, it is possible to prevent the ultraviolet ray of the polymer, antioxidant, It can be seen that it can be used as an additive for various uses such as a flame retardant, an antistatic agent and a metal ion blocking agent.
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