KR20090038191A - Poly(vinylphosphonic acid) and method for preparing the same - Google Patents

Poly(vinylphosphonic acid) and method for preparing the same Download PDF

Info

Publication number
KR20090038191A
KR20090038191A KR1020070103559A KR20070103559A KR20090038191A KR 20090038191 A KR20090038191 A KR 20090038191A KR 1020070103559 A KR1020070103559 A KR 1020070103559A KR 20070103559 A KR20070103559 A KR 20070103559A KR 20090038191 A KR20090038191 A KR 20090038191A
Authority
KR
South Korea
Prior art keywords
polymer
substituted
vinyl phosphate
unsubstituted
azobis
Prior art date
Application number
KR1020070103559A
Other languages
Korean (ko)
Other versions
KR101062923B1 (en
Inventor
윤성철
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to KR1020070103559A priority Critical patent/KR101062923B1/en
Publication of KR20090038191A publication Critical patent/KR20090038191A/en
Application granted granted Critical
Publication of KR101062923B1 publication Critical patent/KR101062923B1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A poly(vinylphosphonic acid) polymer is provided to ensure excellent film characteristic and mechanical strength and to be used as a separation film for a fuel battery, dopant of a conducting material and a hydrogel for medical delivery. A poly(vinylphosphonic acid) polymer is the polymer consisting of a vinylphosphoric acid monomer represented by the chemical formula 1 and has the average molecular weight of 100,000~500,000 and intrinsic viscosity of 2~20 dl/g in 0.1M NaNO3 solution.

Description

비닐인산 중합체 및 이의 제조방법{POLY(VINYLPHOSPHONIC ACID) AND METHOD FOR PREPARING THE SAME}Vinyl Phosphate Polymer and Method for Making the Same {POLY (VINYLPHOSPHONIC ACID) AND METHOD FOR PREPARING THE SAME}

본 발명은 고분자 전해질(polyelectrolyte)인 비닐인산 중합체 및 이의 제조방법에 관한 것이다.The present invention relates to a vinyl phosphate polymer which is a polyelectrolyte and a preparation method thereof.

비닐인산 중합체(poly(vinyl phosphonic acid))는 고분자 전해질 (polyelectrolyte)로서 고분자 체인에 이온화할 수 있는 포스폰산기(-PO3H2)가 달려있어 이온전도성을 보인다. 일반적으로 고분자 전해질의 물성은 고분자 체인에 달린 기능기의 산성 혹은 염기성 정도, 고분자 체인에 달린 기능기간의 거리, 즉 고분자 체인의 전하밀도, 고분자 체인내 기능기의 위치 및 폴리이온의 대응이온(counter ion)에 따라 달라진다.Vinyl phosphonic acid (poly (vinyl phosphonic acid)) is a polyelectrolyte (polyelectrolyte) has a phosphonic acid group (-PO 3 H 2 ) that can be ionized in the polymer chain shows ionic conductivity. In general, the properties of a polymer electrolyte are characterized by the degree of acidity or basicity of the functional groups on the polymer chain, the distance of the functional periods on the polymer chain, that is, the charge density of the polymer chain, the position of the functional groups in the polymer chain, and the counter ions of the polyions. ion).

고분자 전해질은 고분자내 이온의 해리때문에 용액 내에서 이온간 정전기적 상호작용이 일어나는데, 이러한 점이 중성 고분자 용액보다 고분자 전해질 용액의 물성을 복잡하게 만든다. 이러한 고분자 전해질에서는 고분자 수용액에 염을 추가해서 고분자 전해질의 겔화를 방지하고 이의 물성을 측정하게 된다.Electrolyte interaction between ions occurs in the polymer electrolyte due to dissociation of ions in the polymer, which complicates the properties of the polymer electrolyte solution rather than the neutral polymer solution. In such a polymer electrolyte, a salt is added to the polymer aqueous solution to prevent gelation of the polymer electrolyte and its physical properties are measured.

고분자 전해질의 분자량은 정해진 농도의 염용액하에서 광산란법에 의해 측정되고 짐 폴롯(Zimm Plot)을 통해 분자량을 구한다. 고분자 전해질의 고유점도 또한 분자량을 상대적으로 나타내는 물성으로, 정해진 농도의 염용액하에서 측정하는데, 일반적으로 우벨로드(Ubbelode) 점도계를 사용해서 각 고분자 전해질에 대한 흐름시간 측정을 통해 고유점도를 구한다.The molecular weight of the polymer electrolyte is measured by light scattering in a salt solution of a predetermined concentration, and the molecular weight is obtained through a Zimmm Plot. The intrinsic viscosity of the polymer electrolyte is also a physical property that shows the relative molecular weight, and is measured under a salt solution of a predetermined concentration. Generally, an intrinsic viscosity is obtained by measuring the flow time of each polymer electrolyte using an Ubbelode viscometer.

비닐인산 중합체는 폴리아크릴산, 폴리비닐황산 혹은 폴리스티렌황산과 함께 대표적인 산성기를 가진 중합체로서 금속표면의 부식방지제, 난연제, 치아 재료, 연료전지용 분리막, 전도성 재료의 도핑제, 의약전달용 히드로젤, 금속제거용 필터재료, 고흡습성수지, 분산제, 표면개질제, 세제용 첨가제 등 다양한 분야에 응용되고 있다.A vinyl phosphate polymer is a polymer having a typical acidic group together with polyacrylic acid, polyvinyl sulfate or polystyrene sulfuric acid. It is a corrosion inhibitor, flame retardant, tooth material, fuel cell separator, dopant of conductive material, hydrogel for medicine delivery, and metal removal. It is applied to various fields such as filter material, high hygroscopic resin, dispersant, surface modifier and detergent additive.

일반적으로 비닐인산 중합체는 비닐인산 단량체의 라디칼 중합방법을 통해 제조되고 있다. 초기에는 비닐인산 단량체를 알코올 혹은 수용액하에 퍼옥시드(peroxide) 혹은 설페이트(sulfate) 라디칼 개시제를 사용한 중합방법이 보고되었다(독일 특허 1,106,963). 이후 퍼옥시에스테르의 라디칼 개시제와 양성자성(protic) 중합 용매의 양을 변화시켜 중합수율을 증가시켰다(미국특허 4,696,987). 그러나, 두 가지 방법 모두 중합 후 잔류 모노머가 남았으며, 중합체의 특성에 대해서는 보고되지 않았다. In general, vinyl phosphate polymers are prepared through radical polymerization of vinyl phosphate monomers. Initially a polymerization process using peroxide or sulfate radical initiators of vinyl phosphate monomers in alcohol or aqueous solutions has been reported (German Patent 1,106,963). The polymerization yield was then increased by varying the amount of radical initiator and protic polymerization solvent of the peroxyester (US Pat. No. 4,696,987). However, both methods left residual monomer after polymerization and no polymer properties were reported.

이후 윌슨 그룹에서는 아조비스아크릴로니트릴 개시제를 사용하여 비닐인산 중합체를 제조하였고 이를 치과용 재료에 적용하였다(Journal of materials science letter 9, 1058-1060, 1990). The Wilson group then produced vinylphosphate polymers using azobisacrylonitrile initiators and applied them to dental materials (Journal of materials science letter 9, 1058-1060, 1990).

하이닉스 반도체에서는 유기반사방지막 조성물로서 비닐인산 중합체를 제조하였는데 분자량은 4,530정도로 낮았다(KR 564,430, US 7,198,887).In Hynix Semiconductor, a vinyl phosphate polymer was prepared as an organic antireflective coating composition, and its molecular weight was as low as 4,530 (KR 564,430, US 7,198,887).

현재 상업적으로 구매 가능한 비닐인산 중합체의 분자량은 대략 24,000 정도인데, 최근 베그너 그룹에서는 물에 녹는 라디칼 개시제를 사용하여 62,000 의 분자량을 가진 비닐인산 중합체를 제조하고 투석막(dialyzed membrane)을 사용하여 중합체를 분리하였다. 그러나, 이러한 방법은 대량 중합이 어렵고 장시간이 소요되므로 상업적으로 적용하기 어려운 문제점을 가지고 있다. (Macromol. Rapid Commun 27, 1719, 2006). The molecular weight of the currently available commercially available vinyl phosphate polymer is approximately 24,000. Recently, the Wegner Group has produced a vinyl phosphate polymer with a molecular weight of 62,000 using a water-insoluble radical initiator and a dialyzed membrane to prepare the polymer. Separated. However, this method has a problem that it is difficult to apply commercially because mass polymerization is difficult and takes a long time. (Macromol. Rapid Commun 27, 1719, 2006).

또한, 종래의 비닐인산 중합체는 분자량이 낮아 필름 제조 후 깨지거나 내구성이 현저히 떨어지고, 중합체 제조 기술도 상업적으로 적용하기 어려운 분리과정의 문제점을 가지고 있다. In addition, the conventional vinyl phosphate polymer has a low molecular weight is broken after the film production or significantly lower durability, polymer production technology has a problem of separation process difficult to apply commercially.

따라서, 본 발명은 상기한 기술적인 문제점을 해결하기 위하여, 우수한 필름특성과 기계적 강도를 갖는 고분자량의 비닐인산 중합체 및 이의 제조방법을 제공하는 것을 목적으로 한다Accordingly, an object of the present invention is to provide a high molecular weight vinyl phosphate polymer having excellent film properties and mechanical strength, and a method for producing the same, in order to solve the above technical problems.

상기 목적을 달성하기 위하여 본 발명은,The present invention to achieve the above object,

100,000~500,000의 중량평균분자량을 가지며, 0.1M NaNO3 수용액에서 2~20 dl/g의 고유점도(intrinsic viscosity)를 가지는 비닐인산 중합체를 제공한다. It provides a vinyl phosphate polymer having a weight average molecular weight of 100,000 ~ 500,000, having an intrinsic viscosity of 2 ~ 20 dl / g in 0.1M NaNO 3 aqueous solution.

또한, 본 발명은 비닐인산 단량체, 아미딘기를 가진 아조화합물 또는 이미다 졸린기를 가진 아조화합물인 라디칼 개시제, 및 양성자성 용매를 혼합하여 30~70℃의 온도에서 중합하는 단계를 포함하는 비닐인산 중합체의 제조방법을 제공한다.In addition, the present invention is a vinyl phosphate polymer comprising a step of mixing at a temperature of 30 ~ 70 ℃ by mixing a vinyl phosphate monomer, an azo compound having an amidine group or a radical initiator that is an azo compound having an imidazoline group, and a protic solvent It provides a method of manufacturing.

본 발명에 따르면 고분자량의 비닐인산 중합체의 상업공정이 가능하며, 제조된 고분자량의 비닐인산 중합체는 우수한 필름특성 및 기계적 강도를 가지므로 연료전지용 분리막, 전도성 재료의 도핑제, 의약전달용 히드로겔 등 다양한 용도로 사용될 수 있다. According to the present invention, a commercial process of a high molecular weight vinyl phosphate polymer is possible, and the prepared high molecular weight vinyl phosphate polymer has excellent film properties and mechanical strength, so that a membrane for a fuel cell, a dopant for a conductive material, and a hydrogel for pharmaceutical delivery Etc. can be used for various purposes.

이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명은 비닐인산 단량체로 이루어진 중합체로서, 100,000~500,000의 중량평균분자량을 가지며, 0.1M NaNO3 수용액에서 2~20 dl/g의 고유점도(intrinsic viscosity)를 가지는 비닐인산 중합체 및 비닐인산 단량체, 아미딘기를 가진 아조화합물 또는 이미다졸린기를 가진 아조화합물인 라디칼 개시제, 및 양성자성 용매를 혼합하여 30~70℃의 온도에서 중합하는 단계를 포함하는 비닐인산 중합체의 제조방법에 관한 것이다.The present invention is a polymer consisting of a vinyl phosphate monomer, having a weight average molecular weight of 100,000 to 500,000, vinyl phosphate polymer and vinyl phosphate monomer having an intrinsic viscosity of 2 to 20 dl / g in 0.1M NaNO 3 aqueous solution, It relates to a method for producing a vinyl phosphate polymer comprising a step of mixing at a temperature of 30 ~ 70 ℃ by mixing a radical initiator, which is an azo compound having an amidine group or an azo compound having an imidazoline group, and a protic solvent.

상기 비닐인산 단량체는 하기 화학식 1로 표시될 수 있다. The vinyl phosphate monomer may be represented by the following formula (1).

Figure 112007073685752-PAT00001
Figure 112007073685752-PAT00001

상기 아미딘기를 가진 아조화합물은 하기 화학식 2로 표시될 수 있다.Azo compounds having the amidine group may be represented by the following formula (2).

Figure 112007073685752-PAT00002
Figure 112007073685752-PAT00002

상기 화학식 2에서,In Chemical Formula 2,

R1 내지 R5는 서로 같거나 상이하고, 치환 또는 비치환된 C1~C20의 선형 또는 가지 달린 알킬, 치환 또는 비치환된 C3~C20의 시클로알킬, 치환 또는 비치환된 C6~C20의 아릴, 치환 또는 비치환된 C7~C14의 아릴알킬, 치환 또는 비치환된 C2~C20의 알케닐이고,R 1 to R 5 are the same as or different from each other, and substituted or unsubstituted C 1 to C 20 linear or branched alkyl, substituted or unsubstituted C 3 to C 20 cycloalkyl, substituted or unsubstituted C 6 Aryl of ~ C 20 , substituted or unsubstituted C 7 -C 14 arylalkyl, substituted or unsubstituted C 2 -C 20 alkenyl,

R1 내지 R5가 치환기에 의해 치환되는 경우, 상기 치환기는 -OH, -OR, -CO2H, -CO2R 및 -COR 중에서 선택되는 1 이상이며, 여기서 R은 서로 같거나 상이하고, C1~C20의 알킬이다.R 1 To When R 5 is substituted by a substituent, the substituent is one or more selected from -OH, -OR, -CO 2 H, -CO 2 R and -COR, wherein R is the same as or different from each other, C 1 ~ C 20 is alkyl.

상기 이미다졸린기를 가진 아조화합물은 하기 화학식 3으로 표시될 수 있다.The azo compound having an imidazoline group may be represented by the following Formula 3.

Figure 112007073685752-PAT00003
Figure 112007073685752-PAT00003

상기 화학식 3에서,In Chemical Formula 3,

R6 내지 R8은 서로 같거나 상이하고, 치환 또는 비치환된 C1~C20의 선형 또는 가지 달린 알킬, 치환 또는 비치환된 C3~C20의 시클로알킬, 치환 또는 비치환된 C6~C20의 아릴, 치환 또는 비치환된 C7~C14의 아릴알킬, 치환 또는 비치환된 C2~C20의 알케닐이고, R 6 to R 8 are the same as or different from each other, and substituted or unsubstituted C 1 to C 20 linear or branched alkyl, substituted or unsubstituted C 3 to C 20 cycloalkyl, substituted or unsubstituted C 6 Aryl of ~ C 20 , substituted or unsubstituted C 7 -C 14 arylalkyl, substituted or unsubstituted C 2 -C 20 alkenyl,

R6 내지 R8이 치환기에 의해 치환되는 경우, 상기 치환기는 -OH, -OR, -CO2H, -CO2R 및 -COR 중에서 선택되는 1 이상이며, 여기서 R은 서로 같거나 상이하고, C1~C20의 알킬이다.R 6 To When R 8 is substituted by a substituent, the substituent is one or more selected from -OH, -OR, -CO 2 H, -CO 2 R and -COR, wherein R is the same as or different from each other, C 1 ~ C 20 is alkyl.

비닐인산 단량체는 상기 화학식 1로 표시되는 인산기가 달린 극성 올레핀이며, 본 발명에 따라 제조된 비닐인산 중합체도 매우 높은 극성의 중합체로서 용매에 따라 용해도가 달라진다. The vinyl phosphate monomer is a polar olefin having a phosphate group represented by Chemical Formula 1, and the vinyl phosphate polymer prepared according to the present invention is also a polymer of very high polarity, and its solubility varies depending on the solvent.

특히 비닐인산 단량체 혹은 비닐인산 중합체 내에 달린 인산기는 단량체간, 중합체내, 중합체간, 혹은 단량체와 중합체간 수소결합을 형성하거나 축합반응을 통해 무수(anhydride) 형태의 결합을 형성할 수 있음이 알려져 있다 (J. Am. Chem. Soc., 74, 3427, 1952).In particular, it is known that a phosphate group attached to a vinyl phosphate monomer or a vinyl phosphate polymer can form hydrogen bonds between monomers, within polymers, between polymers, or between monomers and polymers or form anhydride bonds through condensation reactions. (J. Am. Chem. Soc., 74, 3427, 1952).

이러한 반응은 용매에 따라 달라지고 이는 중합체의 용해도 및 중합반응에 매우 큰 영향을 준다. 단량체와 중합체의 용해도 특성을 살펴보면, 헥산, 톨루엔과 같은 비극성 용매에 녹지 않으며, THF, 아세톤, 알코올, 물과 같은 극성용매에 대해 단량체는 잘 녹는 반면, 중합체의 용해도는 제조된 중합체의 분자량에 따라 달라지고, 경우에 따라 겔화가 일어난다. 반면, 물 혹은 알코올과 같은 양성자성 용매(protic solvent)에 대해 비닐인산은 우수한 중합 특성을 보이므로 양성자성 용매를 중합용매로 사용할 수 있다. 양성자성 용매로는 예로는 물, 메탄올, 에탄올, 이소프로판올 등이 있으며, 이들로 이루어진 군으로부터 선택되는 1종을 사용할 수 있다.This reaction is solvent dependent and has a very large influence on the solubility and polymerization of the polymer. The solubility characteristics of the monomers and polymers are not soluble in nonpolar solvents such as hexane and toluene, and the monomers are well soluble in polar solvents such as THF, acetone, alcohol and water, while the solubility of the polymer depends on the molecular weight of the polymer produced. And gelation occurs in some cases. On the other hand, since vinyl phosphate shows excellent polymerization characteristics with respect to a protic solvent such as water or alcohol, a protic solvent can be used as a polymerization solvent. Examples of protic solvents include water, methanol, ethanol, isopropanol, and the like. One kind selected from the group consisting of these may be used.

양성자성 용매(중합용매)는 비닐인산 단량체의 중량 대비 1% 내지 100%를 사용하는 것이 바람직하다. 이러한 중합용매는 중합 초기에 단량체와 함께 반응할 수 있고, 중합 반응중 용액의 점도에 따라 중합용매를 적가하면서 중합할 수도 있다. 이러한 방법을 사용하지 않고 벌크 형태 중합을 할 수도 있다. As the protic solvent (polymerization solvent), it is preferable to use 1% to 100% by weight of the vinyl phosphate monomer. Such a polymerization solvent may react with the monomer at the initial stage of the polymerization, or may be polymerized with dropwise addition of the polymerization solvent depending on the viscosity of the solution during the polymerization reaction. Bulk form polymerization can also be carried out without using this method.

비닐인산 단량체, 생성된 비닐인산 중합체 및 양성자성 용매(중합용매)가 모두 극성이기 때문에 라디칼 개시제는 이러한 극성조건과 잘 혼합될 수 있고 라디칼 분해 온도가 낮으며 안정한 라디칼 중간체 구조를 가져야 한다. 이러한 조건을 갖춘 라디칼 개시제로는 아미딘기 혹은 이미다졸린기가 달린 아조화합물이 있다. 아미딘기를 가진 아조화합물은 상기 화학식 2로 표시될 수 있고, 이미다졸린기를 가 진 아조화합물은 상기 화학식 3으로 표시될 수 있다. Since the vinyl phosphate monomer, the resulting vinyl phosphate polymer and the protic solvent (polymer solvent) are all polar, the radical initiator should be well mixed with these polar conditions, have a low radical decomposition temperature and have a stable radical intermediate structure. A radical initiator having such conditions is an azo compound having an amidine group or an imidazoline group. An azo compound having an amidine group may be represented by Formula 2, and an azo compound having an imidazoline group may be represented by Formula 3.

극성용매에 잘 녹는 다른 형태의 라디칼 개시제인 암모늄퍼설페이트((NH4)2S2O8) 혹은 칼륨퍼설페이트(K2S2O8)는 중합반응이 일어나지 않았고 아조형태의 아조비스아크릴로니트릴 혹은 아조비스시아노발러릭아시드 또한 중합 반응이 일어나지 않았다. 이러한 결과를 통해 라디칼 개시제는 극성조건과 잘 혼합될 수 있고 안정한 라디칼 중간체 구조를 가져야 중합반응이 이루어 질 수 있음을 알 수 있다. Ammonium persulfate ((NH 4 ) 2 S 2 O 8 ) or potassium persulfate (K 2 S 2 O 8 ), another radical initiator that is soluble in polar solvents, does not undergo polymerization and is azo-type azobisacryl Nitrile or azobiscyanobalaric acid also did not undergo polymerization. These results indicate that the radical initiator can be well mixed with the polar conditions and have a stable radical intermediate structure so that the polymerization can be performed.

아미딘기 혹은 이미다졸린기를 가진 아조화합물은 40~80℃ 정도의 낮은 중합온도에서 중합을 개시할 수 있고, 아미딘기 혹은 이미다졸기의 공명구조 특성에 의해 안정한 라디칼 중간체 구조를 가질 수 있다. Azo compounds having an amidine group or an imidazoline group can initiate polymerization at a low polymerization temperature of about 40 to 80 ° C., and can have a stable radical intermediate structure due to the resonance structure characteristics of the amidine group or the imidazole group.

이러한 라디칼 개시제의 예를 들면 2,2'-아조비스(2-메틸프로피온아미드), 2,2'-아조비스(N-부틸-2-메틸프로피온아미드), 2,2'-아조비스(N-시클로헥실-2-메틸프로피온아미드), 2,2'-아조비스[N-(2-프로페닐)-2-메틸프로피온아미드], 2,2'-아조비스[N-(2-카르복실에틸)-2-메틸프로피온아미드], 2,2'-아조비스[2-메틸-N-(2-히드록시부틸]프로피온아미드, 2,2'-아조비스{2-메틸-N-[1,1-비스(히드록시메틸)-2-히드록시에틸]프로피온아미드}, 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판], 2,2'-아조비스{2-[1-(2-히드록시에틸)-2-이미다졸린-2-일]프로판} 등이 있다. 또한 이들의 할로겐화물과의 염화합물 또는 수화물이 사용될 수도 있다. Examples of such radical initiators include 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (N-butyl-2-methylpropionamide) and 2,2'-azobis (N -Cyclohexyl-2-methylpropionamide), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis [N- (2-carboxyl Ethyl) -2-methylpropionamide], 2,2'-azobis [2-methyl-N- (2-hydroxybutyl] propionamide, 2,2'-azobis {2-methyl-N- [1 , 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azo Bis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, etc. Also, a salt compound or a hydrate of these halides may be used.

라디칼 개시제의 사용량은 비닐인산 단량체 몰 대비 0.01~1%가 바람직하다. 이러한 라디칼 개시제는 중합 초기에 단량체와 함께 반응시키거나 중합 반응중 소량을 적가하면서 중합할 수 있다. The amount of the radical initiator used is preferably 0.01 to 1% relative to the molar amount of the vinyl phosphate monomer. Such radical initiators may be polymerized with the monomers at the beginning of the polymerization or with a small dropwise addition during the polymerization reaction.

중합 온도 영역은 30~70℃인 것이 바람직하고, 중합 온도는 반응 중에 변화시켜 중합조건을 변화시킬 수 있다. 중합온도가 70℃를 초과하면 비닐인산 중합체의 분자량이 낮아지고, 30℃ 미만이면 중합반응이 원활이 일어나지 않는다. It is preferable that a polymerization temperature range is 30-70 degreeC, and a polymerization temperature can change during reaction and change polymerization conditions. If the polymerization temperature exceeds 70 ℃, the molecular weight of the vinyl phosphate polymer is lowered, if less than 30 ℃ polymerization reaction does not occur smoothly.

본 발명에 따른 중합방법은 비닐인산 단량체와 라디칼 개시제를 양성자성 용매에 혼합하여 중합하고, 라디칼 개시제와 중합용매의 구성 및 정량화를 통해 중합 수율 및 분자량을 조절할 수 있다.The polymerization method according to the present invention can be polymerized by mixing a vinyl phosphate monomer and a radical initiator in a protic solvent, and controlling the polymerization yield and molecular weight through the construction and quantification of the radical initiator and the polymerization solvent.

중합 용액 내 비닐인산 중합체는 인산기에 의한 중합체내 혹은 중합체간 혹은 잔류 단량체와 강한 상호작용을 함으로써 중합체 회수과정에서 중합체내에 잔류단량체가 섞이거나 강하게 뭉치는 경향을 보인다. 그래서 비닐인산 중합체 회수와 관련한 종래기술은 투석막을 통해 장시간 방치해서 잔류 단량체 및 저분자량의 고분자를 제거하여 원하는 중합체를 회수하였다. 이 경우 대량 중합에 적용하기 어려우며 시간이 오래 걸리고 효과적이지 못해 상업적으로 적용하기 어렵다. The vinyl phosphate polymer in the polymerization solution has a strong interaction with the residual monomer in the polymer during the polymer recovery process due to strong interaction between the polymer by the phosphate group, or between the polymer and the residual monomer. Therefore, the related art related to vinyl phosphate polymer recovery has been left for a long time through the dialysis membrane to remove the residual monomer and low molecular weight polymer to recover the desired polymer. In this case, it is difficult to apply to the mass polymerization, it takes a long time and it is not effective and it is difficult to apply commercially.

본 발명의 중합체 회수과정은 다음과 같다. 먼저, 중합후 점도가 높아진 중합 용액을 증류수를 이용하여 적절히 희석한 후, 희석된 중합 용액을 불용매에 적가한다. 이때 불용매를 전단력이 강한 호모제나이저(homogenizer)를 이용하여 교반시킴으로써 비닐인산 중합체의 뭉침을 방지하면서 침전시킬 수 있다. Polymer recovery process of the present invention is as follows. First, after polymerization, the polymerization solution having a high viscosity is appropriately diluted with distilled water, and then the diluted polymerization solution is added dropwise to the non-solvent. At this time, the non-solvent can be precipitated while preventing the aggregation of the vinyl phosphate polymer by stirring using a strong homogenizer (homogenizer).

이때 불용매 선택이 중요한데 잔류 단량체와 잘 섞이면서 침전 중합체의 입자가 균일해지고, 침전 중합체의 뭉침을 방지할 수 있는 것이어야 한다. 이러한 불 용매로는 메탄올, 에탄올, 프로판올, 부탄올 등의 알코올류 또는 아세톤, THF 같은 극성용매가 바람직하고, 이 중 THF가 가장 효과적이다. At this time, the solvent selection is important, but the particles of the precipitated polymer are uniformly mixed with the residual monomers, and it must be able to prevent the aggregation of the precipitated polymer. As such a solvent, alcohols such as methanol, ethanol, propanol and butanol, or polar solvents such as acetone and THF are preferable, and THF is most effective.

이와 같은 중합체 회수 단계를 포함하는 비닐인산 중합체의 제조방법은 침전된 입자들이 서로 뭉치지 않고 안정적으로 존재하여 상업 공정이 가능하다.The manufacturing method of the vinyl phosphate polymer including the polymer recovery step is a commercial process is possible because the precipitated particles are stably present without agglomeration with each other.

이하 본 발명의 실시예를 통해 본 발명에 대해 상세히 설명한다. 그러나 본 발명의 실시예들은 여러 가지 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들로 인하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments of the present invention may be modified in various forms, the scope of the present invention is not limited to the embodiments described below.

<실시예 1> 비닐인산 중합체 제조 Example 1 Vinyl Phosphoric Acid Polymer Preparation

비닐인산(2g, 18.5m㏖)과 2,2'-아조비스(2-메틸프로피온아미드) 디히드로클로라이드 (5.02 mg, 18.5x10-3 mmol)를 100㎖ 쉬렌크 플라스크에 투입하고 밀리퀴(mili-Q) 정제수 1g을 넣어 녹였다. 3회 진공/알곤 퍼징 후 70℃에서 반응시켰다. 반응이 진행되는 동안 반응용액 내 기포가 형성되면서 점도가 증가하였다. 18시간 동안 반응시킨 후 증류수(5㎖)를 넣어 희석하고, 희석한 중합용액을 호모제나이저(homogenizer)를 이용하여 교반하는 THF(200㎖)에 천천히 적가하여 침전된 중합체가 뭉치지 않도록 하였다. 이 과정을 두 번 반복하고, 침전물을 종이필터를 통해 걸러서 회수한 중합체를 진공오븐에서 60℃로 24시간 동안 건조하여 비닐인산 중합체 1.1g(투입된 단량체 총량기준 55 중량%)를 얻었다. Vinyl phosphoric acid (2 g, 18.5 mmol) and 2,2'-azobis (2-methylpropionamide) dihydrochloride (5.02 mg, 18.5x10 -3 mmol) were added to a 100 ml Schlenk flask and milliqui (mili) -Q) 1 g of purified water was dissolved. After vacuum / argon purging three times, the reaction was carried out at 70 ° C. The viscosity increased as bubbles were formed in the reaction solution during the reaction. After reacting for 18 hours, distilled water (5 ml) was added thereto, and the diluted polymer solution was slowly added dropwise to agitated THF (200 ml) using a homogenizer to prevent the precipitated polymer from agglomeration. This process was repeated twice, and the precipitate was filtered through a paper filter, and the recovered polymer was dried at 60 ° C. for 24 hours in a vacuum oven to obtain 1.1 g of vinyl phosphate polymer (55 wt% based on the total amount of monomer injected).

<실시예 2> 비닐인산 중합체 제조 Example 2 Vinyl Phosphoric Acid Polymer Preparation

실시예 1과 동일한 중합 조건하에서, 60℃의 중합온도에서 18시간 동안 중합 하였다. 중합 반응과 중합체 회수 과정은 실시예 1과 동일한 방법으로 실시하여 비닐인산 중합체 1.4g(투입된 단량체 총량기준 68중량%)를 얻었다. Under the same polymerization conditions as in Example 1, the polymerization was carried out for 18 hours at a polymerization temperature of 60 ℃. The polymerization reaction and the polymer recovery process were carried out in the same manner as in Example 1 to obtain 1.4 g of vinyl phosphate polymer (68% by weight based on the total amount of added monomers).

<실시예 3> 추가 중합용매 적가에 의한 비닐인산 중합체 제조 <Example 3> Preparation of vinyl phosphate polymer by dropwise addition of additional polymerization solvent

비닐인산(15g, 138.85mmol)과 2,2'-아조비스(2-메틸프로피온아미드) 디히드로클로라이드(37.7mg, 138.85x10-3mmol)를 250㎖ 쉬렌크 플라스크에 투입하고 밀리퀴 증류수(1g)를 넣어 녹였다. 3회 진공/알곤 퍼징 후 60℃에서 반응시켰다. 1시간 동안 반응 후 반응용액 내 기포가 발생되면서 점도가 증가할 때 증류수(0.5g)를 적가하였다. 이후 1시간 마다 증류수 1g을 7시간 동안 적가하면서 반응시켰다. 10시간 동안 반응시킨 후 증류수(30㎖)를 넣어 희석한 후, 희석한 중합용액을 호모제나이저를 사용하여 강하게 교반하는 THF(1L)에 천천히 적가하여 침전된 중합체가 뭉치지 않도록 하였다. 이 과정을 두 번 반복하고, 침전물을 종이필터를 통해 걸러서 회수한 중합체를 진공오븐에서 60℃로 24 시간 동안 건조하여 비닐인산 중합체 11.5g(투입된 단량체 총량기준 76 중량%)를 얻었다. Vinyl phosphate (15 g, 138.85 mmol) and 2,2'-azobis (2-methylpropionamide) dihydrochloride (37.7 mg, 138.85x10 -3 mmol) were added to a 250 ml Schlenk flask and milliqui distilled water (1 g). ) Melted. After vacuum / argon purging three times, the reaction was carried out at 60 ° C. After the reaction for 1 hour, distilled water (0.5 g) was added dropwise when the viscosity increased as bubbles were generated in the reaction solution. Thereafter, 1 g of distilled water was added dropwise for 7 hours every 1 hour. After reacting for 10 hours and diluting with distilled water (30ml), the diluted polymer solution was slowly added dropwise to THF (1L) with vigorous stirring using a homogenizer to prevent the precipitated polymer from agglomeration. This process was repeated twice, and the precipitate was filtered through a paper filter, and the recovered polymer was dried in a vacuum oven at 60 ° C. for 24 hours to obtain 11.5 g of vinyl phosphate polymer (76 wt% based on the total amount of monomer introduced).

<실시예 4> 비닐인산 중합체 제조 Example 4 Vinyl Phosphate Polymer Preparation

비닐인산(2g, 18.5mmol)과 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]디히드로클로라이드(6.00mg, 18.5x10-3mmol)를 100㎖ 쉬렌크 플라스크에 투입하고 밀리퀴 정제수 1g을 넣어 녹였다. 3회 진공/알곤퍼징 후 70℃에서 반응시켰다. 반응이 진행되는 동안 반응용액 내 기포가 형성되면서 점도가 증가하였다. 18시간 동안 반응시킨 후 증류수(5㎖)를 넣어 희석하고, 희석한 중합용액을 호모제나이저를 사용 하여 강하게 교반하는 THF(200㎖)에 천천히 적가하여 침전된 중합체가 뭉치지 않도록 하였다. 이 과정을 두 번 반복하고, 침전물을 종이필터를 통해 걸러서 회수한 중합체를 진공오븐에서 60℃로 24 시간 동안 건조하여 비닐인산 중합체 1.2g(투입된 단량체 총량기준 60 중량%)를 얻었다.100 ml Schlenk with vinyl phosphate (2 g, 18.5 mmol) and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (6.00 mg, 18.5x10 -3 mmol) Into the flask was dissolved 1g of milliquin purified water. The reaction was carried out at 70 ° C. after three vacuum / argon purging cycles. The viscosity increased as bubbles were formed in the reaction solution during the reaction. After reacting for 18 hours, distilled water (5 mL) was added thereto, and the diluted polymer solution was slowly added dropwise to THF (200 mL) with vigorous stirring using a homogenizer to prevent clumping of the precipitated polymer. This process was repeated twice, and the precipitate was filtered through a paper filter, and the recovered polymer was dried in a vacuum oven at 60 ° C. for 24 hours to obtain 1.2 g of vinyl phosphate polymer (60 wt% based on the total amount of monomer injected).

<실시예 5> 비닐인산 중합체 제조 Example 5 Vinyl Phosphoric Acid Polymer Preparation

실시예 4와 동일한 중합 조건하에서, 60℃ 중합온도에서 18시간 동안 중합하였다. 중합 반응과 중합체 회수 과정은 실시예 1과 동일한 방법으로 실시하여 비닐인산 중합체 1.1g(투입된 단량체 총량기준 55중량%)를 얻었다. Under the same polymerization conditions as in Example 4, the polymerization was carried out at 60 ° C polymerization temperature for 18 hours. Polymerization and polymer recovery were carried out in the same manner as in Example 1 to obtain 1.1 g of vinyl phosphate polymer (55 wt% based on the total amount of monomers introduced).

<실시예 6> 추가 중합용매 적가에 의한 비닐인산 중합체 제조 <Example 6> Preparation of vinyl phosphate polymer by dropwise addition of a polymerization solvent

비닐인산(20g, 185.13mmol)과 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]디히드로클로라이드(60mg, 185.13x10-3mmol)를 250㎖ 쉬렌크 플라스크에 투입하고 밀리퀴 증류수(2g)를 넣어 녹인다. 3회 진공/알곤 퍼징 후 50℃에서 반응시켰다. 2시간 동안 반응 후 반응용액 내 기포가 발생되면서 점도가 증가할 때 증류수(1.0g)를 적가하였다. 이후 1시간 마다 증류수 2g씩 3시간 동안 적가하면서 반응시켰다. 18시간 동안 반응시킨 후 증류수(70㎖)를 넣어 희석하고, 희석한 중합용액을 호모제나이저를 사용하여 강하게 교반하는 THF(1L)에 천천히 적가하여 침전된 중합체가 뭉치지 않도록 하였다. 이 과정을 두 번 반복하고, 침전물을 종이필터를 통해 걸러서 회수한 중합체를 진공오븐에서 60℃로 24 시간 동안 건조하여 비닐인산 중합체 7.8g(투입된 단량체 총량기준 39 중량%)를 얻었다. 250 ml Schlenk flask with vinyl phosphate (20 g, 185.13 mmol) and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (60 mg, 185.13x10 -3 mmol) Add distilled water (2 g) and dissolve it. The reaction was carried out at 50 ° C. after three vacuum / argon purging. After the reaction for 2 hours, distilled water (1.0 g) was added dropwise when the viscosity increased as bubbles were generated in the reaction solution. After 1 hour 2g of distilled water was added dropwise for 3 hours. After reacting for 18 hours, distilled water (70 ml) was added thereto and diluted. The diluted polymerization solution was slowly added dropwise to THF (1 L) with vigorous stirring using a homogenizer to prevent clumping of the precipitated polymer. This process was repeated twice, and the precipitate was filtered through a paper filter, and the recovered polymer was dried in a vacuum oven at 60 ° C. for 24 hours to obtain 7.8 g of vinyl phosphate polymer (39 wt% based on the total amount of monomer injected).

<비교예 1> 칼륨퍼설페이트 라디칼 개시제에 의한 비닐인산 중합체 제조 시도Comparative Example 1 Trial of Production of Vinyl Phosphate Polymer by Potassium Persulfate Radical Initiator

비닐인산(2g, 18.5mmol)과 칼륨퍼설페이트 (12.5mg, 46.25x10-3mmol)를 100㎖ 쉬렌크 플라스크에 투입하고 밀리퀴 정제수 1g을 넣어 녹였다. 3회 진공/알곤 퍼징 후 60oC에서 반응시켰다. 24시간 동안 반응시킨 후 중합 용액을 불용매인 THF(200㎖)에 적가했지만 중합체 침전이 형성되지 않았다. Vinyl phosphate (2 g, 18.5 mmol) and potassium persulfate (12.5 mg, 46.25x10 -3 mmol) were added to a 100 ml Schlenk flask and dissolved in 1 g of milliquique purified water. The reaction was carried out at 60 ° C. after three vacuum / argon purging. After reacting for 24 hours, the polymerization solution was added dropwise to insoluble solvent THF (200 mL), but no polymer precipitate formed.

<비교예 2> 암모늄퍼설페이트 라디칼 개시제에 의한 비닐인산 중합체 제조 시도Comparative Example 2 Attempt to Prepare Vinyl Phosphate Polymer by Ammonium Persulfate Radical Initiator

비닐인산(2g, 18.5mmol)과 암모늄퍼설페이트(10.55mg, 46.25x10-3mmol)를 100㎖ 쉬렌크 플라스크에 투입하고 밀리퀴 정제수 1g을 넣어 녹였다. 3회 진공/알곤 퍼징 후 60℃에서 반응시켰다. 24시간 동안 반응시킨 후 중합용액을 불용매인 THF(200㎖)에 적가했지만 중합체 침전이 형성되지 않았다. Vinyl phosphate (2 g, 18.5 mmol) and ammonium persulfate (10.55 mg, 46.25x10 -3 mmol) were added to a 100 ml Schlenk flask and dissolved in 1 g of milliquique purified water. After vacuum / argon purging three times, the reaction was carried out at 60 ° C. After the reaction for 24 hours, the polymerization solution was added dropwise to THF (200 mL), which is a non-solvent, but no polymer precipitate was formed.

<비교예 3> 4,4'-아조비스(4-시아노발러릭 아시드) 라디칼 개시제에 의한 비닐인산 중합체 제조 시도Comparative Example 3 Attempt to Prepare Vinyl Phosphate Polymer by 4,4'-Azobis (4-Cyanobalic Acid) Radical Initiator

비닐인산(2g, 18.5mmol)과 4,4'-아조비스(4-시아노발러릭 아시드) (12.96mg, 46.25x10-3mmol)를 100㎖ 쉬렌크 플라스크에 투입하고 밀리퀴 정제수 1g을 넣어 녹였다. 3회 진공/알곤 퍼징 후 60℃에서 반응시켰다. 24시간 동안 반응시킨 후 중합 용액을 불용매인 THF(200㎖)에 적가했지만 중합체 침전이 형성되지 않았다. Vinyl phosphate (2g, 18.5mmol) and 4,4'-azobis (4-cyanobalic acid) (12.96mg, 46.25x10 -3 mmol) were added to a 100ml Schlenk flask and 1g of Milliqui purified water. Melted. After vacuum / argon purging three times, the reaction was carried out at 60 ° C. After reacting for 24 hours, the polymerization solution was added dropwise to insoluble solvent THF (200 mL), but no polymer precipitate formed.

<비교예 4> AIBN 라디칼 개시제에 의한 비닐인산 중합체 제조 Comparative Example 4 Preparation of Vinyl Phosphate Polymer by AIBN Radical Initiator

비닐인산(2g, 18.5mmol)과 AIBN (60 mg)을 100㎖ 쉬렌크 플라스크에 투입하고 에틸아세테이드 1g을 넣어 녹였다. 3회 진공/알곤 퍼징 후 80℃에서 반응시켰다. 24시간 동안 반응시킨 후 중합 용액을 증류수에 묽히고, 불용매인 아세톤에 침전시켰다. 이 침전물을 다시 물에 녹이고 아세톤 용매에 침전시키는 과정을 2번 반복한 후 60℃ 진공오븐하에서 24시간 동안 건조하였다. 수율은 1.8 g (90%)이고 중량평균분자량은 5200 정도이었다. Vinyl phosphoric acid (2 g, 18.5 mmol) and AIBN (60 mg) were added to a 100 ml Schlenk flask and 1 g of ethyl acetate was dissolved. After vacuum / argon purging three times, the reaction was carried out at 80 ° C. After reacting for 24 hours, the polymerization solution was diluted with distilled water and precipitated in acetone, which is an insolvent. The precipitate was dissolved in water again and precipitated in acetone solvent twice, followed by drying under vacuum oven at 60 ° C. for 24 hours. The yield was 1.8 g (90%) and the weight average molecular weight was about 5200.

비교예 1~3을 통해 확인할 수 있는 바와 같이 상기한 세가지 라디칼 개시제, 즉 칼륨퍼설페이트, 암모늄퍼설페이트 및 4,4'-아조비스(4-시아노발러릭 아시드)는 수용액에 잘 용해되는 대표적인 라디칼 개시제이지만 비닐인산 단량체를 중합할 수 없는 불안정한 라디칼 개시제 구조이기 때문에 중합반응을 보이지 않았다. 반면 수용성이 아니고 유기용매에 녹는 AIBN 개시제의 경우(비교예 4) 에틸아세테이트 같은 극성용매하에서 중합은 잘 이루어졌지만 분자량이 5200 정도로 매우 낮았다. 이는 중합시 생성된 비닐인산중합체가 극성 유기용매에 대해 용해도가 낮아 고분자량의 중합체가 제조되기 어렵기 때문이다. As can be seen from Comparative Examples 1 to 3, the three radical initiators described above, namely potassium persulfate, ammonium persulfate, and 4,4'-azobis (4-cyanobalaric acid), are representatively soluble in aqueous solution. Although it was a radical initiator, it showed no polymerization reaction because it was an unstable radical initiator structure which cannot polymerize a vinyl phosphate monomer. On the other hand, the AIBN initiator, which is not water soluble and soluble in an organic solvent (Comparative Example 4), was well polymerized under a polar solvent such as ethyl acetate, but had a very low molecular weight of 5200. This is because the vinyl phosphate polymer produced during polymerization has low solubility in polar organic solvents, making it difficult to produce high molecular weight polymers.

<비교예 5> 80℃ 중합온도에서 비닐인산 중합체 제조 Comparative Example 5 Preparation of Vinyl Phosphate Polymer at 80 ° C Polymerization Temperature

실시예 1과 동일한 중합조건하에서, 80℃ 중합온도에서 5시간 동안 중합하였다. 중합 반응과 중합체 회수 과정은 실시예 1과 동일한 방법으로 실시하여 비닐인산 중합체 1.5g(투입된 단량체 총량기준 75중량%)를 얻었다. Under the same polymerization conditions as in Example 1, the polymerization was carried out at 80 ℃ polymerization temperature for 5 hours. The polymerization reaction and the polymer recovery process were carried out in the same manner as in Example 1 to obtain 1.5 g of vinyl phosphate polymer (75 wt% based on the total amount of monomer introduced).

<점도 측정> <Viscosity measurement>

각각 중합온도 80℃, 70℃, 60℃, 50℃ 에서 제조된 상기 비교예 5, 실시예 4, 5, 6의 중합체에 대해 점도측정을 수행하였다. 점도측정장비는 우벨로드 (Ubbelode) 점도계를 사용하고 상온에서 흐름시간은 90.08 초이었다. 용매는 0.1 M NaNO3 용매를 사용하였고 각각의 중합체에 대해 0.1 M NaNO3 용매에 대한 중합체 농도를 변화시켜 흐름시간을 측정하고 이의 상대점도(relative viscosity)를 선형화해서 절편을 구하고 이를 통해 고유점도(intrinsic viscosity)를 구하였다. 점도 측정 결과는 표 1에 나타내었다.Viscosity measurements were performed on the polymers of Comparative Examples 5, 4, 5, and 6 prepared at polymerization temperatures of 80 ° C, 70 ° C, 60 ° C, and 50 ° C, respectively. Viscosity measuring equipment uses a Ubbelode viscometer and the flow time at room temperature was 90.08 seconds. As solvent, 0.1 M NaNO 3 solvent was used, and the polymer concentration of 0.1 M NaNO 3 solvent was changed for each polymer to measure the flow time, and the relative viscosity was linearized to obtain the intercept, thereby obtaining the intrinsic viscosity ( intrinsic viscosity). The viscosity measurement results are shown in Table 1.

구분division 비교예 5Comparative Example 5 실시예 4Example 4 실시예 5Example 5 실시예 6Example 6 중합온도(℃)Polymerization temperature (℃) 8080 7070 6060 5050 고유점도(dl/g)Intrinsic viscosity (dl / g) 1.621.62 2.542.54 3.153.15 4.644.64

표 1에 나타낸 바와 같이, 중합온도가 낮아질수록 중합체의 고유점도가 증가함을 알 수 있다. 이는 중합온도가 낮아짐에 따라 분자량이 증가함을 나타낸다.As shown in Table 1, it can be seen that the intrinsic viscosity of the polymer increases as the polymerization temperature decreases. This indicates that the molecular weight increases as the polymerization temperature decreases.

<동적 광산란에 의한 분자량 측정> <Measurement of molecular weight by dynamic light scattering>

각각 중합온도 80℃, 60℃, 50℃에서 제조된 상기 비교예 5, 실시예 5, 6의 중합체에 대해 동적광산란법에 의한 분자량 측정을 수행하였다. 측정장비는 633nm와 20mW 에서 He-Ne 레이져가 달린 ALV-5000 장비를 사용하였다. 중합체 용액은 10g/L NaH2PO4 표준용매를 사용하여 투석막을 통해 정제하고 0.2~8.0g/l 범위의 농도로 제조하였다. 모든 샘플은 상온에서 실린더 샘플셀을 통해 측정하고 농도에 대한 산란각도에 대해 짐 프롯(Zimm Plot)을 구하고 이로부터 분자량을 구하였다. 또한 농도변화에 대한 굴절율 변화율(dn/dc)은 10g/L NaH2PO4 표준용매를 사용하여 동일 파장에서 스캐닝 미슨 인터페로미터(Scanning Michelson Interferometer)에 의해 측정하였다. 도 2 및 3는 각 중합체에 대한 짐 프롯(Zimm Plot)을 나타낸다. 표 2에는 이에 대한 굴절율 변화율(dn/dc)과 분자량(Mw)을 나타내었다.Molecular weight measurement by dynamic light scattering was performed on the polymers of Comparative Examples 5, 5 and 6 prepared at polymerization temperatures of 80 ° C, 60 ° C and 50 ° C, respectively. The measuring instrument was an ALV-5000 instrument with He-Ne laser at 633 nm and 20 mW. The polymer solution was purified through a dialysis membrane using a 10 g / L NaH 2 PO 4 standard solvent and prepared at a concentration ranging from 0.2 to 8.0 g / l. All samples were measured through a cylinder sample cell at room temperature, and the Zimmm Plot was calculated for the scattering angle with respect to the concentration, and the molecular weight was obtained therefrom. In addition, the refractive index change rate (dn / dc) with respect to the concentration change was measured by a Scanning Michelson Interferometer at the same wavelength using a 10 g / L NaH 2 PO 4 standard solvent. 2 and 3 show the Zimmm Plot for each polymer. Table 2 shows refractive index change rate (dn / dc) and molecular weight (Mw).

구분division 비교예 5Comparative Example 5 실시예 5Example 5 실시예 6Example 6 중합온도(℃)Polymerization temperature (℃) 8080 6060 5050 dn/dc (ml/g)dn / dc (ml / g) 0.2330.233 0.12860.1286 0.12240.1224 MwMw 47,60047,600 125,000125,000 187,000187,000

동적광산란법에 의해 분자량을 측정한 결과, 중합온도 50℃와 60℃에서 제조된 중합체가 100,000 이상의 분자량을 보였다.As a result of measuring the molecular weight by the dynamic light scattering method, the polymer produced at the polymerization temperature of 50 ℃ and 60 ℃ showed a molecular weight of 100,000 or more.

도 1은 비닐인산 중합체의 1H NMR 스펙트럼을 나타낸 도면이다. 1 is a diagram showing a 1 H NMR spectrum of a vinyl phosphate polymer.

도 2는 중합온도 50℃에서 제조된 비닐인산 중합체에 대한 동적 광산란법에 의한 짐 플롯(ZIMM PLOT)을 나타낸 도면이다. FIG. 2 is a diagram showing a ZIMM PLOT by a dynamic light scattering method for a vinyl phosphate polymer prepared at a polymerization temperature of 50 ° C. FIG.

도 3은 중합온도 60℃에서 제조된 비닐인산 중합체에 대한 동적 광산란법에 의한 짐 플롯(ZIMM PLOT)을 나타낸 도면이다.FIG. 3 is a diagram showing a ZIMM PLOT by a dynamic light scattering method for a vinyl phosphate polymer prepared at a polymerization temperature of 60 ° C. FIG.

Claims (11)

하기 화학식 1로 표시되는 비닐인산 단량체로 이루어진 중합체로서, 100,000~500,000의 중량평균분자량을 가지며, 0.1M NaNO3 수용액에서 2~20 dl/g의 고유점도(intrinsic viscosity)를 가지는 비닐인산 중합체.A polymer comprising a vinyl phosphate monomer represented by Formula 1, having a weight average molecular weight of 100,000 to 500,000, and having a intrinsic viscosity of 2 to 20 dl / g in a 0.1 M NaNO 3 aqueous solution. [화학식 1][Formula 1]
Figure 112007073685752-PAT00004
Figure 112007073685752-PAT00004
 상기 화학식 1로 표시되는 비닐인산 단량체, 아미딘기를 가진 아조화합물 또는 이미다졸린기를 가진 아조화합물인 라디칼 개시제, 및 양성자성 용매를 혼합하여 30~70℃의 온도에서 중합하는 단계를 포함하는 비닐인산 중합체의 제조방법.Vinyl phosphate comprising the step of polymerizing at a temperature of 30 ~ 70 ℃ by mixing a vinyl phosphate monomer represented by Formula 1, an azo compound having an amidine group or an azo compound having an imidazoline group and a protic solvent Method of Making Polymers. 청구항 2에 있어서, 상기 아미딘기를 가진 아조화합물은 하기 화학식 2로 표시되는 것인 비닐인산 중합체의 제조방법:The method of claim 2, wherein the azo compound having an amidine group is represented by the following Chemical Formula 2. [화학식 2][Formula 2]
Figure 112007073685752-PAT00005
Figure 112007073685752-PAT00005
 상기 화학식 2에서,In Chemical Formula 2, R1 내지 R5는 서로 같거나 상이하고, 치환 또는 비치환된 C1~C20의 선형 또는 가지 달린 알킬, 치환 또는 비치환된 C3~C20의 시클로알킬, 치환 또는 비치환된 C6~C20의 아릴, 치환 또는 비치환된 C7~C14의 아릴알킬, 치환 또는 비치환된 C2~C20의 알케닐이고, R 1 to R 5 are the same as or different from each other, and substituted or unsubstituted C 1 to C 20 linear or branched alkyl, substituted or unsubstituted C 3 to C 20 cycloalkyl, substituted or unsubstituted C 6 Aryl of ~ C 20 , substituted or unsubstituted C 7 -C 14 arylalkyl, substituted or unsubstituted C 2 -C 20 alkenyl, R1 내지 R5가 치환기에 의해 치환되는 경우, 상기 치환기는 -OH, -OR, -CO2H, -CO2R 및 -COR 중에서 선택되는 1 이상이며, 여기서 R은 서로 같거나 상이하고, C1~C20의 알킬이다.R 1 To When R 5 is substituted by a substituent, the substituent is one or more selected from -OH, -OR, -CO 2 H, -CO 2 R and -COR, wherein R is the same as or different from each other, C 1 ~ C 20 is alkyl. 청구항 2에 있어서, 상기 이미다졸린기를 가진 아조화합물은 하기 화학식 3으로 표시되는 것인 비닐인산 중합체의 제조방법:The method of claim 2, wherein the azo compound having an imidazoline group is represented by the following Chemical Formula 3: [화학식 3][Formula 3]
Figure 112007073685752-PAT00006
Figure 112007073685752-PAT00006
 상기 화학식 3에서,In Chemical Formula 3, R6 내지 R8은 서로 같거나 상이하고, 치환 또는 비치환된 C1~C20의 선형 또는 가지 달린 알킬, 치환 또는 비치환된 C3~C20의 시클로알킬, 치환 또는 비치환된 C6~C20의 아릴, 치환 또는 비치환된 C7~C14의 아릴알킬, 치환 또는 비치환된 C2~C20의 알케닐이고, R 6 to R 8 are the same as or different from each other, and substituted or unsubstituted C 1 to C 20 linear or branched alkyl, substituted or unsubstituted C 3 to C 20 cycloalkyl, substituted or unsubstituted C 6 Aryl of ~ C 20 , substituted or unsubstituted C 7 -C 14 arylalkyl, substituted or unsubstituted C 2 -C 20 alkenyl, R6 내지 R8이 치환기에 의해 치환되는 경우, 상기 치환기는 -OH, -OR, -CO2H, -CO2R 및 -COR 중에서 선택되는 1 이상이며, 여기서 R은 서로 같거나 상이하고, C1~C20의 알킬이다.R 6 To When R 8 is substituted by a substituent, the substituent is one or more selected from -OH, -OR, -CO 2 H, -CO 2 R and -COR, wherein R is the same as or different from each other, C 1 ~ C 20 is alkyl. 청구항 2에 있어서, 상기 양성자성 용매는 상기 비닐인산 단량체 총 중량 대비 1~100%를 사용하는 것인 비닐인산 중합체의 제조방법.The method according to claim 2, wherein the protic solvent is 1 to 100% of the total weight of the vinyl phosphate monomer using a method of producing a vinyl phosphate polymer. 청구항 2에 있어서, 상기 양성자성 용매는 물, 메탄올, 에탄올 및 이소프로 판올로 이루어진 군으로부터 선택되는 1종 이상인 것인 비닐인산 중합체의 제조방법.The method of claim 2, wherein the protic solvent is at least one selected from the group consisting of water, methanol, ethanol, and isopropanol. 청구항 2에 있어서, 상기 라디칼 개시제는 비닐인산 단량체 몰 대비 0.01~1%를 사용하는 것인 비닐인산 중합체의 제조방법.The method of claim 2, wherein the radical initiator uses 0.01 to 1% relative to the mole of vinyl phosphate monomer. 청구항 2에 있어서, 상기 라디칼 개시제는 2,2'-아조비스(2-메틸프로피온아미드), 2,2'-아조비스(N-부틸-2-메틸프로피온아미드), 2,2'-아조비스(N-시클로헥실-2-메틸프로피온아미드), 2,2'-아조비스[N-(2-프로페닐)-2-메틸프로피온아미드], 2,2'-아조비스[N-(2-카르복실에틸)-2-메틸프로피온아미드], 2,2'-아조비스[2-메틸-N-(2-히드록시부틸]프로피온아미드, 2,2'-아조비스{2-메틸-N-[1,1-비스(히드록시메틸)-2-히드록시에틸]프로피온아미드}, 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판], 2,2'-아조비스{2-[1-(2-히드록시에틸)-2-이미다졸린-2-일]프로판} 및 이들의 할로겐화물과의 염화합물 또는 수화물로 이루어진 군으로부터 선택되는 것인 비닐인산 중합체의 제조방법.The method of claim 2, wherein the radical initiator is 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis [N- (2- Carboxyethyl) -2-methylpropionamide], 2,2'-azobis [2-methyl-N- (2-hydroxybutyl] propionamide, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2 ' Vinyl phosphate selected from the group consisting of azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} and their salt compounds or hydrates with halides Method of Making Polymers. 청구항 2에 있어서, 상기 중합 단계 후 수득되는 중합용액을 증류수로 희석한 후, 불용매에 상기 희석한 중합용액을 적가함으로써 중합체를 침전시켜 회수하는 단계를 더 포함하는 것인 비닐인산 중합체의 제조방법. The method of claim 2, further comprising diluting the polymerization solution obtained after the polymerization step with distilled water, and then precipitating and recovering the polymer by dropwise adding the diluted polymerization solution to an insoluble solvent. . 청구항 9에 있어서, 상기 불용매는 메탄올, 에탄올, 프로판올, 부탄올, 아세톤 또는 THF인 것인 비닐인산 중합체의 제조방법.The method of claim 9, wherein the insolvent is methanol, ethanol, propanol, butanol, acetone or THF. 청구항 9에 있어서, 상기 불용매를 교반하는 것인 비닐인산 중합체의 제조방법.The method for producing a vinyl phosphate polymer according to claim 9, wherein the insoluble solvent is stirred.
KR1020070103559A 2007-10-15 2007-10-15 Vinyl Phosphate Polymer and Method for Making the Same KR101062923B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020070103559A KR101062923B1 (en) 2007-10-15 2007-10-15 Vinyl Phosphate Polymer and Method for Making the Same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020070103559A KR101062923B1 (en) 2007-10-15 2007-10-15 Vinyl Phosphate Polymer and Method for Making the Same

Publications (2)

Publication Number Publication Date
KR20090038191A true KR20090038191A (en) 2009-04-20
KR101062923B1 KR101062923B1 (en) 2011-09-06

Family

ID=40762477

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020070103559A KR101062923B1 (en) 2007-10-15 2007-10-15 Vinyl Phosphate Polymer and Method for Making the Same

Country Status (1)

Country Link
KR (1) KR101062923B1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012060515A1 (en) * 2010-11-05 2012-05-10 제일모직 주식회사 Flame retardant and scratch-resistant polycarbonate resin composition
US9005491B2 (en) 2011-06-29 2015-04-14 Cheil Industries Inc. Photosensitive resin composition for color filter and color filter using the same
US9340670B2 (en) 2010-12-14 2016-05-17 Cheil Industries Inc. Flame-retardant polycarbonate resin composition with scratch resistance
US9587058B2 (en) 2010-07-28 2017-03-07 Samsung Sdi Co., Ltd. Transparent thermoplastic resin composition
US9864272B2 (en) 2012-12-07 2018-01-09 Samsung Sdi Co., Ltd. Photosensitive resin composition for color filter, and color filter using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100564430B1 (en) * 2003-07-16 2006-03-28 주식회사 하이닉스반도체 Organic anti-reflective coating polymer, its preparation method and organic anti-reflective coating composition comprising the same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9587058B2 (en) 2010-07-28 2017-03-07 Samsung Sdi Co., Ltd. Transparent thermoplastic resin composition
WO2012060515A1 (en) * 2010-11-05 2012-05-10 제일모직 주식회사 Flame retardant and scratch-resistant polycarbonate resin composition
CN103189447A (en) * 2010-11-05 2013-07-03 第一毛织株式会社 Flame retardant and scratch-resistant polycarbonate resin composition
CN103189447B (en) * 2010-11-05 2015-02-04 第一毛织株式会社 Flame retardant and scratch-resistant polycarbonate resin composition
US9127157B2 (en) 2010-11-05 2015-09-08 Cheil Industries Inc. Flame-retardant and scratch-resistant polycarbonate resin composition
US9340670B2 (en) 2010-12-14 2016-05-17 Cheil Industries Inc. Flame-retardant polycarbonate resin composition with scratch resistance
US9005491B2 (en) 2011-06-29 2015-04-14 Cheil Industries Inc. Photosensitive resin composition for color filter and color filter using the same
US9864272B2 (en) 2012-12-07 2018-01-09 Samsung Sdi Co., Ltd. Photosensitive resin composition for color filter, and color filter using the same

Also Published As

Publication number Publication date
KR101062923B1 (en) 2011-09-06

Similar Documents

Publication Publication Date Title
Roy et al. Sugar-responsive block copolymers by direct RAFT polymerization of unprotected boronic acid monomers
EP0804497B1 (en) Soluble, electroconductive polypyrrole and method for preparing the same
JP4848735B2 (en) Polymers for electrochemical devices of polymerizable imidazole salts
Nakabayashi et al. Synthesis of 1, 2, 4-triazolium salt-based polymers and block copolymers by RAFT polymerization: Ion conductivity and assembled structures
Wang et al. Polymerization-induced self-assembly of acrylonitrile via ICAR ATRP
KR101062923B1 (en) Vinyl Phosphate Polymer and Method for Making the Same
Bray et al. Anionic multiblock core cross-linked star copolymers via RAFT polymerization
CN114478886B (en) Imidazole polyion liquid and preparation method thereof
Kopeć et al. Aqueous RAFT polymerization of acrylonitrile
Fan et al. Facile synthesis of well-controlled poly (1-vinyl imidazole) by the RAFT process
Vygodskii et al. New ionic liquids with hydrolytically stable anions as alternatives to hexafluorophosphate and tetrafluoroborate salts in the free radical polymerization and preparation of ion-conducting composites
Zhu et al. Synthesis of tertiary amine‐based pH‐responsive polymers by RAFT Polymerization
Abraham et al. Synthesis of poly (styrene‐block‐tert‐butyl acrylate) star polymers by atom transfer radical polymerization and micellization of their hydrolyzed polymers
Tamate et al. Photo/thermoresponsive ABC triblock copolymer-based ion gels: photoinduced structural transitions
Hu et al. Synthesis of well‐defined glycoconjugate polyacrylamides via preactivated polymers prepared by ATRP
EP2657265B1 (en) ABA triblock copolymer, thickener, and aqueous composition
JP7310279B2 (en) Composite composed of polythiophene-polystyrene sulfonic acid copolymer and aqueous dispersion containing same
CN110831983B (en) Method for producing vinyl ether polymer having oxyethylene chain by radical polymerization
KR101964200B1 (en) Preparation method of conductive polymer for electrolytic capacitor
KR102472048B1 (en) Manufacturing method of polyacrylonitrile
Ji et al. Linear coupling of spherical block copolymer micelles induced by gradually depositing an insoluble component onto the core–shell interface
Bingöl Synthesis and characterization of poly (vinylphosphonic acid) for proton exchange membranes in fuel cells
Wang et al. Poly (N-isopropylacrylamide) hydrogels fabricated via click chemistry: Well-defined α, ω-bis propargyl linear poly (N-isopropylacrylamide) s as crosslinkers
CA1153497A (en) Poly-(alpha-alkoxy)acrylamide and poly-(alpha-alkoxy) acrylamide complexes
US20130085242A1 (en) Preparation of polymers by controlled free-radical polymerization

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20140716

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20150716

Year of fee payment: 5

FPAY Annual fee payment

Payment date: 20160817

Year of fee payment: 6

FPAY Annual fee payment

Payment date: 20170718

Year of fee payment: 7

FPAY Annual fee payment

Payment date: 20180619

Year of fee payment: 8

FPAY Annual fee payment

Payment date: 20190625

Year of fee payment: 9