KR930002701B1 - Process for preparing phosphoric xylate resin for adsorbing uranium ion - Google Patents
Process for preparing phosphoric xylate resin for adsorbing uranium ion Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/12—Compounds containing phosphorus
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
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- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- 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
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
Abstract
Description
본발명은 우라늄이온 흡착에 유용한 인산계 킬레이트 수지의 제조방법에 관한 것으로서, 더욱 상세하게는 주쇄측에 포스포노기로 전환될 수 있는 구조를 갖는 단위체와 스티렌단위체 등을 중합시키되 디비닐벤젠을 가교제로하여 망목형의 공중합체 수지를 합성하고난뒤, 이들 공중합체 수지의 페닐구조 혹은 그 페닐기에 도입된 클로로알킬기에 포스포노기를 추가도입시키므로써 공중합체 킬레이트 기능기의 기본골격이 벤젠을 공간자(spacer)로하여 요철상태가 되게함은 물론 이들 기능기의 성분도 풍부하게 도입하므로써 우라늄이온에 대한 킬레이트 형성 능력을 강화시킨 우라늄이온 흡착용 인산계 킬레이트수지의 새로운 제조방법에 관한 것이다.The present invention relates to a method for preparing a phosphate chelate resin useful for adsorption of uranium ions, and more particularly, polymerizes a unit and a styrene unit having a structure that can be converted into a phosphono group on the main chain side, but divinylbenzene is used as a crosslinking agent. After synthesizing the mesh type copolymer resin, the phospho group is added to the phenyl structure of the copolymer resin or the chloroalkyl introduced into the phenyl group, so that the basic skeleton of the copolymer chelate functional group is benzene. The present invention relates to a new process for producing phosphate chelate resin for uranium ion adsorption which enhances the ability of chelate formation to uranium ions by introducing abundant components of these functional groups.
우라늄이온(UO2 ++) 1개에 대해 포스포노기능기 2개가 킬레이트 흡착을 하는 것으로 알려져 있다.[Chem. Reproc. Irradi. Nuclear Fuel. 55, 64(1977)].It is known that two phosphono functional groups chelate adsorption for one uranium ion (UO 2 ++ ). [Chem. Reproc. Irradi. Nuclear Fuel. 55, 64 (1977).
지금까지 알려져 있는 인산계 킬레이트 수지는 폴리올수지에다 인산을 에스테르화반응시켜서 제조하거나(고분자화학 10, 117(1953), Ind. Eng. Chem., 46, 1042(1954)], 스티렌계 공중합체의 측쇄인 페닐기에 포스포노기를 도입시켜서 제조하였는바(미국특허 제 2, 764, 562호, 제 2, 764, 564호, 일본특허 공고 제 74-18719, 독일특허 제 2, 500, 744호), 전자의 경우는 산이나 알카리 존재하에서 가수분해가 일어나 인산기 함량이 줄어들게 됨으로써 흡착-탈착의 반복사용에서 오는 재사용 능력에서, 우라늄이온의 흡착효과가 적어지는 문제가 있었으며, 후자의 경우는 공중합체수지의 기본골격으로 볼때 포스포노기의 도입위치가 모두 공중합체 수지의 기본골격의 측쇄위치로 도입되기때문에 킬레이트 형성을 위한 기능성분의 배치가 단순하게 되어 있어서 우라늄이온에 대한 킬레이트 형성능력이 현저하게 떨어지는 문제가 있었다.Phosphoric acid chelate resins known to date are prepared by esterification of phosphoric acid to polyol resins (polymer chemistry 10, 117 (1953), Ind. Eng. Chem., 46, 1042 (1954)), or styrene copolymers. It was prepared by introducing a phosphono group into the side chain phenyl group (US Pat. Nos. 2,764,562, 2,764,564, Japanese Patent Publication No. 74-18719, German Patents 2,500,744). In the former case, the hydrolysis occurs in the presence of acid or alkali, and the content of phosphate groups decreases, thereby reducing the adsorption effect of uranium ions in the reusability resulting from repeated use of adsorption and desorption. In view of the basic skeleton, since all of the phosphono groups are introduced into the side chain positions of the basic skeleton of the copolymer resin, the arrangement of functional components for chelate formation is simplified, and There was a problem that the ability to form chelates significantly decreased.
따라서, 우라늄이온의 흡착을 위한 보다 개선된 새로운 인산계 킬레이트 수지의 개발이 요구되어 왔다.Accordingly, there has been a need for the development of new and improved phosphoric acid chelate resins for adsorption of uranium ions.
이와같은 배경에서 근래들어서 개발된 우라늄이온 흡착용 인산계 킬레이트 수지는 인산기(포스포노기)의 기능구조가 산이나 알카리에 의해 가수분해가 일어나지 않도록 하기위해 공중합체 수지의 기본골격을 중심으로 볼때 측쇄위치의 탄소원자에 직접 포스포노기가 도입되도록 하였고, 또 우라늄이온에 대한 킬레이트 형성능력이 좋아지도록 하기위해 포스포노기 구조를 공중합체수지의 기본골격인 주쇄와 그 측쇄위치에 보다 많이 도입시켜서 킬레이트 기능이 향상되도록 하였다.The phosphate-based chelate resin for uranium ion adsorption that has been recently developed in this background has a side chain when the functional structure of the phosphate group (phosphono group) is centered on the basic skeleton of the copolymer resin to prevent hydrolysis caused by acid or alkali. The phosphono group was introduced directly into the carbon atom at the position, and in order to improve the ability of chelate formation for uranium ions, the phosphono group structure was introduced into the main chain and the side chain position, which is the basic skeleton of the copolymer resin, to chelate function. This was to be improved.
즉, 그동안 이러한 인산계 킬레이트 수지들을 제조하기 위해 스티렌, 디비닐벤젠으로부터 얻은 공중합체 수지에 포스포노기를 도입하였는데, 그 방법은 이들 공중합체수지의 측쇄인 페닐기 자체에 포스포노기를 그대로 도입하거나 혹은 그 페닐기 구조를 클로로메틸화시킨후 포스포노기를 도입하는 방법들[J. Appl. Polym. Sci., 29, 2045(1984)]이었다.In other words, in order to produce such phosphate chelate resins, phosphono groups were introduced into copolymer resins obtained from styrene and divinyl benzene, and the method introduced phosphono groups into the phenyl group itself, which is a side chain of these copolymer resins, or Methods of introducing phosphono groups after chloromethylation of the phenyl group structure [J. Appl. Polym. Sci., 29, 2045 (1984).
그러나, 이러한 방법들은 모두 포스포노기 구조를 공중합체 기본골격의 측쇄인 페닐기쪽에만 도입하는 경우로서, 페닐기에 대한 포스포노기의 도입은 페닐기의 오르소(ortho-) 위치에는 입체장애 때문에 반응하기가 어려우며, 주로 파라위치에만 도입된다.However, all of these methods introduce the phosphono group structure only to the phenyl group, which is the side chain of the copolymer backbone, and the introduction of the phosphono group to the phenyl group reacts due to steric hindrance at the ortho- position of the phenyl group. Is difficult and is mainly introduced only in the para position.
여기서, 페닐기상에 도입된 포스포노기는 이들 공중합체 수지의 기본골격을 중심으로볼때는, 측쇄 한쪽에만 치우침으로써 킬레이트 형성기능기인 포스포노기의 입체 분산 효과가 적고 우라늄이온에 대한 킬레이트 형성능력이 크게 떨어지는 경향을 보였다.Here, when the phosphono groups introduced on the phenyl group are centered on the basic skeleton of these copolymer resins, the phosphono group, which is a chelate-forming functional group, is less steric-dispersed and has a large chelate-forming ability for uranium ions by being oriented only on one side chain. It showed a tendency to fall.
따라서, 본발명은 상기와 같은 종래의 방법들과는 달리 공중합체 수지의 기본골격인 주쇄에 킬레이트 형성이 가능한 인산기(포스포노기) 구조를 도입하고, 또다시 공중합체수지의 측쇄인 페닐기 혹은 그 페닐기에 도입된 클로로알킬기에 킬레이트 형성을 위한 포스포노기를 도입하여서, 공중합체수지의 기본골격내에서 측쇄인 페닐기 혹은 그 페닐기에 도입된 클로로알킬기에 치환된 포스포노기를 정점으로 요철구조가 이루어지도록 함으로써, 킬레이트 형성능력을 보다 크게 유지되도록 하여 우라늄이온의 흡착력을 크게하였다.Therefore, the present invention, unlike the conventional methods as described above, introduces a phosphate group (phosphono group) structure capable of chelation in the main chain, which is a basic skeleton of the copolymer resin, and again a phenyl group or a phenyl group, which is a side chain of the copolymer resin. By introducing a phosphono group for chelate formation into the introduced chloroalkyl group, the uneven structure is formed in a phenyl group which is a side chain or a phosphono group substituted with a chloroalkyl group introduced into the phenyl group in the backbone of the copolymer resin. Adsorption capacity of uranium ions was increased by maintaining the formation capacity larger.
이러한 포스포노기능기는 탄소원자에 직접 결합된 구조를 취하는 것으로 흡착-탈착의 반복되는 재생과정에서 이용되는 산 또는 알카리 용액들에 의한 가수분해가 일어나지 않도록 함으로써 재사용능력이 현저하게 개선되어지도록 하는 인산계 킬레이트 수지의 제조방법을 제공하는데 그 목적이 있다.These phosphono functional groups have a structure directly bonded to a carbon atom, so that the reusability is remarkably improved by preventing hydrolysis by acid or alkali solutions used in repeated regeneration of adsorption-desorption. It is an object of the present invention to provide a method for preparing a chelate resin.
이하, 본발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본발명은 우라늄이온 흡착용 킬레이트 수지를 제조하는데 있어서, 스티렌, 디비닐벤젠 및 비닐포스폰네이트의 한 종류인 비스-(2-클로로에틸)비닐포스폰네이트(이하 "CEVP"라 약칭함)의 단위체을 현탁공중합 반응시킨후 가수분해시켜 공중합체를 만들고, 그 공중합체 기본골격의 측쇄인 페닐기 혹은 그 페닐기에 도입된 클로로 알킬기에 대해 삼염화인을 반응시키고 가수분해시켜서 제조함을 그 특징으로 한다.The present invention, in the preparation of uranium ion adsorption chelate resin, of bis- (2-chloroethyl) vinyl phosphonate (hereinafter abbreviated as "CEVP") which is a kind of styrene, divinylbenzene and vinyl phosphonate The copolymer is prepared by suspending the co-polymerization reaction of the unit, followed by hydrolysis, to prepare a copolymer by reacting and hydrolyzing phosphorus trichloride with respect to a phenyl group which is a side chain of the main skeleton of the copolymer or a chloroalkyl group introduced into the phenyl group.
아와같은 본발명을 더욱 상세히 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본발명은 우라늄이온 흡착용 인산계 킬레이트 수지를 제조하는데 있어서, 포스포노기로 전환될 수 있는 구조를 갖는 단위체로서 CEVP와 스티렌 및 디비닐벤젠의 비닐단위체들을 공중합시킨후 가수분해시킴으로써 공중합체 수지의 기본골격 내에 킬레이트 형성이 가능한 포스포노기 구조를 만들고, 또 다시 공중합체 기본골격의 측쇄인 페닐기 혹은 그 페닐기에 도입된 클로로알킬기에 삼염화인을 반응시켜서 킬레이트 형성을 위한 포스포노기로의 전환 가능한 구조를 만든후 가수분해와 동시에 산화하여 포스포노기로 전환하였다.The present invention is to prepare a phosphate chelate resin for adsorption of uranium ion, a unit having a structure that can be converted into a phosphono group, copolymerizes CEVP, vinyl units of styrene and divinylbenzene, and then hydrolyzes the base of the copolymer resin. A phosphono group structure capable of chelate formation in the backbone was formed, and a phosphorus trichloride was reacted with a phenyl group, which is a side chain of the main skeleton of the copolymer, or a chloroalkyl group introduced into the phenyl group, thereby converting a phosphono group for chelate formation. It was then oxidized at the same time as hydrolysis and converted to phosphono groups.
이들 킬레이트 공중합체수지는 기본골격의 주쇄 및 측쇄에 모두 포스포노기를 갖는데, 측쇄인 페닐기 혹은 그 페닐기에 도입된 클로로알킬기에 치환된 포스포노기를 정점으로 요철(凹凸)구조가 이루어지게 함으로써 킬레이트 형성능력이 보다 크게 유지되도록 한 것이다.These chelate copolymer resins have a phosphono group in both the main chain and the side chain of the basic skeleton, and has a chelate-forming ability by forming a concave-convex structure with a phenyl group as a side chain or a phosphono group substituted with a chloroalkyl group introduced into the phenyl group. It is kept larger than this.
또, 이러한 본발명의 인산계 킬레이트수지는 포스포노기능기가 탄소원자에 직접 결합된 구조를 갖고있어 흡착-탈착과정이 반복되는 재생시 산이나 알카리 용액 등의 존재하에서 가수분해에 의해 포스포노기 구조의 탈리가 없기때문에 양호한 킬레이트 형성과 아울러 재사용이 가능한 내구성을 갖게끔 되는 것이다.In addition, the phosphate chelate resin of the present invention has a structure in which a phosphono functional group is directly bonded to a carbon atom, so that the phosphono group structure is hydrolyzed in the presence of an acid or alkaline solution during regeneration in which the adsorption-desorption process is repeated. Since there is no desorption, it has good chelate formation and durability that can be reused.
이러한 본발명에 다른 인산계 킬레이트수지의 제조방법을 개략적인 반응식으로 나타내면 다음과 같이 나타낼 수 있다.In the present invention, a method of preparing a phosphate chelate resin according to the present invention may be represented as follows.
이러한 본발명을 좀더 상세히 설명하면 먼저 스티렌, 디비닐벤젠, CEVP(알킬비닐포스폰네이트도 포함)등의 단위체에 톨루엔을 희석제로 첨가하여 라디칼 개시제를 가하여 40∼100℃에서 2∼50시간 현탁중합시킨후, 얻어진 공중합체 수지를 산촉매 존재하에서 40∼130℃에서 1∼60시간 가수분해시키게되면 공중합체 수지의 주쇄에 포스포노기가 함유된 수지가 제조되게 된다.The present invention will be described in more detail. First, toluene is added to a unit such as styrene, divinylbenzene, or CEVP (including alkylvinylphosphonate) as a diluent, and a radical initiator is added to suspend polymerization at 40 to 100 ° C for 2 to 50 hours. After the reaction, the obtained copolymer resin is hydrolyzed at 40 to 130 ° C. for 1 to 60 hours in the presence of an acid catalyst to prepare a resin containing a phosphono group in the main chain of the copolymer resin.
여기서, 친수성이 있는 CEVP 단위체와 친유성의 스티렌단위체간의 공중합은 현탁중합방법으로써, 중합체의 모양이 구상(球狀)으로 형성되어 구성의 안쪽은 친유성의 스티렌구조가 많이 포함되게되고 구상의 바깥쪽은 친수성이 큰 CEVP 구조가 많이 배열되게 된다.Here, the copolymerization between the hydrophilic CEVP unit and the lipophilic styrene unit is a suspension polymerization method, in which the polymer is formed into a spherical shape, and the inside of the composition includes a large amount of lipophilic styrene structure and the outside of the sphere. Pages are arranged with many hydrophilic CEVP structures.
즉, 우라늄이온 흡착을 위한 기능기 도입에 이용되는 CEVP 구조는 킬레이트수지 구상표면에 더많이 배열되기 때문에 평균기대치보다 높은 CEVP 구조가 구상표면에 도입되는 것이다.That is, the CEVP structure used to introduce the functional group for uranium ion adsorption is arranged more on the surface of the chelate resin, so that the CEVP structure higher than the average expected value is introduced on the surface.
본발명에 따르면, 이들 인산계 공중합체 수지 구조중에서 공중합체 기본골격의 측쇄인 페닐기 혹은 그 페닐기에 도입된 클로로알킬기에 삼염화인을 40∼100℃에서 2∼50시간 반응시켜 산촉매존재하에서 40∼130℃에서 1∼60시간 가수분해와 동시에 산화시킴으로써 포스포노기 구조가 보다 풍부하게되었다.According to the present invention, phosphoric trichloride is reacted at 40 to 100 DEG C for 2 to 50 hours in a phenyl group which is a side chain of the copolymer main skeleton or a chloroalkyl group introduced into the phenyl group in these phosphoric acid copolymer resin structures, and 40 to 130 in the presence of an acid catalyst. By oxidizing at the same time with hydrolysis at 1 to 60 hours, the phosphono group structure became more abundant.
이들 공중합체의 측쇄인 페닐기에 도입된 포스포노기를 정점으로 주쇄의 포스포노기와 요철(凹凸) 상태의 배치가 이루어져 양호한 킬레이트 형성능력을 나타나게 하는 인산계 킬레이트 수지를 제조할 수가 있게된다.It is possible to produce a phosphate chelate resin that exhibits a good chelating ability by arranging the phosphono groups introduced into the phenyl group, which is the side chain of these copolymers, at the apex and the uneven state of the main chain.
한편, 본발명에서 사용되는 비닐포스폰네이트의 한 종류인 CEVP는 공중합체 전체조성의 0.45mol% 이내(용액중합에서의 최대치)로 사용하는 것이 좋은데, 만일 CEVP의 함량이 0.45mol% 이상이 되면 사용된 단위체의 공중합체 CEVP 구조의 입체 장애관계, CEVP의 단독중합 가능성 및 CEVP 자신에 대한 연쇄이동 반응등으로 공중합수율이 떨어지고 반응시간도 매우 길어지기 때문에 바람직하지 못하다.On the other hand, CEVP, a kind of vinyl phosphonate used in the present invention, is preferably used within 0.45 mol% (maximum value in solution polymerization) of the total composition of the copolymer, and if the content of CEVP is 0.45 mol% or more, It is not preferable because the copolymer yield decreases and the reaction time is very long due to the steric hindrance of the copolymer CEVP structure, the possibility of homopolymerization of CEVP, and the chain transfer reaction to CEVP itself.
또한, 본발명에서 공중합시 가교제로 사용되는 디비닐벤젠의 사용량은 상기의 사용된 단위체 총량에 대하여 2.0∼30중량%의 비율로 투입하여 사용하는 것이 좋다.In addition, in the present invention, the amount of divinylbenzene used as a crosslinking agent in the copolymerization may be used in a ratio of 2.0 to 30% by weight based on the total amount of the used monomers.
즉, 상기 디비닐벤젠은 스트렌계 구상 공중합체에 대해 기계적인 강도를 주며 우라늄이 드나들 수 있는 망상구조의 사다리 역할을 해주는 가교제로서, 상기의 사용량 보다 적으면 망상구조가 사다리역할을 못하기 때문에 좋지않고, 또 많으면 가교도가 커짐으로인해 표면적이 작아지고 흡착효과가 감소되어 좋지않게 된다.In other words, the divinylbenzene is a crosslinking agent that gives mechanical strength to the styrene-based spheroidal copolymer and acts as a ladder of the network structure through which uranium can enter, and when the amount is less than the amount used, the network structure does not act as a ladder. It is not good, and if it is large, the surface area becomes small due to the increase of the degree of crosslinking and the adsorption effect is reduced, which is not good.
그리고, 본발명에서 공중합시 사용될 수 있는 톨루엔, 싸이클로헥산등 소량의 유기희석제는 사용된 단위체 총량에 대하여 2.0∼20중량%의 비율로 투입사용되는데, 이들은 공중합반응시 침전제로써 구상(球狀) 공중합체의 물리적인 요철(凹凸)구조를 만드는데 쓰이고 반응후는 구상 공중합체내에 물리적으로 혼합되어 있는 상태이며, 이들을 건조시킴으로써 구상공중합체의 비표면적이 커진다.In addition, a small amount of organic diluent such as toluene, cyclohexane, etc. which can be used during copolymerization in the present invention is used at a ratio of 2.0 to 20% by weight based on the total amount of the monomers used, and they are spherical air as a precipitant during the copolymerization reaction. It is used to make physical concavo-convex structure of the copolymer, and after the reaction, it is physically mixed in the spherical copolymer, and the specific surface area of the spherical copolymer is increased by drying them.
한편, 본발명에서는 라디칼중합방법을 사용하게되는바, 이때 라디칼 개시제로써는 과산화벤조일, P, P'-디클로로과산화벤조일, 메틸에틸케톤퍼옥사이드, 큐멘하이드로퍼옥사이드, 디-t-부틸퍼옥사이드, 과유산칼륨 또는 과유산암모늄 등의 과산화물 개시제나 비스아조이소부틸로니트릴등의 아조계 라디칼 개시제등을 모두 사용할 수 있다.Meanwhile, in the present invention, a radical polymerization method is used, wherein as the radical initiator, benzoyl peroxide, P, P'-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, di-t-butyl peroxide, and Both peroxide initiators, such as potassium lactate or ammonium persulfate, and azo radical initiators, such as bis azoisobutylonitrile, can be used.
또한, 본발명의 공중합 방법은 라디칼 현탁 중합법을 사용하는데, 이때의 현탁제로서는 메틸셀룰로오즈, 부분가수분해화 폴리비닐알콜, 폴리비닐피롤리돈 또는 이들의 혼합물이 사용된다. 여기서 현탁제의 사용량은 투입되는 사용된 단위체 총량에 대하여 0.01∼4.0중량%이고, 특히 0.1∼2.0중량%가 바람직하다.In addition, the copolymerization method of the present invention uses a radical suspension polymerization method, wherein the suspending agent is methyl cellulose, partially hydrolyzed polyvinyl alcohol, polyvinylpyrrolidone or a mixture thereof. The amount of the suspending agent used herein is 0.01 to 4.0% by weight, particularly 0.1 to 2.0% by weight based on the total amount of used monomers.
일반적으로 이러한 현탁중합은 수분산상(aqueous dispersion)에서 이루어지므로 본발명의 공중합 방법에서도 라디칼중합은 수분산상에서 일어나게되고, 이때 유기단위체들에 대한 물의 중량 비율은 0.5∼15중량비가 좋다.In general, such suspension polymerization is carried out in an aqueous dispersion (aqueous dispersion), so even in the copolymerization method of the present invention, radical polymerization takes place in the water dispersion phase, wherein the weight ratio of water to organic units is preferably 0.5 to 15 weight ratio.
만일, 물이 0.5중량비보다 적게 투입되면 점도가 너무커져서 균일한 수분산상을 얻기가 어렵고, 반면에 15중량비 보다 많게 투입되면 생산성이 낮아지고 많은양의 물을 가열해야하므로 에너지소비량이 많아지게 되어 좋지 않게된다.If less than 0.5 weight ratio of water is added, the viscosity becomes so large that it is difficult to obtain a uniform aqueous phase. On the other hand, if more than 15 weight ratio is added, productivity decreases and a large amount of water needs to be heated. Will not.
본발명에 따르면, 여기서 사용된 현탁제의 사용량과 수분산상에서 물과 유기단위체들간의 중량 비율로부터 구상공중합체 입자크기를 조절하게 된다.According to the present invention, the size of the spherical copolymer particles is adjusted from the amount of the suspending agent used herein and the weight ratio between the water and the organic units in the aqueous phase.
이렇게 본발명에서 얻어진 인산계 공중합체에 대한 가수분해는 건조한 공중합체 수지 중량당 2∼10배 중량비의 에탄올과 1∼20배 중량비의 진한 염산을 주가하고 40∼130℃에서 1∼60시간 동안 유지시키면 되며, 그후의 정제는 휘발성 성분을 날려보내고 잔류물을 물과 메탄올로 씻은 다음 건조하면 된다.The hydrolysis of the phosphoric acid copolymer obtained in the present invention is added to the ethanol of 2 to 10 times by weight and the concentrated hydrochloric acid of 1 to 20 times by weight per dry copolymer resin and maintained at 40 to 130 ℃ for 1 to 60 hours Subsequent purification can be accomplished by blowing off the volatile components, washing the residue with water and methanol and then drying.
한편, 본발명에서 얻어진 인산계 공중합체 수지의 측쇄인 페닐기 혹은 그 페닐기에 도입된 클로로알킬기에 대한 추가 포스포노기 도입방법은 건조한 공중합체 수지 중량당 2∼20배 중량비의 싸이클로헥산 용액중에서 0.01∼10배 중량비의 염화알루미늄을 촉매로하여, 0.01∼15배 중량비의 삼염화인을 40∼100℃에서 2∼50시간 후리델-크라프트(Friedel-Crafts) 반응시킨다.On the other hand, the additional phosphono group introduction method for the phenyl group which is the side chain of the phosphate copolymer resin obtained in the present invention or the chloroalkyl group introduced into the phenyl group is 0.01 to 20 to 20 times by weight of the cyclohexane solution per dry copolymer resin weight. Using a 10-fold weight ratio of aluminum chloride as a catalyst, 0.01 to 15-fold weight ratio of phosphorus trichloride is reacted for 2 to 50 hours at Friedel-Crafts at 40 to 100 ° C.
여기서 공중합체 수지 기본골격의 측쇄인 페닐기에 대한 클로로알킬기의 도입을 위해서는 상기의 공중합체 중량당 1∼30배 중량비의 시클로헥산 용액중에서 0.01∼10배 중량비의 염화알루미늄을 촉매로 하여, 0.01∼15배 중량비의 클로로알킬알킬에테르를 반응시킨다.In order to introduce a chloroalkyl group to the phenyl group, which is a side chain of the copolymer resin basic skeleton, 0.01 to 10 times by weight of aluminum chloride in a 1 to 30 times weight ratio of cyclohexane solution per weight of the copolymer is used as a catalyst. The chloroalkyl alkyl ether in the weight ratio is reacted.
그다음에는 이 반응물을 여과 분리시킨후 증류수와 메탄올로 세척하고, 추가 도입된 포스피노구조의 기능성분을 포스포노기로 활성화 시키기 위해서는 1∼30중량% 농도의 질산용액을 건조된 반응물 수지 중량당 2∼50배의 중량비로 주가하여 40∼130℃에서 1∼60시간동안 가수분해와 동시에 산화시킨다. 이때 얻어진 최종 제품은 여과분리후 물과 메탄올로 씻어 건조하면 된다.Next, the reaction product was separated by filtration, washed with distilled water and methanol, and a nitric acid solution having a concentration of 1 to 30% by weight was added at a weight of 2 to 30% by weight of the reactant resin to activate the phosphino structure. The stock is added at a weight ratio of 50 times and oxidized simultaneously with hydrolysis at 40 to 130 ° C. for 1 to 60 hours. The final product thus obtained may be washed with water and methanol after filtration and dried.
상술한 바와같은 본발명과 관련하여 우라늄이온의 흡착회수에는 트리부틸포스페이트의 기능구조를 많이 이용하고 있다.In connection with the present invention as described above, the functional structure of tributyl phosphate is widely used for adsorption recovery of uranium ions.
따라서, 본발명의 인산계 킬레이트 수지의 제조에 있어서는 킬레이트의 기능부분(O=P구조)에 대한 배위권 설계시에 우라늄이온에 대한 트리부틸포스페이트의 기능과 동일하다고 생각되는 포스포노구조를 킬레이트 기능기로하여 선택하고 포스포노기 함량의 영향, 킬레이트 공중합체 기본골격내에서 포스포노기의 주쇄 및 측쇄의 위치변화에 따른 영향, 가교제함량 및 비표면적 크기에 따른 영향, 흡착-탈착에서 오는 재사용 능력등을 고려함으로써, 종래의 제품에 비하여 우라늄이온에 대한 흡착성과 재사용 능력이 현저하게 개선된 인산계 킬레이트 수지를 제조할 수가 있게 되는 것이다.Therefore, in the production of the phosphate chelate resin of the present invention, the phosphono structure, which is considered to be the same as the function of tributyl phosphate for uranium ion, in the design of the coordination band for the functional portion of the chelate (O = P structure) The effect of phosphono group content, the effect of the positional change of the main and side chains of the phosphono group in the chelate copolymer backbone, the effect of crosslinking agent content and specific surface area size, and the reusability from adsorption-desorption, etc. In consideration of the above, it is possible to produce a phosphate chelate resin with remarkably improved adsorption and reusability to uranium ions compared to conventional products.
이하, 본발명을 실시예에 의거 상세히 설명하면 다음과 같은바, 본발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.
[실시예 1∼10]EXAMPLES 1-10
교반기가 있는 반응기에 스티렌, 디비닐벤젠, 비스-(2-클로로에틸)비닐포스폰네이트(CEVP), 톨루엔등을 넣고, 여기에다 중합개시제로는 과산화벤조일을 단위체들에 대해 0.2중량% 사용했으며, 상기 단위체들과의 수비(
현탁중합반응은 70℃에서 25시간 유지하여 생성된 중합반응물은 여과수세하였으며, 이것을 60℃가 유지된 진공건조기에서 48시간 건조시킨뒤 60/80메쉬(mesh)의 체(sieve)로 걸렀다.The suspension polymerization was maintained at 70 ° C. for 25 hours, and the resulting polymerization product was filtered and washed with water. The resultant was dried for 48 hours in a vacuum dryer maintained at 60 ° C., and then filtered through a 60/80 mesh sieve.
공중합체수지의 주쇄에 대한 포스포노기의 도입은 공중합 반응하여 얻은 건조된 수지의 중량당 매탄올 4중량비와 진한 염산 3중비를 주가하고 90℃에서 42시간 동안 환류시켜 가수분해를 통해 이루었으며, 이것의 정제는 휘발성분을 날려보내고 잔류물을 증류수로 씻은다음 건조하였다.The introduction of the phosphono group into the main chain of the copolymer resin was carried out by hydrolysis by refluxing at 90 ° C. for 42 hours, adding 4 parts by weight of methanol and triple hydrochloric acid per weight of the dried resin obtained by the copolymerization reaction. Its purification gave off volatiles, washed the residue with distilled water and dried.
이후 공중합체 수지 기본골격의 측쇄인 페닐기에 대한 포스포노기의 도입을 위해 상기 주쇄에만 포스포노기가 도입된 킬레이트 수지 중량당 8중량비의 싸이클로헥산 용액을 이용, 0.25중량비의 염화알루미늄 촉매 존재하에서 0.25중량비의 삼염화인을 70℃에서 30시간 동안 반응시킨뒤, 이 반응물을 여과분리후 물과 메탄올로 세척하고 건조하였다.Then, in order to introduce a phosphono group to the phenyl group, which is a side chain of the copolymer resin skeleton, an 8 weight ratio cyclohexane solution per weight of the chelating resin in which the phosphono group is introduced into the main chain was used, and 0.25 weight ratio was present in the presence of 0.25 weight ratio aluminum chloride catalyst. Phosphorus trichloride was reacted at 70 ° C. for 30 hours, and the reaction mixture was filtered and washed with water and methanol and dried.
여기서 건조된 반응물을 중량당 2% 농도의 질산용액을 10중량비로 80℃에서 20시간 동안 가수분해와 동시에 산화시켰다. 그다음에는 이것을 60℃에서 48시간동안 진공건조하여 노란색의 구상 킬레이트 수지를 제조하였다. 얻어진 인신계 킬레이트 수지의 조성, 인함량 및 우라늄이온 흡착량은 다음 표 1에 기재된 바와 같았다.Here, the dried reactant was oxidized at the concentration of 2% nitric acid solution per weight at the same time with hydrolysis at 80 ° C. for 20 hours. This was then vacuum dried at 60 ° C. for 48 hours to produce a yellow spherical chelate resin. The composition, phosphorus content and uranium ion adsorption amount of the obtained human phosphorus chelate resin were as shown in Table 1 below.
[표 1]TABLE 1
a 상기표에서, 우라늄이온의 흡착량은 pH=4.27, 21.2ppm 농도의 우라늄이온 용액 20ml에 0.2g의 시료를 넣고 28시간 교반후 용액의 농도차이로 계산함.a In the above table, the adsorption amount of uranium ion is calculated as the concentration difference of the solution after adding 0.2 g of sample to 20 ml of uranium ion solution of pH = 4.27, 21.2 ppm concentration and stirring for 28 hours.
b 공중합에 사용된 량은 전부 반응함 것으로 간주함.b All amounts used for copolymerization are considered to be reacted.
c 염소분석에 의해 계산함.c Calculated by chlorine analysis.
d 주쇄 및 측쇄에 대한 각 반응에서 얻어진 생성물의 조성은 그 반응 전후의 중량변화로부터 계산함.d The composition of the product obtained in each reaction for the main and side chains is calculated from the weight change before and after the reaction.
e 중량퍼센트임e weight percent
[비교예 1∼5]Comparative Examples 1 to 5
교반기가 있는 반응기에 스티렌, 디비닐벤젠 등을 넣고, 여기에다 중합개시제로는 과산화벤조일을 단위체들에 대해 0.2중량% 사용했으며, 단위체들 과의 수비(
현탁중합반응은 70℃에서 25시간 유지하여 생성된 중합반응물을 여과수세하였으며, 이것을 60℃가 유지된 진공건조기에서 48시간 건조시킨뒤 50/80메쉬(mesh)의 체(sieve)로 걸렀다.The suspension polymerization reaction was maintained at 70 ° C. for 25 hours, and the resulting polymerized product was washed with water. The resultant was dried for 48 hours in a vacuum dryer maintained at 60 ° C. and filtered through a 50/80 mesh sieve.
이후 공중합체 수지 기본골격의 측쇄인 페닐기에 대해 포스포노기의 도입을 위해 공중합체 수지 중량당 8중량비의 싸이클로헥산 용액중에서 0.25중량비의 염화알루미늄 촉매 존재하에 0.25중량비의 삼염화인을 70℃에서 30시간동안 반응시킨뒤 이 반응물을 여과분리후 물과 메탄올로 세척하고 건조하였다. 여기서 건조된 반응물은 단위중량당 2% 농도의 질산용액을 10중량비로 70℃에서 20시간동안 가수분해와 동시에 산화시켰다.Then, in order to introduce a phosphono group to the phenyl group, which is the side chain of the copolymer resin skeleton, a 0.25 weight ratio of phosphorus trichloride was added in an 8 weight ratio cyclohexane solution per weight of the copolymer resin in the presence of 0.25 weight ratio of aluminum chloride catalyst at 70 ° C for 30 hours. The reaction was filtered, washed with water and methanol and dried. Here, the dried reactant was oxidized at the concentration of 2% nitric acid solution per unit weight at the same time by hydrolysis at 70 ° C. for 20 hours.
그다음에는 이것을 60℃에서 48시간 동안 진공건조하여 황색의 구상 킬레이트 수지를 제조하였다. 얻어진 킬레이트 수지의 조성, 인함량 및 우라늄이온 흡착량은 표 2에 기재된 바와 같았다.This was then vacuum dried at 60 ° C. for 48 hours to produce a yellow spherical chelate resin. The composition, phosphorus content and uranium ion adsorption amount of the obtained chelate resin were as shown in Table 2.
[비교예 6∼10]Comparative Examples 6 to 10
교반기가 있는 반응기에 스티렌, 디비닐벤젠을 넣고, 여기에다 중합개시제로는 과산화벤조일을 단위체들에 대해 0.2중량% 사용했으며, 단위체들과의 수비(
현탁 중합반응은 70℃에서 25시간 유지하여 생성된 중합반응물을 여과수세하였으며, 이것을 60℃로 유지된 진공건조기에서 48시간 건조시킨뒤 50/80메쉬의 체(sieve)로 질렀다.The suspension polymerization was maintained at 70 ° C. for 25 hours, and the resulting polymerization product was filtered and washed with water. The resultant was dried for 48 hours in a vacuum dryer maintained at 60 ° C., and then sieved with a 50/80 mesh sieve.
그다음 공중합체 수지 기본골격의 측쇄인 페닐기에 대한 클로로메틸기를 도입시키기 위해 상기 공중합체 수지 중량당 10중량비의 싸이클로헥산 용액중에서 0.3중량비의 염화알루미늄 촉매 존재하에 1중량비의 클로로메틸 메틸에테르와 80℃에서 20시간 동안 반응시키고 난뒤 여과하고 50℃로 유지된 진공건조기에서 48시간 건조하였다.Then, in order to introduce chloromethyl group to the phenyl group, which is the side chain of the copolymer resin backbone, at 80 ° C with 1 part by weight of chloromethyl methyl ether in the presence of 0.3 part by weight of aluminum chloride catalyst in 10 parts by weight of cyclohexane solution After reacting for 20 hours, the mixture was filtered and dried for 48 hours in a vacuum dryer maintained at 50 ℃.
이후 공중합체 수지 기본골격의 측쇄인 클로로벤질기에 대해 포스포노기의 도입을 위해 공중합체 수지 중량당 8중량비의 싸이클로헥산 용액중에서 0.25중량비의 염화알루미늄 촉매존재하에 0.25중량비의 삼염화인을 80℃에서 30시간 동안 반응시키고 이 반응물을 여과분리후 물과 메탄올로 세척하고 건조하였다. 여기서 건조된 반응물은 중량당 2% 농도의 질산용액을 10중량비 사용하여 20시간 동안 가수분해와 동시에 산화시켰다. 그다음에는 이것을 60℃에서 48시간 동안 건조하여 노란색의 구상 킬레이트 수지를 제조하였다. 얻어진 인산계 킬레이트 수지의 조성, 인함량 및 우라늄이온 흡착량은 다음 표 2에 기재된 바와 같았다.Then, in order to introduce a phosphono group to the chlorobenzyl group, which is the side chain of the basic skeleton of the copolymer resin, a 0.25 weight ratio of phosphorus trichloride was added at 80 ° C in a presence of 0.25 weight ratio of aluminum chloride catalyst in an 8 weight ratio cyclohexane solution per copolymer resin weight. The reaction was carried out for a period of time and the reaction was filtered, washed with water and methanol and dried. Here, the dried reactant was oxidized simultaneously with hydrolysis for 20 hours using 10% by weight of a nitric acid solution at a concentration of 2% per weight. This was then dried at 60 ° C. for 48 hours to give a yellow spherical chelate resin. The composition, phosphorus content and uranium ion adsorption amount of the obtained phosphate chelate resin were as described in Table 2 below.
[표 2]TABLE 2
a 상기표에서, 우라늄이온의 흡착량은 pH=4.27, 21.2ppm 농도의 우라늄이온 용액 20ml에 0.2g의 시료를 넣고 28시간 교반후 용액의 농도차이로 계산함.a In the above table, the adsorption amount of uranium ion is calculated as the concentration difference of the solution after adding 0.2 g of sample to 20 ml of uranium ion solution of pH = 4.27, 21.2 ppm concentration and stirring for 28 hours.
b 공중합에 사용한 량은 전부 반응함 것으로 간주함.b All the amount used for copolymerization is considered to react.
c 염소분석에 의해 계산함.c Calculated by chlorine analysis.
d 주쇄 및 측쇄에 대한 각 반응에서 얻어진 생성물의 조성은 그 반응 전후의 중량 변화로부터 계산함.d The composition of the product obtained in each reaction for the main and side chains is calculated from the weight change before and after the reaction.
e 중량퍼센트임e weight percent
Claims (5)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900008342A KR930002701B1 (en) | 1990-06-07 | 1990-06-07 | Process for preparing phosphoric xylate resin for adsorbing uranium ion |
| JP3162437A JPH0692446B2 (en) | 1990-06-07 | 1991-06-07 | Method for producing phosphoric acid chelate resin for uranium ion adsorption |
| US08/224,057 US5489616A (en) | 1990-06-07 | 1993-04-07 | Process for manufacturing phosphoric acid-type chelate resin as uranyl ion absorbents |
| US08/160,128 US5457163A (en) | 1990-06-07 | 1993-11-30 | Phosphonic acid chelating resins for uranyl ion adsorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900008342A KR930002701B1 (en) | 1990-06-07 | 1990-06-07 | Process for preparing phosphoric xylate resin for adsorbing uranium ion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR920000812A KR920000812A (en) | 1992-01-29 |
| KR930002701B1 true KR930002701B1 (en) | 1993-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019900008342A KR930002701B1 (en) | 1990-06-07 | 1990-06-07 | Process for preparing phosphoric xylate resin for adsorbing uranium ion |
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| Country | Link |
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| JP (1) | JPH0692446B2 (en) |
| KR (1) | KR930002701B1 (en) |
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| JP6359879B2 (en) * | 2014-06-03 | 2018-07-18 | 丸善石油化学株式会社 | Process for producing polyvinylphosphonic acid |
| CN113527552B (en) * | 2021-07-08 | 2022-04-05 | 北京科技大学 | Chlorine ball modification method for modifying dialkyl phosphinic acid functional group |
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1990
- 1990-06-07 KR KR1019900008342A patent/KR930002701B1/en not_active IP Right Cessation
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| Publication number | Publication date |
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| JPH04239006A (en) | 1992-08-26 |
| KR920000812A (en) | 1992-01-29 |
| JPH0692446B2 (en) | 1994-11-16 |
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