JP2604008B2 - Iodine-substituted aromatic cross-linked polymer - Google Patents
Iodine-substituted aromatic cross-linked polymerInfo
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- JP2604008B2 JP2604008B2 JP16588188A JP16588188A JP2604008B2 JP 2604008 B2 JP2604008 B2 JP 2604008B2 JP 16588188 A JP16588188 A JP 16588188A JP 16588188 A JP16588188 A JP 16588188A JP 2604008 B2 JP2604008 B2 JP 2604008B2
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- iodine
- polymer
- crosslinking
- crosslinked polymer
- substituted aromatic
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Description
【発明の詳細な説明】 ［発明の目的］ （産業上の利用分野） 本発明は固形Ｘ線造影剤またはプラスチック用難燃剤
等として有用な高架橋度の沃素置換芳香族架橋重合体に
関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to an iodine-substituted aromatic crosslinked polymer having a high degree of crosslinking, which is useful as a solid X-ray contrast agent or a flame retardant for plastics.
（従来技術） 芳香族架橋重合体の沃素化に関しては、例えば、スチ
レンとジビニルベンゼンの架橋重合体を沃素化したもの
が記載されている（工業化学雑誌、第64巻、第１号（19
61）232〜235頁）。しかし、この技術ではジビニルベン
ゼンの使用量が少ないため、得られる架橋重合体は架橋
度が非常に低いものである。(Prior Art) Regarding iodination of an aromatic cross-linked polymer, for example, a product obtained by iodinating a cross-linked polymer of styrene and divinylbenzene is described (Industrial Chemistry Magazine, Vol. 64, No. 1, (19)
61) p.232-235). However, since the amount of divinylbenzene used in this technique is small, the resulting crosslinked polymer has a very low degree of crosslinking.
［発明の構成］ （問題を解決するための手段） 本発明の高架橋度の沃素置換芳香族架橋重合体は、芳
香族ビニルモノマーと２官能性以上の芳香族ビニルモノ
マーとを共重合させて得られた重合体を沃素化した高架
橋度の沃素置換芳香族架橋重合体であって、架橋度が５
％以上であり、沃素含有率が１〜70重量％であることを
特徴とする。[Constitution of the Invention] (Means for Solving the Problem) The iodine-substituted aromatic cross-linked polymer having a high degree of cross-linking of the present invention is obtained by copolymerizing an aromatic vinyl monomer and a bifunctional or higher aromatic vinyl monomer. A highly crosslinked iodine-substituted aromatic crosslinked polymer having a degree of crosslinking of 5
% Or more, and the iodine content is 1 to 70% by weight.
本発明の高架橋度の沃素置換芳香族架橋重合体の沃素
の置換位置は、特に制限されるものではない。この沃素
含有率は、JIS Ｋ−6388に規定されている酸素フラス
コ燃焼法に準じて、試料重合体を燃焼させ、吸収液につ
いてイオンクロマトグラフィーにより定量される値であ
る。The iodine substitution position of the iodine-substituted aromatic crosslinked polymer having a high degree of crosslinking of the present invention is not particularly limited. This iodine content is a value determined by burning a sample polymer and ion-chromatography of an absorbing solution in accordance with the oxygen flask combustion method defined in JIS K-6388.
高架橋度の沃素置換芳香族架橋重合体の沃素含有率が
１重量％未満であると、Ｘ線造影剤として適用した場合
に造影効果が不十分であり、70重量％を超えると、その
製造に際して高温で長時間反応させる必要があり、それ
にともない、沃素化剤として用いた塩化沃素が分解した
り、生成した重合体の化学安定性を低下させる副反応が
生じるために好ましくない。If the iodine content of the iodine-substituted aromatic cross-linked polymer having a high degree of cross-linking is less than 1% by weight, the contrast effect is insufficient when applied as an X-ray contrast agent. It is necessary to carry out the reaction at a high temperature for a long period of time, which is not preferable because iodine chloride used as an iodination agent is decomposed or a side reaction occurs which lowers the chemical stability of the produced polymer.
本発明の高架橋度の沃素置換芳香族架橋重合体の沃素
含有率は、上限が70重量％の範囲内で、好ましくは５重
量％以上であり、さらに好ましくは20重量％以上であ
り、最も好ましくは30重量％以上である。The iodine content of the highly crosslinked iodine-substituted aromatic crosslinked polymer of the present invention has an upper limit of 70% by weight, preferably 5% by weight or more, more preferably 20% by weight or more, and most preferably. Is 30% by weight or more.
本発明の芳香族架橋重合体の架橋度が５％以上である
ことが必要である理由は、低架橋度の芳香族架橋重合体
を沃素化した場合は、沃素置換芳香族架橋重合体中に僅
かに溶媒に抽出される副生物が生成し、これを完全に除
去することが困難であるため、固形Ｘ線造影剤の安全性
が低下するためである。こうした副生物が生成しないよ
うにするためには、芳香族架橋重合体の架橋度は５％以
上であることが必要であり、更に架橋度が８％以上であ
ることが好ましく、さらに好ましくは８〜20％である。
また芳香族架橋重合体の架橋度があまりに高い場合に
は、芳香族架橋重合体を沃素化する反応が困難になり、
所望の沃素含有率の沃素置換芳香族架橋重合体を得るこ
とができず、重合体の精製、粉砕も困難になるので好ま
しくない。The reason that the degree of crosslinking of the aromatic crosslinked polymer of the present invention is required to be 5% or more is that when the aromatic crosslinked polymer having a low degree of crosslinking is iodinated, the iodine-substituted aromatic crosslinked polymer has This is because by-products slightly extracted by the solvent are generated, and it is difficult to completely remove the by-products, so that the safety of the solid X-ray contrast agent is reduced. In order to prevent such by-products from being generated, the degree of crosslinking of the aromatic cross-linked polymer needs to be 5% or more, more preferably 8% or more, more preferably 8% or more. ~ 20%.
If the degree of crosslinking of the aromatic cross-linked polymer is too high, the reaction of iodinating the aromatic cross-linked polymer becomes difficult,
It is not preferable because an iodine-substituted aromatic crosslinked polymer having a desired iodine content cannot be obtained, and purification and pulverization of the polymer become difficult.
本発明で用いる芳香族架橋重合体の製造に用いる芳香
族ビニルモノマーとしては、スチレン、ビニルトルレ
ン、ビニルナフタレンなどを例示することができる。Examples of the aromatic vinyl monomer used in the production of the aromatic cross-linked polymer used in the present invention include styrene, vinyltoluene, and vinylnaphthalene.
本発明で用いる２官能性以上の芳香族ビニルモノマー
としては、ジビニルベンゼン、トリビニルベンゼン、ジ
ビニルトルエン、ジビニルジフェニルエーテル、エチレ
ングリコールジメタクリレート、トリメチロールプロパ
ントリメタクリレートなどを例示することができる。Examples of the bifunctional or higher aromatic vinyl monomer used in the present invention include divinylbenzene, trivinylbenzene, divinyltoluene, divinyldiphenylether, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate.
芳香族ビニルモノマーと２官能性以上の芳香族ビニル
モノマーとを共重合させる方法は、特に制限されるもの
ではなく、公知の重合方法を適用することができる。The method for copolymerizing the aromatic vinyl monomer and the bifunctional or higher aromatic vinyl monomer is not particularly limited, and a known polymerization method can be applied.
重合反応時には、過酸化ベンゾイル、アルキルヒドロ
キシペルオキシド、過酸化ジアルキル、過酸化アセチル
などの重合触媒、トルエン、デドカン、ヘキサン、ヘプ
タン、ブタノール、線状芳香族重合体などの多孔質化剤
などを併用することができる。At the time of the polymerization reaction, a polymerization catalyst such as benzoyl peroxide, alkylhydroxy peroxide, dialkyl peroxide, or acetyl peroxide, and a porous agent such as toluene, dedocan, hexane, heptane, butanol, or a linear aromatic polymer are used in combination. be able to.
本発明で用いる高架橋度の芳香族重合体としては、ス
チレンとジビニルベンゼンから得られる架橋重合体は本
発明の目的を特に有利に達成するため好ましい。As the aromatic polymer having a high degree of crosslinking used in the present invention, a crosslinked polymer obtained from styrene and divinylbenzene is preferable because the object of the present invention is particularly advantageously achieved.
本発明の高架橋度の芳香族架橋重合体を得るには、芳
香族ビニルモノマーと２官能性以上の芳香族ビニルモノ
マーの使用量を調節することにより達成される。すなわ
ち、芳香族ビニルモノマー95モル％以下に対し、２官能
性以上の芳香族ビニルモノマー５モル％以上とすること
により、本発明の目的とする架橋度５％以上の芳香族架
橋重合体が得られる。更に、芳香族ビニルモノマー80〜
92モル％に対し、２官能性以上の芳香族ビニルモノマー
８〜20モル％とすることにより、本発明において好まし
い架橋度８〜20％の芳香族架橋重合体が得られる。The aromatic crosslinked polymer having a high degree of crosslinking of the present invention can be obtained by controlling the amounts of the aromatic vinyl monomer and the bifunctional or higher aromatic vinyl monomer. That is, the aromatic cross-linked polymer having a cross-linking degree of 5% or more, which is the object of the present invention, can be obtained by adjusting the aromatic vinyl monomer having a bifunctionality of 5 mol% or more to 95 mol% or less of the aromatic vinyl monomer. Can be Furthermore, aromatic vinyl monomer 80 ~
By setting the bifunctional or more aromatic vinyl monomer to 8 to 20 mol% with respect to 92 mol%, an aromatic cross-linked polymer having a preferable degree of cross-linking of 8 to 20% in the present invention can be obtained.
本発明の高架橋度の沃素置換芳香族重合体は、高架橋
度の芳香族架橋重合体を沃素化して、沃素を置換させる
ことにより達成される。高架橋度の芳香族架橋重合体を
沃素化する方法としては、公知の沃素化反応を採用する
ことができる。すなわち、高架橋度の芳香族架橋重合体
に反応溶媒中で塩化沃素を作用させる方法、または五酸
化沃素のような酸化剤の存在下に沃素を作用させる方法
等である。これらの方法中で、塩化沃素を作用させる方
法は、沃素含有率の高い沃素置換芳香族架橋重合体を得
るのにより好ましい方法である。The iodine-substituted aromatic polymer having a high degree of crosslinking of the present invention is achieved by iodinating an aromatic crosslinked polymer having a high degree of crosslinking to substitute iodine. As a method for iodinating the aromatic crosslinked polymer having a high degree of crosslinking, a known iodination reaction can be employed. That is, a method in which iodine chloride is allowed to act on a highly crosslinked aromatic crosslinked polymer in a reaction solvent, or a method in which iodine is caused to act in the presence of an oxidizing agent such as iodine pentoxide. Among these methods, the method of reacting with iodine chloride is a more preferable method for obtaining an iodine-substituted aromatic crosslinked polymer having a high iodine content.
使用する反応溶媒としては、塩化沃素を作用させる場
合は、四塩化炭素、ジクロルエタン、トリクロルエタン
など、五酸化沃素の存在下に沃素を作用させる場合は、
ニトロベンゼンなどを例示することができる。As a reaction solvent to be used, when iodine chloride is allowed to act, carbon tetrachloride, dichloroethane, trichloroethane, and the like, when iodine is caused to act in the presence of iodine pentoxide,
Examples thereof include nitrobenzene.
反応温度は０℃以上、好ましくは60℃以上で、かつ溶
媒の還流温度以下の温度で反応を行うことが好ましい。
反応温度があまり低いと反応速度が低下するため好まし
くない。The reaction is preferably carried out at a temperature of at least 0 ° C., preferably at least 60 ° C., and at most the reflux temperature of the solvent.
If the reaction temperature is too low, the reaction rate decreases, which is not preferable.
沃素化反応後に、必要に応じて反応系に残存する沃素
化剤および触媒などを水またはNaOH、KOH、Na2CO3、NaO
CH3、などのアルカリ水溶液で分解除去する工程、自然
過、フィルタープレス、減圧過、カラム洗浄などの
方法により単離する工程、粉砕処理工程および乾燥工程
などの処理を施すことにより、本発明の高架橋度の沃素
置換芳香族架橋重合体を得ることができる。After the iodination reaction, if necessary, the iodination agent and catalyst remaining in the reaction system are replaced with water or NaOH, KOH, Na 2 CO 3 , NaO
CH 3 , etc., by subjecting it to a process of decomposing and removing with an aqueous alkaline solution, a natural process, a filter press, a vacuum process, a process of isolation by a method such as column washing, a crushing process and a drying process. An iodine-substituted aromatic crosslinked polymer having a high degree of crosslinking can be obtained.
沃素置換芳香族架橋重合体の製造方法について、あら
かじめ沃素化された沃素置換線状重合体もしくは沃素置
換芳香族ビニル単量体を用いて、これらの間に交叉結合
を形成させて沃素置換芳香族架橋重合体をうる方法で
は、目的とする沃素置換芳香族架橋重合体の収率が低い
ため工業的製造方法としては問題があり、更に得られる
架橋重合体の架橋反応における架橋度の調節が困難であ
ることから、本発明の高架橋度の芳香族架橋重合体を沃
素化する方法は工業的な有用性が大きい。Regarding the method for producing the iodine-substituted aromatic crosslinked polymer, an iodine-substituted aromatic polymer is prepared by using a pre-iodinated iodine-substituted linear polymer or an iodine-substituted aromatic vinyl monomer to form a cross bond therebetween. In the method for obtaining a crosslinked polymer, there is a problem as an industrial production method because the yield of the objective iodine-substituted aromatic crosslinked polymer is low, and it is difficult to control the degree of crosslinking in the crosslinking reaction of the resulting crosslinked polymer. Therefore, the method of iodinating the aromatic crosslinked polymer having a high degree of crosslinking of the present invention has great industrial utility.
（実施例） 以下、実施例により本発明を更に詳細に説明するが、
本発明はこれらの実施例によって何ら限定されるもので
はない。(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited by these examples.
なお、本発明の高架橋度の沃素置換架橋重合体中の沃
素含有率の分析は、次の方法により行った。The iodine content in the iodine-substituted crosslinked polymer having a high degree of crosslinking of the present invention was analyzed by the following method.
沃素含有率の分析 まず試料0.01gを無灰紙に包み、0.01％過酸化水素
水を吸収液とし、酸素を満たした燃焼フラスコ中で燃焼
させた。その後吸収液を0.1NのKOH水溶液で中和し、100
mlにメスアップしたものを試料溶液とした。この溶液10
0μをイオンクロマトグラフィーのカラム（東ソー、C
CPDシステム）に注入し、そのピーク面積と予め作成し
ておいた検量線から、試料溶液中の沃素イオンを定量し
た。Analysis of iodine content First, 0.01 g of a sample was wrapped in ashless paper, and was burned in a combustion flask filled with oxygen using 0.01% hydrogen peroxide as an absorbing solution. After that, the absorbing solution was neutralized with a 0.1N aqueous KOH solution,
The sample solution was made up to a volume of ml and used as a sample solution. This solution 10
0μ is an ion chromatography column (Tosoh, C
CPD system) and iodine ions in the sample solution were quantified from the peak area and a previously prepared calibration curve.
実施例１ まず、水500mlおよびポリビニルアルコール1gを反応
器にとり、撹拌しながら80〜90℃に加熱した。これに予
め準備しておいたスチレン10g、ジビニルベンゼン1g、
トルエン5g、ドデカン5gおよび過酸化ベンゾイル0.2gの
混合溶液を添加し、80〜90℃で激しく撹拌を行った。そ
の後、24時間重合を続けたのち、ろ過、熱水洗浄、乾燥
処理を経て、スチレン単位からなる重合体がジビニルベ
ンゼン単位で架橋結合された10gの高架橋度の架橋重合
体を得た（架橋度９％）。Example 1 First, 500 ml of water and 1 g of polyvinyl alcohol were placed in a reactor and heated to 80 to 90 ° C. with stirring. 10 g of styrene and 1 g of divinyl benzene prepared in advance
A mixed solution of 5 g of toluene, 5 g of dodecane and 0.2 g of benzoyl peroxide was added, and vigorously stirred at 80 to 90 ° C. Thereafter, polymerization was continued for 24 hours, followed by filtration, washing with hot water, and drying treatment to obtain 10 g of a crosslinked polymer having a high degree of crosslinking in which a polymer composed of styrene units was crosslinked with divinylbenzene units (crosslinking degree). 9%).
次に、高架橋度の架橋重合体25gおよびジクロルエタ
ン100mlからなる懸濁液を室温下で撹拌しながら、これ
に一塩化沃素75gを60分かけて添加した。その後、一塩
化沃素の添加が終了したのち、還流下２時間反応させ
た。次いで、水40ml、続いて48％NaOH水溶液60gを加え
て中和した。その後、生成した高架橋度の沃素置換芳香
族架橋重合体をろ過し、ジクロルエタンによる洗浄、さ
らに乾燥、粉砕処理を経て、沃素含有率52重量％の本発
明の高架橋度の沃素置換芳香族架橋重合体49gを得た
（以下、沃素置換架橋重合体１と略記する）。Next, 75 g of iodine monochloride was added thereto over 60 minutes while stirring a suspension comprising 25 g of a crosslinked polymer having a high degree of crosslinking and 100 ml of dichloroethane at room temperature. Thereafter, after the addition of iodine monochloride was completed, the reaction was carried out under reflux for 2 hours. Then, the mixture was neutralized by adding 40 ml of water and subsequently 60 g of a 48% aqueous NaOH solution. Thereafter, the resulting high-cross-linked iodine-substituted aromatic crosslinked polymer having a high degree of cross-linking is filtered, washed with dichloroethane, further dried and pulverized to obtain a highly cross-linked iodine-substituted aromatic cross-linked polymer of the present invention having an iodine content of 52% by weight. 49 g (hereinafter abbreviated as iodine-substituted crosslinked polymer 1) was obtained.
実施例２ 多孔質化剤であるトルエンおよびドデカンを添加しな
かったことを除いては、実施例１の場合と全く同一の方
法により10gの高架橋度の架橋重合体を得た（架橋度９
％）。Example 2 10 g of a crosslinked polymer having a high degree of crosslinking was obtained in exactly the same manner as in Example 1 except that the porous agents toluene and dodecane were not added (degree of crosslinking 9).
%).
この高架橋度の架橋重合体を25g用いたことを除いて
は、実施例１の方法と同一の方法により、沃素含有率62
重量％の本発明の高架橋度の沃素置換芳香族架橋重合体
55gを得た（以下、沃素置換架橋重合体２と略記す
る）。An iodine content of 62% was obtained in the same manner as in Example 1 except that 25 g of the crosslinked polymer having a high degree of crosslinking was used.
% By weight of the highly crosslinked iodine-substituted aromatic crosslinked polymer of the present invention
55 g was obtained (hereinafter abbreviated as iodine-substituted crosslinked polymer 2).
実施例３ 実施例１の高架橋度の架橋重合体が25g、ニトロベン
ゼン100mlからなる懸濁液を90℃で撹拌しながら、これ
に予め調製しておいた沃素20g、五酸化沃素10g、四塩化
炭素30mlおよび50％硫酸60mlからなる溶液を60分で添加
した。その後90℃で十時間反応させた。次いで、水100m
lを加えて、水層と有機層を分離した。その後、有機層
は30％NaOH水溶液で洗浄し、さらに乾燥、粉砕処理を経
て、沃素含有率42重量％の高架橋度の沃素置換芳香族架
橋重合体41gを得た（以下、沃素置換架橋重合体３と略
記する）。Example 3 While stirring a suspension composed of 25 g of the highly crosslinked polymer of Example 1 and 100 ml of nitrobenzene at 90 ° C., 20 g of iodine prepared in advance, 10 g of iodine pentoxide, and carbon tetrachloride were added thereto. A solution consisting of 30 ml and 60 ml of 50% sulfuric acid was added in 60 minutes. Thereafter, the reaction was carried out at 90 ° C. for 10 hours. Then, 100m of water
l was added and the aqueous and organic layers were separated. Thereafter, the organic layer was washed with a 30% aqueous NaOH solution, dried and pulverized to obtain 41 g of an iodine-substituted aromatic cross-linked polymer having a high degree of cross-linking with an iodine content of 42% by weight (hereinafter, iodine-substituted cross-linked polymer). 3).
実施例４ 実施例２の高架橋度の架橋重合体２が25gであること
を除いては、実施例３と同一の方法により、沃素含有率
45重量％の高架橋度の沃素置換芳香族架橋重合体43gを
得た（以下、沃素置換架橋重合体４と略記する）。Example 4 An iodine content was obtained in the same manner as in Example 3 except that the amount of the highly crosslinked polymer 2 of Example 2 was 25 g.
43 g of an iodine-substituted aromatic crosslinked polymer having a high degree of crosslinking of 45% by weight was obtained (hereinafter abbreviated as iodine-substituted crosslinked polymer 4).
実施例５ スチレン10gに対し、ジビニルベンゼン0.6gであるこ
とを除いては、実施例１と同一の方法により、9.8gの高
架橋度の架橋重合体を得た（架橋度5.5％）。Example 5 9.8 g of a crosslinked polymer having a high degree of crosslinking was obtained in the same manner as in Example 1 except that 0.6 g of divinylbenzene was used for 10 g of styrene (5.5% of crosslinking).
この高架橋度の架橋重合体を25g用いたことを除いて
は、実施例１と同一の方法により、沃素含有率63重量％
の本発明の高架橋度の沃素置換芳香族架橋重合体56gを
得た（以下、沃素置換架橋重合体５と略記する）。An iodine content of 63% by weight was obtained in the same manner as in Example 1 except that 25 g of the crosslinked polymer having a high degree of crosslinking was used.
Thus, 56 g of an iodine-substituted aromatic crosslinked polymer having a high degree of crosslinking of the present invention was obtained (hereinafter abbreviated as iodine-substituted crosslinked polymer 5).
比較例１ （低架橋度の沃素置換芳香族重合体の合成） スチレン10gに対し、ジビニルベンゼン0.4gであるこ
とを除いては、実施例１と同一の方法により9.5gの低架
橋度の架橋重合体を得た（架橋度3.7％）。Comparative Example 1 (Synthesis of low-crosslinking iodine-substituted aromatic polymer) 9.5 g of low-crosslinking crosslinked polymer was obtained in the same manner as in Example 1 except that divinylbenzene was 0.4 g per 10 g of styrene. A polymer was obtained (3.7% degree of crosslinking).
この低架橋度の架橋重合体を25g用いたことを除いて
は、実施例１と同一の方法により、沃素含有率64重量％
の低架橋度の沃素置換芳香族架橋重合体48gを得た（以
下、比較例１重合体と略記する）。An iodine content of 64% by weight was obtained in the same manner as in Example 1 except that 25 g of the crosslinked polymer having a low degree of crosslinking was used.
Thus, 48 g of an iodine-substituted aromatic crosslinked polymer having a low degree of crosslinking was obtained (hereinafter abbreviated as a polymer of Comparative Example 1).
比較例２ （沃素置換芳香族ビニル単量体を用いた沃素置換芳香族
架橋重合体の合成） 水500mlとポリビニルアルコール1gとを反応器にと
り、撹拌しながら80〜90℃に加熱し、これに予め準備し
ておいたパラヨードスチレン20g、ジビニルベンゼン2g
および過酸化ベンゾイル0.2gの混合溶液を添加した。次
に、80〜90℃で激しく撹拌を行い、24時間重合を続けた
のち、生成した固形物を、ろ過し、熱水洗浄、ジクロル
エタンによる洗浄、さらに乾燥粉砕処理を経て、沃素含
有率55重量％の沃素置換芳香族架橋重合体10gを得た。Comparative Example 2 (Synthesis of Crosslinked Iodine-Substituted Aromatic Polymer Using Iodine-Substituted Aromatic Vinyl Monomer) 500 ml of water and 1 g of polyvinyl alcohol were placed in a reactor and heated to 80 to 90 ° C. while stirring. 20 g of paraiodostyrene and 2 g of divinylbenzene prepared in advance
And a mixed solution of 0.2 g of benzoyl peroxide. Next, the mixture was vigorously stirred at 80 to 90 ° C., and polymerization was continued for 24 hours. After that, the resulting solid was filtered, washed with hot water, washed with dichloroethane, and further subjected to dry pulverization to obtain an iodine content of 55% by weight. % Of iodine-substituted aromatic crosslinked polymer was obtained.
比較試験（高架橋度及び低架橋度沃素置換芳香族架橋重
合体を用いた溶出成分試験） 以上の実施例１〜５で合成した本発明の高架橋度の沃
素置換芳香族架橋重合体および比較例1,2において合成
した２種の沃素置換芳香族重合体を用い、有機溶媒によ
る定性的な抽出試験を行った。Comparative test (elution component test using iodine-substituted aromatic cross-linked polymer with high and low cross-linking degree) Highly cross-linked iodine-substituted aromatic cross-linked polymer of the present invention synthesized in Examples 1 to 5 and Comparative Example 1 A qualitative extraction test with an organic solvent was performed using the two kinds of iodine-substituted aromatic polymers synthesized in Examples 2 and 3.
有機溶媒としては、95％エタノールとジクロルエタン
を用いて抽出を行った。抽出は、沃素置換芳香族架橋重
合体5gに対し抽出用溶媒10gを比色管に入れた後、これ
を振とう機により10分間振とうした後、抽出液につい
て、分光光度計により550〜330nmにおける紫外可視領域
の吸収の有無を測定し、その結果を比較した。Extraction was performed using 95% ethanol and dichloroethane as organic solvents. Extraction, after 5 g of iodine-substituted aromatic cross-linked polymer 5 g of extraction solvent was placed in a colorimetric tube, this was shaken for 10 minutes with a shaker, and the extract was subjected to a spectrophotometer at 550 to 330 nm. The presence or absence of absorption in the ultraviolet and visible regions was measured, and the results were compared.
その結果を下表にまとめた（上記の紫外可視領域にお
いて、−は抽出物による吸収を認められなかったこと、
±はこん跡程度の吸収が認められること、＋は明確な吸
収が認められたことを表す）。The results are summarized in the following table (in the above ultraviolet-visible region,-indicates that no absorption by the extract was observed,
± indicates that a trace of absorption was observed, and + indicates that a clear absorption was observed).
［発明の効果］ 本発明の高架橋度の沃素置換芳香族架橋重合体は、優
れたＸ線造影効果を有するものである。 [Effect of the Invention] The iodine-substituted aromatic crosslinked polymer having a high degree of crosslinking of the present invention has an excellent X-ray contrast effect.
さらに高架橋度であることから、強固な三次元構造を
有し、その特有の不溶性および不融性の効果が強く発揮
されるために、Ｘ線造影剤として使用した場合にも安全
性が高い。また該重合体はプラスチック用難燃剤とし
て、さらに各種の官能基を導入した高架橋度の芳香族架
橋重合体を形成させるための反応性中間体としても有用
である。Furthermore, since it has a high degree of cross-linking, it has a strong three-dimensional structure, and its unique insolubility and infusibility effects are strongly exhibited, so that it is highly safe even when used as an X-ray contrast agent. The polymer is also useful as a flame retardant for plastics and as a reactive intermediate for forming an aromatic crosslinked polymer having a high degree of crosslinking into which various functional groups are introduced.
Claims (1)
香族ビニルモノマーとを共重合させて得られた重合体を
沃素化した高架橋度の沃素置換芳香族架橋重合体であっ
て、架橋度が５％以上であり、沃素含有率が１〜70重量
％であることを特徴とする高架橋度の沃素置換芳香族架
橋重合体。1. An iodine-substituted aromatic cross-linked polymer having a high degree of crosslinking obtained by iodinating a polymer obtained by copolymerizing an aromatic vinyl monomer and an aromatic vinyl monomer having two or more functional groups. Is 5% or more, and the iodine content is 1 to 70% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16588188A JP2604008B2 (en) | 1988-07-05 | 1988-07-05 | Iodine-substituted aromatic cross-linked polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16588188A JP2604008B2 (en) | 1988-07-05 | 1988-07-05 | Iodine-substituted aromatic cross-linked polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0216102A JPH0216102A (en) | 1990-01-19 |
| JP2604008B2 true JP2604008B2 (en) | 1997-04-23 |
Family
ID=15820753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16588188A Expired - Lifetime JP2604008B2 (en) | 1988-07-05 | 1988-07-05 | Iodine-substituted aromatic cross-linked polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2604008B2 (en) |
-
1988
- 1988-07-05 JP JP16588188A patent/JP2604008B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0216102A (en) | 1990-01-19 |
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