JPH06228225A - Production of crosslinked polymer particle - Google Patents
Production of crosslinked polymer particleInfo
- Publication number
- JPH06228225A JPH06228225A JP5016684A JP1668493A JPH06228225A JP H06228225 A JPH06228225 A JP H06228225A JP 5016684 A JP5016684 A JP 5016684A JP 1668493 A JP1668493 A JP 1668493A JP H06228225 A JPH06228225 A JP H06228225A
- Authority
- JP
- Japan
- Prior art keywords
- group
- crosslinked polymer
- functional group
- particles
- polymer particles
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
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
- C08F8/00—Chemical modification by after-treatment
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は液体クロマトグラフィー
の充てん剤またはその基材等として好適な架橋重合体粒
子の製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing crosslinked polymer particles suitable as a packing material for liquid chromatography or a base material thereof.
【０００２】[0002]
【従来の技術】一般に、ポリマー粒子の重合法は乳化重
合法（この中の一態様にソープフリー重合がある）、分
散重合法、懸濁重合法に大別される。これらの内、乳化
重合法、分散重合法によれば、得られるポリマ粒子の粒
径分布は比較的狭いものとなり、また、懸濁重合法では
粒径分布が非常に広いものとなる。2. Description of the Related Art Generally, the polymerization method of polymer particles is roughly classified into an emulsion polymerization method (soap-free polymerization is one mode among them), a dispersion polymerization method and a suspension polymerization method. Among them, according to the emulsion polymerization method and the dispersion polymerization method, the particle size distribution of polymer particles obtained is relatively narrow, and the suspension polymerization method has a very wide particle size distribution.
【０００３】ところで、硬度、強度、耐熱性あるいは耐
溶剤性に優れた重合体粒子を得るためには架橋性のモノ
マーを相当の割合で含有するモノマー溶液を重合して架
橋重合体粒子とすればよい。懸濁重合法によって架橋性
モノマーを多量に含有する重合性モノマーを重合する場
合には重合安定性には特に問題は無いが、粒径コントロ
ールが困難であり粒径分布が広くなり、架橋した粒径分
布の狭い重合体粒子は得られない。By the way, in order to obtain polymer particles excellent in hardness, strength, heat resistance or solvent resistance, a monomer solution containing a crosslinkable monomer in a considerable ratio is polymerized to form crosslinked polymer particles. Good. When polymerizing a polymerizable monomer containing a large amount of a crosslinkable monomer by the suspension polymerization method, there is no particular problem with the polymerization stability, but it is difficult to control the particle size and the particle size distribution becomes wider, resulting in crosslinked particles. Polymer particles having a narrow size distribution cannot be obtained.
【０００４】また、従来公知の乳化重合法や分散重合法
によって架橋重合体を製造する場合においては、モノマ
ー溶液中の架橋性モノマーの割合が、５モル％以上にな
ると重合反応系の安定性が非常に悪くなり、このため多
量の凝集物が生成し、架橋重合体粒子の製造効率がきわ
めて低くなる。また、重合中にモノマーが粒子核に吸収
されず固形化（ゲル化）したり、所望しない微粒子が生
成する。したがって、これらの方法では実際上、粒度分
布の狭い架橋した真球状の重合体粒子は製造することが
出来ないという問題点がある。Further, in the case of producing a crosslinked polymer by a conventionally known emulsion polymerization method or dispersion polymerization method, the stability of the polymerization reaction system is improved when the proportion of the crosslinkable monomer in the monomer solution is 5 mol% or more. It becomes very bad, and thus a large amount of aggregates are formed, and the production efficiency of the crosslinked polymer particles becomes extremely low. Further, during the polymerization, the monomer is not absorbed by the particle nuclei and solidifies (gels), or undesired fine particles are generated. Therefore, these methods have a problem in that crosslinked true spherical polymer particles having a narrow particle size distribution cannot be practically produced.
【０００５】このため、乳化重合や分散重合で合成した
粒径分布の狭い非架橋又は低架橋（架橋率３％以下）粒
子を基（種粒子）に架橋性モノマーを吸収させシード重
合法により架橋した例がある（特開昭６３−１８９４１
３、特開平３−８２９６３のように）。しかしながらこ
れらは、種粒子への架橋性モノマーの吸収に時間がかか
り、種粒子に比べ粒径が大きくなり、また、未吸収の架
橋モノマーが所望しない微粒子を作ったり、膨潤粒子同
士が合一し、粗大粒子を生じ易く、粒径分布が大きくな
る等の欠点がある。Therefore, non-crosslinked or low-crosslinked (crosslinking ratio of 3% or less) particles having a narrow particle size distribution synthesized by emulsion polymerization or dispersion polymerization are used as a base (seed particles) to absorb a crosslinkable monomer and crosslinked by a seed polymerization method. There is an example (Japanese Patent Laid-Open No. 63-18941).
3, as in JP-A-3-82963). However, in these, it takes time to absorb the crosslinkable monomer into the seed particles, the particle size becomes larger than that of the seed particles, and the unabsorbed crosslinkable monomer forms undesired fine particles, or the swollen particles coalesce with each other. However, there are drawbacks such that coarse particles are easily generated and the particle size distribution becomes large.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記従来技術
の問題点を解決し、種粒子に対する吸収時間が短く、粒
径が種粒子とほとんど変わりなく、粒径分布が種粒子と
同様に狭く、所望しない微粒子を生成せずに架橋重合体
の粒子を効率よく合成できる架橋重合体粒子の製造法を
提供するものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, that is, the absorption time for seed particles is short, the particle size is almost the same as the seed particles, and the particle size distribution is as narrow as the seed particles. The present invention provides a method for producing crosslinked polymer particles, which enables efficient synthesis of crosslinked polymer particles without producing undesired fine particles.
【０００７】[0007]
【課題を解決するための手段】本発明は、一般式（Ｉ）
で示されるモノマーを５モル％以上含有するモノマー溶
液を乳化重合法、分散重合法又はソープフリー重合で重
合して、非架橋の重合体粒子とし、前記粒子の有する官
能基Ｘと反応する官能基を二つ以上含む化合物により、
前記粒子を架橋する架橋重合体粒子の製造法The present invention has the general formula (I)
A functional group which reacts with the functional group X contained in the non-crosslinked polymer particles by polymerizing a monomer solution containing 5 mol% or more of the monomer represented by the above-mentioned by emulsion polymerization method, dispersion polymerization method or soap-free polymerization. Depending on the compound containing two or more,
Process for producing crosslinked polymer particles for crosslinking the particles
【化２】 （式中、Ｘは官能基を表し、Ｒ1、Ｒ2及びＲ3は各々独
立して一価の有機基を表し、Ｙは２価の有機基を表わす
か、Ｙは含まれずＸが直接炭素原子に結合していてもよ
い）に関する。[Chemical 2] (In the formula, X represents a functional group, R 1 , R 2 and R 3 each independently represent a monovalent organic group, Y represents a divalent organic group, or Y is not included and X is directly Optionally bonded to a carbon atom).
【０００８】以下、本発明を更に詳細に説明する。一般
式（Ｉ）におけるＸの官能基としては、反応性基であれ
ば特に制限はないが、例えば、Ｃｌ、Ｂｒ等のハロゲン
類、カルボキシル基、−ＮＨ2、＝ＮＨ等のアミノ基、
水酸基、グリシジル基などが挙げられる。これらのう
ち、グリシジル基が好ましい。The present invention will be described in more detail below. The functional group of X in the general formula (I) is not particularly limited as long as it is a reactive group, for example, halogens such as Cl and Br, a carboxyl group, an amino group such as —NH 2 , ═NH,
Examples thereof include a hydroxyl group and a glycidyl group. Of these, a glycidyl group is preferred.
【０００９】一般式（Ｉ）におけるＲ1、Ｒ2及びＲ3と
しては１価の有機基であれば特に制限はないが、例え
ば、水素原子、アルキル基、アリール基等が挙げられ
る。また、Ｙとしては２価の有機基であれば特に制限が
なく、例えば、エーテル結合、エステル結合等が挙げら
れる。なお、場合によってはＹがなく、Ｘが直接炭素原
子に結合していてもよい。R 1 , R 2 and R 3 in the general formula (I) are not particularly limited as long as they are monovalent organic groups, and examples thereof include a hydrogen atom, an alkyl group and an aryl group. Further, Y is not particularly limited as long as it is a divalent organic group, and examples thereof include an ether bond and an ester bond. In some cases, Y may be absent and X may be directly bonded to a carbon atom.
【００１０】本発明においては、一般式（Ｉ）で示され
るモノマーを５モル％以上含有するモノマー溶液を用い
ることが必要である。５モル％未満であると架橋性が不
足する。モノマー溶液には、必要に応じて一般式（Ｉ）
で示されるモノマー以外のモノマーを用いてもよいが、
そのようなモノマーとしては特に制限はなく、一般式
（Ｉ）で示されるモノマーと均一に溶解し、官能基Ｘと
反応する官能基を持たないラジカル重合性モノマーであ
ればよい。In the present invention, it is necessary to use a monomer solution containing 5 mol% or more of the monomer represented by the general formula (I). If it is less than 5 mol%, the crosslinkability will be insufficient. If necessary, the monomer solution may have the general formula (I)
Although a monomer other than the monomer shown by may be used,
The monomer is not particularly limited and may be a radical-polymerizable monomer that does not have a functional group that dissolves uniformly with the monomer represented by the general formula (I) and that reacts with the functional group X.
【００１１】重合法は、乳化重合法、分散重合法又はソ
ープフリー重合法が用いられる。一般に、乳化重合法は
多量の乳化剤でミセルを形成して油滴を安定化し、水溶
性開始剤の存在下重合を行うものであり、ソープフリー
重合法とは乳化剤無しに、水溶性開始剤に起因する油滴
の安定効果のみで球状粒子を重合する方法であり、ま
た、分散重合はモノマーは溶解するが、生々する重合体
は溶解しない溶媒の存在下、モノマー重合体の溶解性差
を利用し粒子化する重合法である。As the polymerization method, an emulsion polymerization method, a dispersion polymerization method or a soap-free polymerization method is used. Generally, the emulsion polymerization method forms a micelle with a large amount of an emulsifier to stabilize oil droplets, and performs polymerization in the presence of a water-soluble initiator.The soap-free polymerization method is an emulsifier-free water-soluble initiator. It is a method of polymerizing spherical particles only by the resulting stabilizing effect of oil droplets, and dispersion polymerization utilizes the difference in solubility of the monomer polymer in the presence of a solvent in which the monomer dissolves but the polymer does not dissolve. This is a polymerization method in which particles are formed.
【００１２】重合終了後は沈降分離、遠心分離、デカン
テーション等の操作により、粒子を回収し、メタノール
等で洗浄し、必要ならば真空乾燥する。After the completion of the polymerization, the particles are collected by operations such as sedimentation, centrifugation, decantation and the like, washed with methanol or the like, and dried in vacuum if necessary.
【００１３】この後、上記の操作で得られた官能基Ｘを
有する粒度分布の狭い非架橋の重合体粒子を官能基Ｘと
反応する官能基を二つ以上含んだ化合物で架橋する。Thereafter, the non-crosslinked polymer particles having a narrow particle size distribution and having the functional group X obtained by the above operation are crosslinked with a compound containing two or more functional groups which react with the functional group X.
【００１４】官能基Ｘと反応する官能基を二つ以上含む
化合物は、官能基Ｘに対して反応する官能基を有してい
れば特に制限されず、例えば、官能基Ｘとしてのハロゲ
ン類、カルボキシル基、アミノ基、水酸基、グリシジル
基等と反応する官能基をそれぞれ二つ以上含む化合物が
挙げられる。官能基Ｘと反応する官能基としては、水酸
基、カルボキシル基、アミノ基、グリシジル基等が挙げ
られる。これらのうち、アミノ基、カルボキシル基及び
水酸基が好ましい。The compound containing two or more functional groups that react with the functional group X is not particularly limited as long as it has a functional group that reacts with the functional group X. For example, halogens as the functional group X, Examples thereof include compounds each containing two or more functional groups that react with a carboxyl group, an amino group, a hydroxyl group, a glycidyl group, and the like. Examples of the functional group that reacts with the functional group X include a hydroxyl group, a carboxyl group, an amino group, and a glycidyl group. Of these, amino groups, carboxyl groups and hydroxyl groups are preferred.
【００１５】二つ以上含む化合物としては、具体的に
は、エチレングリコール、プロピレングコール、トリメ
チレングリコール等の脂肪族ジアルコール、ヒドロベン
ゾイン、ベンズピコナール等の芳香族ジアルコール、シ
クロペンタン−１，２ジオール等の環状ジアルコール等
のジアルコール類また、糖アルコール等のｎ価（ｎ＞
２）のポリアルコール類、シュウ酸、マロン酸、コハク
酸、グルタル酸等の脂肪族ジカルボン酸、フタル酸、イ
ソフタル酸、テレフタル酸等の芳香族ジカルボン酸等の
ジカルボン酸類、ポリアクリル酸等のポリカルボン酸
類、エチレンジアミン、１，３−ジアミノプロパン等の
脂肪族ジアミン、ｍ−キシレンジアミン、メタフェニレ
ンジアミン、ジアミノジフェニルメタン等の芳香族ジア
ミン等のジアミン類、ジエチレントリアミン、イミノビ
スプロピルアミン、トリエチレンテトラミン等のポリア
ミン類、ポリエチレンイミン、ポリプロピレンイミン等
のイミン類の化合物、更にエチレングリコールジグリシ
ジルエステル等が挙げられる。Specific examples of the compound containing two or more compounds include aliphatic dialcohols such as ethylene glycol, propylene glycol and trimethylene glycol, aromatic dialcohols such as hydrobenzoin and benzpiconal, and cyclopentane-1. , Didiols such as cyclic dialcohols such as diols, and n-values such as sugar alcohols (n>
2) Polyalcohols, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid and glutaric acid, dicarboxylic acids such as aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and polyacrylic acids such as polyacrylic acid. Carboxylic acids, aliphatic diamines such as ethylenediamine and 1,3-diaminopropane; diamines such as aromatic diamines such as m-xylenediamine, metaphenylenediamine and diaminodiphenylmethane; diethylenetriamine, iminobispropylamine, triethylenetetramine, etc. Examples thereof include compounds of imines such as polyamines, polyethyleneimine, polypropyleneimine, and ethylene glycol diglycidyl ester.
【００１６】架橋反応を行なう際の溶媒は、水又は上述
の官能基Ｘと反応する官能基を二つ以上含む化合物を溶
解でき、官能基Ｘを有する重合体粒子を溶解しない、官
能基Ｘに対して不活性な有機溶剤が用いられる。このよ
うな有機溶剤としては、アセトン、メチルエチルケト
ン、トルエン、テトラヒドロフラン、メタノール等が挙
げられる。架橋反応を行う際の溶媒が非架橋の重合体粒
子を膨潤するものであれば架橋を内部まで進行させるこ
とができ、膨潤しない溶媒ならば重合体粒子の表面のみ
を架橋することができる。The solvent for carrying out the crosslinking reaction can dissolve water or a compound containing two or more functional groups which react with the above-mentioned functional group X, but does not dissolve polymer particles having the functional group X, into the functional group X. On the other hand, an inert organic solvent is used. Examples of such organic solvents include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, methanol and the like. If the solvent used for the crosslinking reaction swells the non-crosslinked polymer particles, the crosslinking can proceed to the inside, and if the solvent does not swell, only the surface of the polymer particles can be crosslinked.
【００１７】架橋反応は、官能基Ｘを有する非架橋の重
合体粒子１０ｇに対し、溶媒１０〜１０００ｇを用い、
上述のＸと反応する官能基を二つ以上含む化合物を任意
の割合で溶解し（溶媒に対し好ましくは１（重量）％〜
５０（重量）％）、温度３０℃以上 （好ましくは４０
℃〜８０℃）で数分〜１０時間行えばよい。必要に応じ
て、水酸化ナトリウム、水酸化カリウム等のアルカリを
加えても良い。こうして得られた架橋重合体粒子はメタ
ノール、水、必要ならば塩酸等で洗浄することができ
る。In the crosslinking reaction, 10 to 1000 g of a solvent is added to 10 g of non-crosslinked polymer particles having a functional group X,
A compound containing two or more functional groups that react with X described above is dissolved at an arbitrary ratio (preferably 1 (wt)% to the solvent).
50 (weight)%, temperature 30 ° C or higher (preferably 40)
C. to 80.degree. C.) for several minutes to 10 hours. You may add alkalis, such as sodium hydroxide and potassium hydroxide, as needed. The crosslinked polymer particles thus obtained can be washed with methanol, water and, if necessary, hydrochloric acid.
【００１８】以上のようにして得られた架橋重合体は高
度に架橋しており、また、その粒径分布は狭く、架橋前
の粒子である非架橋の重合体粒子と比べ粒径及び粒度分
布はほとんど変化することがない。本発明の架橋重合体
粒子の製造法を用いれば、液体クロマトグラフィーの充
てん剤またはその基材等として有効な粒度分布の狭い重
合体粒子が容易に製造出来る。The crosslinked polymer obtained as described above is highly crosslinked, and its particle size distribution is narrow, and the particle size and particle size distribution are higher than those of non-crosslinked polymer particles which are particles before crosslinking. Hardly changes. By using the method for producing crosslinked polymer particles of the present invention, polymer particles having a narrow particle size distribution, which are effective as a packing material for liquid chromatography or a base material thereof, can be easily produced.
【００１９】[0019]
実施例１ （ａ）官能基Ｘ（グリシジル基）を有する非架橋の重合
体粒子の製造 ポリビニルピロリドン７．５ｇ、グリシジルメタクリレ
ート５０ｇ及び２，２−アゾビスイソブチロニトリル
０．５ｇをエタノール３５０ｇ中に溶解させ、窒素ガス
で溶存酸素を置換後、７０℃で１２時間分散重合を行っ
た。放冷後、ポリマ粒子を遠心分離（１０００rpm、１
０min）し、デカンテーションで単離し、水洗した。Example 1 (a) Production of non-crosslinked polymer particles having functional group X (glycidyl group) 7.5 g of polyvinylpyrrolidone, 50 g of glycidyl methacrylate and 0.5 g of 2,2-azobisisobutyronitrile in 350 g of ethanol. Was dissolved in the solution, the nitrogen gas was substituted for the dissolved oxygen, and dispersion polymerization was carried out at 70 ° C. for 12 hours. After allowing to cool, the polymer particles are centrifuged (1000 rpm, 1
It was isolated by decantation and washed with water.
【００２０】（ｂ）官能基Ｘと反応する官能基を二つ以
上含んだ化合物による架橋反応 （ａ）で得られた非架橋の重合体粒子２ｇをメタノール
４０ml及びエチレンジアミン１４．４mlの混合溶液中に
入れ良くかく拌した。これを５０℃で加熱し、３時間か
く拌し反応を行った。反応後は冷却し、得られた架橋重
合体粒子をメタノール洗浄及び水洗をした。(B) Cross-linking reaction with a compound containing two or more functional groups that react with the functional group X 2 g of the non-crosslinked polymer particles obtained in (a) are mixed in a mixed solution of 40 ml of methanol and 14.4 ml of ethylenediamine. And stir well. This was heated at 50 ° C. and stirred for 3 hours to carry out a reaction. After the reaction, the mixture was cooled, and the obtained crosslinked polymer particles were washed with methanol and water.
【００２１】（ｃ）架橋重合体粒子の評価方法 膨潤度 粒子１．０ｇを計り１０mlのメスシリンダに入れる。バ
イブレーターで平にしその時の体積を読む（ａml）。そ
の後、アセトンを５mlまで入れ、バイブレーターで平に
する。アセトンを１０mlまで入れて１０分靜置後の体積
（ｂml）を読み、膨潤度ｂ／ａを求めた。 耐溶剤性 粒子１ｇを１０mlのアセトンに入れ、２４時間放置した
後の状況で判断した。粒子の溶解、べたつきが認められ
たもの「×」、溶解の兆候が認められなかったもの
「○」で示した。 平均粒径 体積平均粒径（ｄｖ）及び数平均粒径（ｄｎ）をコール
ターカウンターにより測定し、分散度のファクターとし
てｄｖ／ｄｎを求めた。この値が少ないほど、粒径分布
が狭く優れる。 所望しない粒子の生成率 重合反応終了後、遠心分離した上澄み溶液はメタノール
でよく洗浄し、分散剤等を除き、さらにもう一度高速で
遠心分離し、上澄みを除き、残りの溶液を蒸発乾燥させ
微粒子を回収し重量を測定した（ｃｇ）。また、遠心分
離した粒子はメタノールでよく洗浄し、粒子をメタノー
ルで分散し、３３０メッシュのふるいで凝集物を除去し
た。凝集物及び３３０メッシュ以下の製品を乾燥後それ
ぞれ重量を測定した（凝集物ｄｇ、製品ｅｇ）。所望し
ない粒子の生成率＝（ｃ＋ｄ）／（ｃ＋ｄ＋ｅ）×１０
０として求めた。それぞれの測定結果を表１にまとめて
示した。(C) Method for evaluating crosslinked polymer particles Swelling degree: 1.0 g of particles is weighed and put into a 10 ml measuring cylinder. Flatten with a vibrator and read the volume at that time (aml). After that, add acetone up to 5 ml and flatten with a vibrator. Acetone was added up to 10 ml and the volume (b ml) after 10 minutes of standing was read to determine the swelling degree b / a. Solvent resistance: 1 g of particles was put in 10 ml of acetone and allowed to stand for 24 hours. The particles were found to be dissolved or sticky "X", and no signs of dissolution were observed "O". Average particle size The volume average particle size (dv) and number average particle size (dn) were measured by a Coulter counter, and dv / dn was determined as a factor of the degree of dispersion. The smaller this value, the narrower the particle size distribution and the better. Unwanted particle production rate After completion of the polymerization reaction, the centrifuged supernatant solution is thoroughly washed with methanol to remove the dispersant and the like, and then centrifuged again at high speed to remove the supernatant, and the remaining solution is evaporated to dryness to form fine particles. It was recovered and weighed (cg). The centrifuged particles were thoroughly washed with methanol, the particles were dispersed with methanol, and a 330 mesh sieve was used to remove aggregates. The aggregates and products of 330 mesh or less were dried and then weighed (aggregates dg, product eg). Undesired particle generation rate = (c + d) / (c + d + e) × 10
It was calculated as 0. The respective measurement results are summarized in Table 1.
【００２２】実施例２ （ａ）官能基Ｘ（クロルメチル基）を有する粒度分布の
狭い非架橋重合体粒子の製造 クロルメチルスチレン１００ｇ、ドデシルベンゼンスル
ホン酸ソーダ１０ｇ、過硫酸カリウム０．４ｇ及び水２
００ｇをかく拌しながら窒素ガス中で７０℃に昇温して
６時間重合を行った。放冷後、遠心分離、デカンテーシ
ョンで粒子を回収、洗浄した。架橋反応及び評価は実施
例１と同様に行った。その結果を表１に示した。Example 2 (a) Production of non-crosslinked polymer particles having a narrow particle size distribution having a functional group X (chloromethyl group) 100 g of chloromethylstyrene, 10 g of sodium dodecylbenzenesulfonate, 0.4 g of potassium persulfate and 2 parts of water
While stirring 00 g, the temperature was raised to 70 ° C. in nitrogen gas to carry out polymerization for 6 hours. After cooling, the particles were collected and washed by centrifugation and decantation. The crosslinking reaction and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
【００２３】比較例１ 実施例１で合成した非架橋の重合体粒子を対照のため膨
潤度及び耐溶剤性について試験した。その結果を表１に
併記した。Comparative Example 1 The non-crosslinked polymer particles synthesized in Example 1 were tested for swelling and solvent resistance as controls. The results are also shown in Table 1.
【００２４】比較例２ 従来法（乳化重合）のみで架橋度１０％の粒子合成を試
みた。水５００ｇ、開始剤としての過酸化カリウム０．
５ｇ、乳化剤としてのドデシルベンゼンスルホン酸ソー
ダ０．５ｇ、モノマーとしてのアクリル酸を９０ｇ及び
架橋剤としてのジエチレングリコールジメタクリレート
１０ｇを用い窒素雰囲気下、７０度で６時間重合した。
しかし、ゲル化し球状粒子は得られなかった。Comparative Example 2 An attempt was made to synthesize particles having a crosslinking degree of 10% only by the conventional method (emulsion polymerization). 500 g of water, potassium peroxide as an initiator of 0.
5 g, 0.5 g of sodium dodecylbenzene sulfonate as an emulsifier, 90 g of acrylic acid as a monomer, and 10 g of diethylene glycol dimethacrylate as a cross-linking agent were used to perform polymerization at 70 ° C. for 6 hours in a nitrogen atmosphere.
However, it was gelated and spherical particles could not be obtained.
【００２５】比較例３ 実施例１で合成した非架橋の重合体粒子を種粒子として
シード重合で架橋を行った。アゾビスイソブチロニトリ
ル０．３５ｇ、ジエチレングリコールジメタクリレート
３５ｇ、ジクロロエタン２８ｇ、ドデシル硫酸ナトリウ
ム０．６ｇ及び水３００ｇをかく拌し乳化液を作った。
この液に、実施例１で合成した非架橋の重合体粒子を種
粒子として、この種粒子１０ｇをドデシル硫酸ナトリウ
ム０．１ｇ及び水１００ｇ中に投入して、種粒子を含む
溶液とし、この溶液をさきに調整した乳化液に投入し、
そのまま１３時間常温で撹拌して油滴となった乳化液を
粒子に吸収させた。ついで、２重量％ポリビニルアルコ
ール水溶液２５０ｇを加え、７０℃で８時間重合を行っ
た。得られた粒子は実施例１と同様に評価を行った。そ
の結果を表１に示す。Comparative Example 3 Crosslinking was carried out by seed polymerization using the non-crosslinked polymer particles synthesized in Example 1 as seed particles. 0.35 g of azobisisobutyronitrile, 35 g of diethylene glycol dimethacrylate, 28 g of dichloroethane, 0.6 g of sodium dodecyl sulfate and 300 g of water were stirred to prepare an emulsion.
To this solution, the non-crosslinked polymer particles synthesized in Example 1 were used as seed particles, and 10 g of the seed particles were put into 0.1 g of sodium dodecyl sulfate and 100 g of water to give a solution containing seed particles. Add to the previously prepared emulsion,
The emulsion was stirred as it was for 13 hours at room temperature to form oil droplets, which were then absorbed by the particles. Then, 250 g of a 2 wt% polyvinyl alcohol aqueous solution was added, and polymerization was carried out at 70 ° C. for 8 hours. The obtained particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】実施例１、実施例２は本発明の製造法に沿
って合成した架橋重合体粒子であり、比較例１は非架橋
の重合体粒子である。実施例１のものは比較例１に比ら
べ膨潤度も小さく耐溶剤性もあることから十分架橋され
ていることが分かる。比較例２は通常の乳化重合で架橋
粒子を製造した例である。架橋度を高くしようとすると
球状粒子が得られないことが分かる。比較例３はシード
重合を用いて架橋した例である。実施例１は所望しない
粒子の生成がなくｄｖ／ｄｎも変わらないが、比較例３
は所望しない粒子がかなり発生しており、ｄｖ／ｄｎも
大きくなっていることが分かる。Examples 1 and 2 are crosslinked polymer particles synthesized according to the production method of the present invention, and Comparative Example 1 is non-crosslinked polymer particles. Compared to Comparative Example 1, Example 1 has a smaller degree of swelling and solvent resistance, and thus it can be seen that it is sufficiently crosslinked. Comparative Example 2 is an example in which crosslinked particles are produced by ordinary emulsion polymerization. It can be seen that spherical particles cannot be obtained when the degree of crosslinking is increased. Comparative Example 3 is an example of cross-linking using seed polymerization. In Example 1, no undesired particles are generated and dv / dn does not change, but Comparative Example 3
It can be seen that a large number of undesired particles are generated and dv / dn is also large.
【００２８】[0028]
【発明の効果】本発明の製造法によって、粒径分布の狭
い架橋重合体粒子を効率よく得ることができる。The crosslinked polymer particles having a narrow particle size distribution can be efficiently obtained by the production method of the present invention.
Claims (3)
ル％以上含有するモノマー溶液を乳化重合法、分散重合
法又はソープフリー重合で重合して、非架橋の重合体粒
子とし、前記粒子の有する官能基Ｘと反応する官能基を
二つ以上含む化合物により、前記粒子を架橋する架橋重
合体粒子の製造法。 【化１】 （式中、Ｘは官能基を表し、Ｒ1、Ｒ2及びＲ3は各々独
立して一価の有機基を表し、Ｙは２価の有機基を表わす
か、Ｙは含まれずＸが直接炭素原子に結合してもよい）1. A non-crosslinked polymer particle is obtained by polymerizing a monomer solution containing 5 mol% or more of the monomer represented by the general formula (I) by emulsion polymerization method, dispersion polymerization method or soap-free polymerization. A method for producing crosslinked polymer particles, wherein the particles are crosslinked with a compound containing two or more functional groups that react with the functional group X of the above. [Chemical 1] (In the formula, X represents a functional group, R 1 , R 2 and R 3 each independently represent a monovalent organic group, Y represents a divalent organic group, or Y is not included and X is directly May be attached to a carbon atom)
応する官能基がアミノ基、カルボキシル基又は水酸基で
ある請求項１記載の架橋重合体粒子の製造法。2. The method for producing crosslinked polymer particles according to claim 1, wherein X is a glycidyl group, and the functional group which reacts with the functional group X is an amino group, a carboxyl group or a hydroxyl group.
ゲン化メチルスチレンであり、官能基Ｘと反応する官能
基がアミノ基又は水酸基である請求項１記載の架橋重合
体粒子の製造法。3. The method for producing crosslinked polymer particles according to claim 1, wherein the monomer represented by the general formula (I) is halogenated methylstyrene, and the functional group which reacts with the functional group X is an amino group or a hydroxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5016684A JPH06228225A (en) | 1993-02-04 | 1993-02-04 | Production of crosslinked polymer particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5016684A JPH06228225A (en) | 1993-02-04 | 1993-02-04 | Production of crosslinked polymer particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06228225A true JPH06228225A (en) | 1994-08-16 |
Family
ID=11923150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5016684A Pending JPH06228225A (en) | 1993-02-04 | 1993-02-04 | Production of crosslinked polymer particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06228225A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999019370A1 (en) * | 1997-10-15 | 1999-04-22 | Amersham Pharmacia Biotech K.K. | Process for producing polymer particles with uniform particle size |
| JP2010070615A (en) * | 2008-09-17 | 2010-04-02 | Univ Of Tsukuba | Crosslinked polymer composition for surface treatment of support |
| WO2011114993A1 (en) * | 2010-03-15 | 2011-09-22 | 日立化成工業株式会社 | Cross-linked polymer particle and method for producing same |
| WO2011158761A1 (en) * | 2010-06-17 | 2011-12-22 | 日立化成工業株式会社 | Cross-linked polymer particles, production method and electrically conductive particles thereof |
| CN111072874A (en) * | 2019-12-25 | 2020-04-28 | 苏州为度生物技术有限公司 | Construction method for highly ordered arrangement of carboxyl on surface of magnetic microsphere |
-
1993
- 1993-02-04 JP JP5016684A patent/JPH06228225A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999019370A1 (en) * | 1997-10-15 | 1999-04-22 | Amersham Pharmacia Biotech K.K. | Process for producing polymer particles with uniform particle size |
| JP2010070615A (en) * | 2008-09-17 | 2010-04-02 | Univ Of Tsukuba | Crosslinked polymer composition for surface treatment of support |
| WO2011114993A1 (en) * | 2010-03-15 | 2011-09-22 | 日立化成工業株式会社 | Cross-linked polymer particle and method for producing same |
| WO2011158761A1 (en) * | 2010-06-17 | 2011-12-22 | 日立化成工業株式会社 | Cross-linked polymer particles, production method and electrically conductive particles thereof |
| CN111072874A (en) * | 2019-12-25 | 2020-04-28 | 苏州为度生物技术有限公司 | Construction method for highly ordered arrangement of carboxyl on surface of magnetic microsphere |
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