JPH04139206A - Production of polymer gel bead having heat-sensitive characteristic - Google Patents
Production of polymer gel bead having heat-sensitive characteristicInfo
- Publication number
- JPH04139206A JPH04139206A JP26055890A JP26055890A JPH04139206A JP H04139206 A JPH04139206 A JP H04139206A JP 26055890 A JP26055890 A JP 26055890A JP 26055890 A JP26055890 A JP 26055890A JP H04139206 A JPH04139206 A JP H04139206A
- Authority
- JP
- Japan
- Prior art keywords
- beads
- aqueous solution
- polymerization
- polymer
- isopropylacrylamide
- 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
- 239000011324 bead Substances 0.000 title claims abstract description 32
- 229920000642 polymer Polymers 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 11
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 230000002441 reversible effect Effects 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 18
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- -1 AIBN (α Chemical class 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は可塑的感熱特性を有するミクロンサイズのポリ
マーゲルビーズの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing micron-sized polymer gel beads having plastic thermosensitive properties.
更に詳しくいえば、本発明は吸着剤、化粧品等に利用し
・うる加温により収縮及び脱水する感熱特性を有するミ
クロンサイズのポリマーケルビーズの製造方法に関する
ものである。More specifically, the present invention relates to a method for producing micron-sized polymer Kel beads that can be used in adsorbents, cosmetics, etc. and have thermosensitive properties that shrink and dehydrate when heated.
（従来の技術）
可逆的感熱性を有するポリマーケルビーズの製造方法と
しては、溶媒−界面活性剤−ブリケル水溶液からなろ逆
相懸濁重合法（広瀬美冶、網屋毅之、広用能嗣、日中豐
−５第１回高分子ゲル研究討論会資料、３９ （＋９８
８））や、カチオン界面活性剤あるいはアニオン界面活
性剤を臨界ミセル濃度以上の濃度で添加して得られる水
溶液系でのエマルション重合法（伊藤昭二、平佐興彦、
藤重昇永、その他、Ｐｏｌｙｍｅｒ Ｐｒｅｐｒｉｎｔ
ｓ、 Ｊａｐａｎ ｖｏｌ、３９． Ｎｏ３（１９９０
））などがある。(Prior art) As a method for producing polymer Kel beads having reversible heat sensitivity, the Naro reverse phase suspension polymerization method (Yoshihiro Hirose, Takeyuki Amiya, Yoshitsugu Hiroyo, Japan-China Fyo-5 1st Polymer Gel Research Conference Materials, 39 (+98
8)) or an emulsion polymerization method in an aqueous solution system obtained by adding a cationic surfactant or anionic surfactant at a concentration higher than the critical micelle concentration (Shoji Ito, Okihiko Heisa,
Shonaga Fujishige, others, Polymer Preprint
s, Japan vol, 39. No. 3 (1990)
))and so on.
前者は、溶媒として有機溶剤であるｎ−ヘキサンを用い
る必要がある。また、この方法で得られるビーズの流体
力学的直径は膨潤状態では約８゜Ｏｎｍ、収縮状態では
約２００ｎｍ〜３００ｎ汀１である。後者は、水溶液系
でポリマーケルを得ることかできるが、この方法で得ら
れるビーズの流体力学的直径は膨潤状態で約７５ｎｍ〜
１５００ｍ、収縮状態では約６５ｎｍ〜１１００ｎであ
る。In the former case, it is necessary to use n-hexane, which is an organic solvent, as a solvent. The hydrodynamic diameter of the beads obtained by this method is about 8° Onm in the swollen state and about 200 nm to 300 nm in the contracted state. In the latter case, it is possible to obtain a polymer gel in an aqueous solution system, but the hydrodynamic diameter of the beads obtained by this method is approximately 75 nm to 75 nm in the swollen state.
1500m, and about 65nm to 1100n in the contracted state.
（発明か解決しようとする課題）
上記ナノメーターサイズのポリマーケルビーズよりも粒
径のさらに大きな可逆的感熱特性を有するビーズが製造
できればポリマーケルビーズ単体を容易に分取すること
が可能となり用途の拡大か其月待されろ。(Problem to be solved by the invention) If it is possible to produce beads with a larger particle size and reversible heat-sensitive properties than the nanometer-sized polymer Kel beads mentioned above, it will be possible to easily separate individual polymer Kel beads, which can be used for various purposes. I'll have to wait for the next month to expand.
本発明は粒径がミクロンサイズであり可逆的感熱特性を
有するポリマーケルビーズの製造方法を提供することを
目的としてなされたものである。The object of the present invention is to provide a method for producing polymer Kel beads having micron-sized particles and reversible heat-sensitive properties.
（課題を解決するための手段）
本発明者らは鋭意研究を重ねた結果、Ｎ−イソプロピル
アクリルアミド及び架橋性モノマーを必須成分とし、必
要に応して共重合可能なその他ビニルモノマーを配合し
て成る水溶液に、分散安定剤としてポリアクリル酸ナト
リウムを添加して均一な水溶液を調製し、撹拌下におい
て重合することにより前記課題を達成しうろことを見い
出し、本発明を完成するに至った。(Means for Solving the Problems) As a result of extensive research, the present inventors have found that N-isopropylacrylamide and a crosslinkable monomer are essential components, and other copolymerizable vinyl monomers are blended as necessary. The inventors have discovered that the above object can be achieved by adding sodium polyacrylate as a dispersion stabilizer to the aqueous solution to prepare a homogeneous aqueous solution, and polymerizing the solution under stirring, thereby completing the present invention.
即ち、本発明はＮ−イソプロピルアクリルアミド及び架
橋性モノマーを必須成分とし、必要に応じてその他共重
合可能なビニルモノマーを配合して成る水溶液に、分散
安定剤としてポリアクリル酸ナトリウムを単量体に対し
て０．０５重量％〜４重量％の濃度範囲で添加して均一
な水溶液を調整し、撹拌下において重合を行なうことを
特徴とする可逆的感熱特性を有するミクロンサイズのポ
リマーケルビーズ製造方法である。That is, the present invention involves adding sodium polyacrylate as a monomer as a dispersion stabilizer to an aqueous solution containing N-isopropylacrylamide and a crosslinking monomer as essential components, and optionally containing other copolymerizable vinyl monomers. A method for producing micron-sized polymer Kel beads with reversible heat-sensitive properties, characterized by adding the polymer in a concentration range of 0.05% to 4% by weight to prepare a uniform aqueous solution, and polymerizing under stirring. It is.
本発明に用いるＮ−イソプロピルアクリルアミドの構造
式は下記のように表わされる。The structural formula of N-isopropylacrylamide used in the present invention is expressed as follows.
本発明で用いる架橋性モノマーとしては、通常の架橋性
モノマーが使用できる。例えば、本発明で用いる架橋性
モノマーとしてはメチレンビスアクリルアミドがあげら
れる。As the crosslinkable monomer used in the present invention, ordinary crosslinkable monomers can be used. For example, the crosslinking monomer used in the present invention includes methylene bisacrylamide.
共重合可能なビニルモノマーとしては、例えばアクリル
酸モノマー等のイオン性モノマーが使われ、ポリマーケ
ルビーズの１＃潤度向上を目的とする。As the copolymerizable vinyl monomer, for example, an ionic monomer such as an acrylic acid monomer is used, and the purpose is to improve the 1# moisture content of polymer Kel beads.
重合反応媒体としての水は、イオン交換水、蒸留水、上
水等が使用される。As water as a polymerization reaction medium, ion-exchanged water, distilled water, tap water, etc. are used.
重合を開始する方法としては、通常知られている任意の
方法を用いることができる。例えば、重合開始剤として
はＡＩＢＮ （α、α′−アゾヒスイソブチロニトリル
）等のアソ化合物、ＢＰＯ（過酸化ヘンジイル）等の過
酸化物をあげることができる。また、重合開始剤を２種
以上使用することも可能である。重合開始剤の使用量は
、単量体に対し通常０．０１〜１０重量％、好ましくは
０．０５〜８重量％である。重合温度は使用する開始剤
によって異なるが通常４０℃以上の温度で行なわれる。Any commonly known method can be used to initiate polymerization. For example, examples of the polymerization initiator include aso compounds such as AIBN (α, α'-azohisisobutyronitrile) and peroxides such as BPO (hendiyl peroxide). It is also possible to use two or more kinds of polymerization initiators. The amount of the polymerization initiator used is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight based on the monomer. The polymerization temperature varies depending on the initiator used, but it is usually carried out at a temperature of 40°C or higher.
本発明では分散安定剤としてポリアクリル酸ナトリウム
を用いる。ポリアクリル酸ナトリウムの重合度は特に限
定するものではないが、概ね重合度１０００〜１０００
００の範囲のものが使用できる。本発明のミクロンサイ
ズのポリマーゲルビーズを得るには、その使用範囲は単
量体に対し０．０５〜４重量％、好ましくは０．１〜３
重量％である。また、生成するポリマーの曇点を著しく
変えない範囲、且つ重合系の安定性に支障をおこさない
範囲において、他の水溶性高分子、難溶性の微粉末状の
無機化合物、あるいは界面活性剤を加えてもかまわない
。In the present invention, sodium polyacrylate is used as a dispersion stabilizer. The degree of polymerization of sodium polyacrylate is not particularly limited, but the degree of polymerization is generally 1000 to 1000.
00 range can be used. To obtain the micron-sized polymer gel beads of the present invention, the usage range is 0.05 to 4% by weight, preferably 0.1 to 3% by weight based on the monomer.
Weight%. In addition, other water-soluble polymers, poorly soluble finely powdered inorganic compounds, or surfactants may be added to the extent that they do not significantly change the cloud point of the resulting polymer and do not affect the stability of the polymerization system. You can add it.
ポリアクリル酸ナトリウムを上記記載の濃度範囲で添加
したＮ−イソプロピルアクリルアミド及び架橋性モノマ
ーを必須成分とした水溶液を調製し、撹拌下において重
合させ、得られたポリマーケルビーズを濾過することて
水相から分取する。An aqueous solution containing N-isopropylacrylamide and a crosslinking monomer as essential components to which sodium polyacrylate has been added in the concentration range described above is prepared, polymerized under stirring, and the resulting polymer Kelbeads are filtered to form an aqueous phase. Separate from.
分取したポリマーケルビーズを数回純水にて洗浄するこ
とにより精製を行なう。このようにして可逆的感熱特性
を有するミクロンサイズのポリマーゲルビーズを得るこ
とができる。Purification is performed by washing the collected polymer Kel beads several times with pure water. In this way, micron-sized polymer gel beads with reversible thermosensitive properties can be obtained.
本発明のポリマーケルビーズの粒径及び粒度分布をレー
ザ回折式粒度分布測定装置ＬＡ−５００（（株）堀場製
作所）を用いて測定すると、このケルビーズは重合条件
にもよるが概ね膨潤状態では４０μｍ〜６０μｍの範囲
、収縮状態ては２０μｍ〜３０μｍの範囲である。When the particle size and particle size distribution of the polymer Kel beads of the present invention were measured using a laser diffraction particle size distribution analyzer LA-500 (Horiba, Ltd.), the diameter of the Kel beads in the swollen state was approximately 40 μm, depending on the polymerization conditions. ~60 μm, and in the contracted state, it is in the range of 20 μm to 30 μm.
（発明の効果）
本発明により得られるポリマーケルビーズは、溶媒−界
面活性剤−ブリケル水溶液からなる逆相懸濁重合法（広
瀬美治、網屋毅之、広用能嗣、日中豊−第１目高分子ケ
ル研究討論会資料、３９（１９８８））や、カチオン界
面活性剤あるいはアニオン界面活性剤を臨界ミセル濃度
以上の濃度で添加して得られる水溶液系でのエマルジョ
ン重合法（伊藤昭二、平佐興彦、藤重昇永、その他、Ｐ
ｏｌｙｍｅｒ Ｐｒｅｐｒｉｎｔｓ、Ｊａｐａｎ ｖｏ
ｌ、３９．Ｎｏ３（１９９０））なとより得られるビー
ズに比べはるかに粒径が大きい特徴を有する。このポリ
マーゲルビーズは濾過することで容易にポリマー単量体
を分取することができ、さらに広範囲の用途が期待され
る。(Effects of the Invention) Polymer Kel beads obtained by the present invention can be obtained by a reverse-phase suspension polymerization method consisting of a solvent-surfactant-Brickel aqueous solution (Yoshiharu Hirose, Takeyuki Amiya, Yoshitsugu Hiroyo, Yutaka Naka-D. 1st Polymer Kel Research Discussion Materials, 39 (1988)), and an emulsion polymerization method in an aqueous solution system obtained by adding a cationic or anionic surfactant at a concentration higher than the critical micelle concentration (Shoji Ito, Okihiko Heisa, Shonaga Fujishige, others, P
olymer Preprints, Japan vo
l, 39. No. 3 (1990)) is characterized by a much larger particle size than beads obtained from other beads. These polymer gel beads can be easily separated into polymer monomers by filtration, and are expected to be used in a wider range of applications.
（実施例）
以下、実施例により本発明を説明するが本発明はこれに
限定されるものではない。(Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.
実施例１
５００ ｍ ｌの三つロフラスコの中に、Ｎ−イソプロ
ピルアクリルアミドｌＯｇ、純水２００ｇ、メチレンヒ
スアクリルアミドＯ０Ｉｇ、ＢＰＯ０６１ｇ、ポリアク
リル酸ナトリウム（重合度２２００〜７００００）０．
０！５ｇを入れ、窒素気流下に撹拌（２０Ｏｒｐｍ）Ｌ
ながら８０℃で３時間重合を行なわせた。重合の進行と
共に白色のポリマービーズか生成した。このようにして
合成されたポリマー酒漬を濾過し、純水にて繰り返し処
理することてポリマーゲルビーズを得た。Example 1 In a 500 ml three-neck flask, 10 g of N-isopropylacrylamide, 200 g of pure water, 01 g of methylenehisacrylamide, 061 g of BPO, and 0.0 g of sodium polyacrylate (degree of polymerization 2200-70000).
Add 0.5g and stir under nitrogen stream (20Orpm) L
Polymerization was carried out at 80° C. for 3 hours. As the polymerization progressed, white polymer beads were produced. The polymer gel beads synthesized in this manner were filtered and repeatedly treated with pure water to obtain polymer gel beads.
このようにして得られたゲルビーズの平均粒径をレーザ
回折式粒度分布測定装置ＬＡ−５００（（株）堀場製作
所）を用い測定した。ゲルビーズを含む水溶液を測定装
置（超音波バス）に入れ分散した。測定温度は２５℃、
３５℃とした。測定結果を表−１に示す。The average particle size of the gel beads thus obtained was measured using a laser diffraction particle size distribution analyzer LA-500 (manufactured by Horiba, Ltd.). An aqueous solution containing gel beads was placed in a measuring device (ultrasonic bath) and dispersed. The measurement temperature was 25℃,
The temperature was 35°C. The measurement results are shown in Table-1.
表
ポリマーゲルビーズの平均粒径
比較例１
５００ ｍ ｌの三つロフラスコの中に、Ｎ−イソプロ
ピルアクリルアミド１ｏｇ、純水２００ｇ、メチしンヒ
スアクリルアミト０．１ｇ、ＢＰＯ００１ｇ、実施例１
と同しポリアクリル酸ナトリウム０．５ｇを入れ、窒素
気流下に撹拌（２０Ｏｒｐｍ）しながら８０℃で３時間
重合を行なわせた。重合の進行と共に白色のポリマービ
ーズが生成するが、平均粒径を測定すると３５℃で０．
５０μｍてあった。Table Average Particle Size of Polymer Gel Beads Comparative Example 1 In a 500 ml three-bottle flask, 1 og of N-isopropylacrylamide, 200 g of pure water, 0.1 g of methicine his-acrylamide, 001 g of BPO, Example 1
0.5 g of the same sodium polyacrylate was added, and polymerization was carried out at 80° C. for 3 hours while stirring (20 rpm) under a nitrogen stream. As the polymerization progresses, white polymer beads are produced, and the average particle size is measured at 35°C and is 0.
It was 50 μm.
比較例２
５００ ｍ ｌの三つロフラスコの中に、Ｎ−イソプロ
ピルアクリルアミド１０ｇ、純水２００ｇ、メチレンビ
スアクリルアミドＯ，Ｉｇ、ＢＰＯ０，１ｇ、実施例１
と同しポリアクリル酸ナトリウム０．００１ｇを入れ、
窒素気流下に撹拌（２０Ｏｒｐｍ）しなから８０°Ｃて
３時間重合を行なわせた。Comparative Example 2 In a 500 ml three-necked flask, 10 g of N-isopropylacrylamide, 200 g of pure water, 0.1 g of methylenebisacrylamide O, Ig, and 0.1 g of BPO, Example 1
Add 0.001g of the same sodium polyacrylate,
Polymerization was carried out at 80° C. for 3 hours while stirring (20 rpm) under a nitrogen stream.
重合の進行と共に白色のポリマービーズか生成するか、
重合開始から１時間３０分後に粒の凝集がみられた。粒
の取得はできなかった。As the polymerization progresses, white polymer beads are formed.
Aggregation of particles was observed 1 hour and 30 minutes after the start of polymerization. It was not possible to obtain grains.
比較例３
５００ ｍ ｌの三つロフラスコの中に、Ｎ−イソプロ
ピルアクリルアミド１０ｇ、純水：２００ ｇ、メチし
ンヒスアクリルアミト０．１ｇ、ＢＰＯＯ，１ｇを入れ
、窒素気流下に撹拌（２０Ｏｒｐｍ）しながら８０°Ｃ
て３時間重合を行なわせた。重合の進行と共に粒の凝集
がみられた。粒の取得ばてきなかった。Comparative Example 3 10 g of N-isopropylacrylamide, 200 g of pure water, 0.1 g of methicinehisacrylamide, and 1 g of BPOO were placed in a 500 ml three-necked flask, and the mixture was stirred under a nitrogen stream (20 rpm). 80°C while
Polymerization was carried out for 3 hours. Agglomeration of particles was observed as the polymerization progressed. I couldn't get the grains.
Claims (1)
を必須成分とし、必要に応じてその他共重合可能なビニ
ルモノマーを配合して成る水溶液に、分散安定剤として
ポリアクリル酸ナトリウムを単量体に対して０．０５重
量％〜４重量％の濃度範囲で添加して均一な水溶液を調
製し、撹拌下において重合を行なうことを特徴とする可
逆的感熱特性を有するミクロンサイズのポリマーゲルビ
ーズの製造方法。Add sodium polyacrylate as a dispersion stabilizer to an aqueous solution containing N-isopropylacrylamide and a crosslinking monomer as essential components and, if necessary, other copolymerizable vinyl monomers. 1. A method for producing micron-sized polymer gel beads having reversible thermosensitivity, characterized by adding a homogeneous aqueous solution by adding in a concentration range of .05% to 4% by weight, and polymerizing under stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26055890A JPH04139206A (en) | 1990-10-01 | 1990-10-01 | Production of polymer gel bead having heat-sensitive characteristic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26055890A JPH04139206A (en) | 1990-10-01 | 1990-10-01 | Production of polymer gel bead having heat-sensitive characteristic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04139206A true JPH04139206A (en) | 1992-05-13 |
Family
ID=17349628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26055890A Pending JPH04139206A (en) | 1990-10-01 | 1990-10-01 | Production of polymer gel bead having heat-sensitive characteristic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04139206A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995021876A1 (en) * | 1994-02-10 | 1995-08-17 | Kohjin Co., Ltd. | Temperature-sensitive water-absorbing/desorbing polymer composition |
| JPH09136921A (en) * | 1995-11-17 | 1997-05-27 | Agency Of Ind Science & Technol | Ph-sensitive and heat-sensitive microbead and its production |
| WO1999003435A1 (en) * | 1997-07-16 | 1999-01-28 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Diaper with a heat-sensitive or ph-sensitive superabsorber |
| EP1072617A1 (en) * | 1999-07-30 | 2001-01-31 | Universiteit van Utrecht | Temperature sensitive polymers |
| WO2006040990A1 (en) * | 2004-10-08 | 2006-04-20 | Nisshinbo Industries, Inc. | Method for producing acicular or oval-spherical organic polymer particle |
| JP2011246507A (en) * | 2010-05-24 | 2011-12-08 | Hymo Corp | Temperature-sensitive fine particle gel dispersion liquid having high concentration and high separation stability and method for producing the same |
| JP2011246508A (en) * | 2010-05-24 | 2011-12-08 | Hymo Corp | Filler treatment agent and paper containing filler treated by the same |
-
1990
- 1990-10-01 JP JP26055890A patent/JPH04139206A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995021876A1 (en) * | 1994-02-10 | 1995-08-17 | Kohjin Co., Ltd. | Temperature-sensitive water-absorbing/desorbing polymer composition |
| US5672656A (en) * | 1994-02-10 | 1997-09-30 | Kohjin Co., Ltd. | Temperature sensitive water absorbing and discharging polymer composition |
| JPH09136921A (en) * | 1995-11-17 | 1997-05-27 | Agency Of Ind Science & Technol | Ph-sensitive and heat-sensitive microbead and its production |
| WO1999003435A1 (en) * | 1997-07-16 | 1999-01-28 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Diaper with a heat-sensitive or ph-sensitive superabsorber |
| EP1072617A1 (en) * | 1999-07-30 | 2001-01-31 | Universiteit van Utrecht | Temperature sensitive polymers |
| WO2001009198A1 (en) * | 1999-07-30 | 2001-02-08 | Stichting Voor De Technische Wetenschappen | Temperature sensitive polymers |
| WO2006040990A1 (en) * | 2004-10-08 | 2006-04-20 | Nisshinbo Industries, Inc. | Method for producing acicular or oval-spherical organic polymer particle |
| JP2011246507A (en) * | 2010-05-24 | 2011-12-08 | Hymo Corp | Temperature-sensitive fine particle gel dispersion liquid having high concentration and high separation stability and method for producing the same |
| JP2011246508A (en) * | 2010-05-24 | 2011-12-08 | Hymo Corp | Filler treatment agent and paper containing filler treated by the same |
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