JP3086478B2 - Porous fine particles - Google Patents
Porous fine particlesInfo
- Publication number
- JP3086478B2 JP3086478B2 JP29708690A JP29708690A JP3086478B2 JP 3086478 B2 JP3086478 B2 JP 3086478B2 JP 29708690 A JP29708690 A JP 29708690A JP 29708690 A JP29708690 A JP 29708690A JP 3086478 B2 JP3086478 B2 JP 3086478B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- porous fine
- transition temperature
- polyetheretherketone
- glass transition
- 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.)
- Expired - Fee Related
Links
- 239000010419 fine particle Substances 0.000 title claims description 33
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 10
- 229920002530 polyetherether ketone Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 7
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000000034 method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は耐熱性、耐薬品性に秀れた、空孔率の高い球
状多孔性微粒子に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to spherical porous fine particles having excellent heat resistance and chemical resistance and high porosity.
本発明の微粒子は、クロマトグラフィーの支持体、吸
着剤、菌体の支持体、触媒の担体、濾過材、及び濾過材
の洗浄材等に適用可能である。The fine particles of the present invention are applicable to a support for chromatography, an adsorbent, a support for bacterial cells, a carrier for a catalyst, a filter material, a cleaning material for a filter material, and the like.
高分子微粒子の製法としては種々の方法が提案されて
いる。乳化重合、懸濁重合法などによってモノマーから
合成する方法、高分子溶液に非溶媒を加えて沈澱や二成
分相分離により微粒子を得る方法などである。Various methods have been proposed for producing polymer fine particles. Examples thereof include a method of synthesizing from a monomer by an emulsion polymerization method and a suspension polymerization method, and a method of adding a non-solvent to a polymer solution to obtain fine particles by precipitation or two-component phase separation.
これらの方法で得られる微粒子のうち、モノマーから
合成されるタイプは一般に架橋構造を持っている。した
がって耐熱性は高いが耐薬品性が低く、膨潤しやすいと
いう問題点があり、さらに、多孔性の高いものが得にく
い。Of the fine particles obtained by these methods, the type synthesized from the monomer generally has a crosslinked structure. Therefore, there is a problem that the heat resistance is high, but the chemical resistance is low, and it is easy to swell, and it is difficult to obtain a material having high porosity.
一方、高分子溶液を沈殿させたり相分離させる方法に
よれば多孔性の高い微粒子が得られるものの、溶剤可溶
であるために耐薬品性が低く、また、耐熱性も充分では
なかった。On the other hand, according to the method of precipitating or phase-separating a polymer solution, fine particles having high porosity can be obtained, but the solvent resistance is low due to the solubility in a solvent, and the heat resistance is not sufficient.
本発明は架橋構造を持たないにもかかわらず、高い耐
熱性、耐薬品性を持ち、しかも高い空孔率と充分な強度
を持つ球状多孔性微粒子を提供するものである。The present invention is to provide spherical porous fine particles having high heat resistance and chemical resistance despite having no crosslinked structure, and also having high porosity and sufficient strength.
本発明はガラス転移温度が130℃以上の熱可塑性の結
晶性高分子であるポリエーテルエーテルケトンあるいは
ポリエーテルケトンからなる平均粒子径１μｍ〜40μ
ｍ、空孔率60％〜95％の非架橋性の球状多孔性微粒子に
関する。The present invention relates to a thermoplastic crystalline polymer having a glass transition temperature of 130 ° C. or higher, polyetheretherketone or polyetherketone.
m, non-crosslinkable spherical porous fine particles having a porosity of 60% to 95%.
本発明に用いられるガラス転移温度が130℃以上の熱
可塑性結晶性高分子としては、ポリエーテルエーテルケ
トン（PEEK）、ポリエーテルケトンPEK等があげられ
る。PEEKは繰り返し単位 で代表的に示されるポリマー類である。Examples of the thermoplastic crystalline polymer having a glass transition temperature of 130 ° C. or higher used in the present invention include polyetheretherketone (PEEK) and polyetherketone PEK. PEEK is a repeating unit Are polymers typically represented by
また、PEKは繰り返し単位 で代表的に示されるポリマー類である。PEK is a repeating unit Are polymers typically represented by
本発明の多孔性微粒子は、粒子径１〜40μｍの範囲で
所望の大きさをとりうる。The porous fine particles of the present invention can have a desired size within a particle size range of 1 to 40 μm.
球状の粒子１コ１コは、0.1〜２μｍから選ばれるほ
ぼ同じ大きさの空隙を多数有しており、粒子表面は粒子
を形成するポリマーが薄い鱗片状または糸状をなして外
へ向って突出した形状をとっている。この様子を図面に
示した。Each spherical particle has a large number of voids of substantially the same size selected from 0.1 to 2 μm, and the surface of the particle has a polymer forming the particle protruding outward in the form of a thin scale or thread. The shape is taken. This is shown in the drawing.
第１図はこの発明の粒子の構造の一例を示す電子顕微
鏡写真（倍率4000倍）である。FIG. 1 is an electron micrograph (magnification: 4000) showing an example of the structure of the particles of the present invention.
本願の微粒子はひじょうに高い空孔率を有する。しか
も、空孔率が高いにもかかわらず大きな強度（圧縮）を
持つている。また、高い耐薬品性を示すが、これは恐ら
く個個の微粒子の高い結晶性に由来しているものと思わ
れる。The microparticles of the present application have a very high porosity. Moreover, it has high strength (compression) despite its high porosity. It also shows high chemical resistance, probably due to the high crystallinity of the individual microparticles.
空孔率は60％未満では吸着剤、担体、濾過材としての
性能が不充分であり、一方、95％を越えると微粒子の強
度が弱くなり実用的でない。If the porosity is less than 60%, the performance as an adsorbent, a carrier, and a filter material is insufficient. On the other hand, if the porosity exceeds 95%, the strength of the fine particles becomes weak, which is not practical.
ここで微粒子の空孔率Pr（％）とは 微粒子を微粒子の含水時の重量W1（ｇ）、乾燥後の重
量W0（ｇ）、および原料の結晶性高分子の比重をρとす
るとき、 で表わされる値を云う。Here, the porosity Pr (%) of the fine particles is defined as ρ, where ρ is the weight W 1 (g) of the fine particles when they contain water, the weight W 0 (g) after drying, and the specific gravity of the crystalline polymer as the raw material. When Means the value represented by
含水時の重量は、まず乾燥微粒子約1gを100mlのエタ
ノール中に加えて細孔内に充分エタノールを湿潤させ、
濾紙でこし、残った微粒子をかわかす事なく水中に分散
させてから、濾紙で10回繰り返してこし、充分に水に濡
れた微粒子を得、それを乾いた濾紙上に拡げ余分な水分
をとってから重量を測定すれば良い。乾燥は水分をとば
すために、100℃で24時間の真空乾燥をすれば充分であ
る。Weight when wet, first add about 1 g of dry microparticles in 100 ml of ethanol to wet ethanol sufficiently in the pores,
Strain with filter paper, disperse the remaining fine particles in water without dough, then repeat with filter paper 10 times to obtain sufficiently wet fine particles, spread it on dry filter paper and take excess water. The weight can be measured from. For drying, vacuum drying at 100 ° C. for 24 hours is sufficient to remove moisture.
本発明の多孔性微粒子は、例えばガラス転移温度が13
0℃以上の熱可塑性結晶性高分子であるポリエーテルエ
ーテルケトンを、加熱したスルホラン中に溶解してから
冷却し、得られたゲル状物を水中で超音波分散させる事
により得られる。The porous fine particles of the present invention have, for example, a glass transition temperature of 13
It is obtained by dissolving polyetheretherketone, which is a thermoplastic crystalline polymer having a temperature of 0 ° C. or higher, in heated sulfolane, cooling, and ultrasonically dispersing the obtained gel in water.
乾燥物を得るためには、濾紙でこしてから減圧あるい
は加熱乾燥すれば良い。凝集を防ぐためには、凍結して
から減圧乾燥が好ましい。In order to obtain a dried product, it may be rubbed with filter paper and then dried under reduced pressure or heat. In order to prevent agglomeration, it is preferable to freeze and then dry under reduced pressure.
他の方法としては、ポリマーを溶解した加熱スルホラ
ン溶液をノズルから空気中に噴霧し、水中あるいは適当
な溶媒中に捕集することによって得られる。As another method, it can be obtained by spraying a heated sulfolane solution in which a polymer is dissolved from a nozzle into the air, and collecting it in water or an appropriate solvent.
得られる微粒子の空孔率は、スルホラン溶液の中のポ
リマー濃度によりコントロールでき、空孔率の高いもの
は溶液の濃度を下げる事により得られる。The porosity of the obtained fine particles can be controlled by the polymer concentration in the sulfolane solution, and those having a high porosity can be obtained by lowering the concentration of the solution.
また、微粒子の大きさは冷却速度あるいは噴霧時の液
滴の大きさによりコントロールでき、１〜40μｍのもの
を作ることができる。Further, the size of the fine particles can be controlled by the cooling rate or the size of the droplet at the time of spraying.
実施例 ICI社製のPEEKのガラス転移温度をパーキンエルマー
社製示差熱分析計（DSC）により測定したところ、143℃
であった。Example When the glass transition temperature of PEEK manufactured by ICI was measured by a differential thermal analyzer (DSC) manufactured by Perkin Elmer, it was 143 ° C.
Met.
このPEEK7gを加熱したスルホラン（東京化成製）93g
中に入れ、287℃窒素シール下で８時間撹拌し、かっ色
の透明溶液を得た。93g of sulfolane (manufactured by Tokyo Chemical Industry) heated with 7g of this PEEK
The mixture was stirred at 287 ° C. under a nitrogen blanket for 8 hours to obtain a clear brown solution.
これを容器ごと空気中で放冷し、灰色のゲル状物を得
た。このゲル状物を容器からとり出し、１の水中に入
れ、超音波を１時間かけたところ、白濁した液が得られ
た。This was left to cool in the air together with the container to obtain a gray gel. The gel was taken out of the container, placed in water (1), and subjected to ultrasonic wave for 1 hour. As a result, a cloudy liquid was obtained.
これを濾紙でこしてから残査を再び１の水中に加
え、超音波を１時間かけた。これをAl板上に数滴落と
し、乾燥させて電子顕微鏡（SEM）で観察したところ、
粒径約16μｍの微粒子が生成していた。この微粒子の構
造を第２図（4000倍）に示した。一方、この分散液を再
び濾紙でこし、得た残査を90℃で真空乾燥した。得られ
た微粒子の重量は、約6.5g、空孔率は91％であった。This was rubbed with filter paper, and the residue was again added to 1 water, and ultrasonic waves were applied for 1 hour. A few drops of this were dropped on an Al plate, dried and observed with an electron microscope (SEM).
Fine particles having a particle size of about 16 μm were formed. The structure of the fine particles is shown in FIG. 2 (4000 times). On the other hand, this dispersion was rubbed again with filter paper, and the obtained residue was vacuum-dried at 90 ° C. The weight of the obtained fine particles was about 6.5 g, and the porosity was 91%.
参考例 実施例で得られた微粒子1gをエタノール50g中に分散
させ、吸引びんに取付けたG4のガラスフィルター（65
φ）上へ注ぎ、吸引してガラスフィルター上に微粒子の
層を形成させた。層上に純水１を注ぎ、吸引して微粒
子層を水洗した。さらに球径1.09μｍのポリスチレンラ
テックス球の水分散液を注ぎ、吸引濾過したところ、ラ
テックスの微粒子層透過率は２％以下であった。Reference Example 1 g of the fine particles obtained in the example was dispersed in 50 g of ethanol, and a G4 glass filter (65 g) attached to a suction bottle was used.
φ) Poured over and suctioned to form a layer of fine particles on the glass filter. Pure water 1 was poured on the layer, and the fine particle layer was washed with water by suction. Further, an aqueous dispersion of polystyrene latex spheres having a sphere diameter of 1.09 μm was poured and suction-filtrated. As a result, the fine particle layer transmittance of the latex was 2% or less.
一方、微粒子層を形成させないガラスフィルターを用
いた以外は上記と同じ方法を繰返し、球径1.09μｍのポ
リスチレンラテックスの吸引濾過を行ったところ、ラテ
ックスは100％透過した。On the other hand, the same method as described above was repeated except that a glass filter not forming a fine particle layer was used, and suction filtration of polystyrene latex having a sphere diameter of 1.09 μm resulted in 100% transmission of the latex.
第１図は、この発明の粒子の構造の例を示す電子顕微鏡
写真である。 第２図は、この発明の実施例により得られた粒子の構造
を示す電子顕微鏡写真である。FIG. 1 is an electron micrograph showing an example of the structure of the particles of the present invention. FIG. 2 is an electron micrograph showing the structure of the particles obtained according to the example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−280749（ＪＰ，Ａ) 特開 昭62−215638（ＪＰ，Ａ) 特開 平１−278541（ＪＰ，Ａ) 特開 昭63−260935（ＪＰ，Ａ) 特開 昭63−112634（ＪＰ，Ａ) 特開 昭51−107346（ＪＰ，Ａ) 特開 平３−140340（ＪＰ，Ａ) 特開 平３−185028（ＪＰ，Ａ) 特表 平４−506675（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 9/00 - 9/42 C08J 3/12 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-280749 (JP, A) JP-A-62-215638 (JP, A) JP-A-1-278541 (JP, A) JP-A 63-80741 260935 (JP, A) JP-A-63-112634 (JP, A) JP-A-51-107346 (JP, A) JP-A-3-140340 (JP, A) JP-A-3-185028 (JP, A) Special Table Hei 4-506675 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C08J 9/00-9/42 C08J 3/12
Claims (4)
結晶性高分子であるポリエーテルエーテルケトンあるい
はポリエーテルケトンからなる平均粒子径１μｍ〜40μ
ｍ、空孔率60％〜95％の非架橋性の球状の多孔性微粒子1. An average particle size of polyetheretherketone or polyetherketone, which is a thermoplastic crystalline polymer having a glass transition temperature of 130 ° C. or more, is 1 μm to 40 μm.
m, non-crosslinkable spherical porous fine particles with a porosity of 60% to 95%
ほぼ同じ大きさの空隙を多数有しており、粒子表面は粒
子を形成するポリマーが薄い鱗片状または糸状をなして
外へ向かって突出した形状である事を特徴とする請求項
２記載の多孔性微粒子2. The porous fine particles have a large number of voids of substantially the same size selected from 0.1 to 2 μm, and the polymer forming the particles protrudes outward in the form of thin scales or threads. The porous fine particles according to claim 2, wherein the porous fine particles have a shaped shape.
ルエーテルケトンまたはポリエーテルケトンを加熱した
スルホラン中に溶解してから冷却する事を特徴とする請
求項１記載の多孔性微粒子を製造する方法3. The method for producing porous fine particles according to claim 1, wherein polyetheretherketone having a glass transition temperature of 130 ° C. or higher is dissolved in heated sulfolane and then cooled.
ルエーテルケトンまたはポリエーテルケトンを加熱した
スルホラン中に溶解して得た加熱溶液をノズルから空気
中に噴霧し、水中あるいは適当な溶媒中に捕集すること
を特徴とする請求項１記載の多孔性微粒子を製造する方
法4. A heated solution obtained by dissolving polyetheretherketone or a polyetherketone having a glass transition temperature of 130 ° C. or more in heated sulfolane is sprayed from a nozzle into the air, and the solution is dissolved in water or an appropriate solvent. The method for producing porous fine particles according to claim 1, wherein the fine particles are collected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29708690A JP3086478B2 (en) | 1990-11-05 | 1990-11-05 | Porous fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29708690A JP3086478B2 (en) | 1990-11-05 | 1990-11-05 | Porous fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04170445A JPH04170445A (en) | 1992-06-18 |
| JP3086478B2 true JP3086478B2 (en) | 2000-09-11 |
Family
ID=17842021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29708690A Expired - Fee Related JP3086478B2 (en) | 1990-11-05 | 1990-11-05 | Porous fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3086478B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021049900A1 (en) * | 2019-09-11 | 2021-03-18 | (주)엘지하우시스 | Thermoplastic polymer particles and method for manufacturing same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2386378C (en) * | 1999-11-16 | 2006-04-11 | Asahi Kasei Kabushiki Kaisha | Porous beads and method for producing the same |
| CN109432494B (en) * | 2018-11-20 | 2021-04-23 | 中国科学院长春应用化学研究所 | A kind of PEEK microsphere with special topological morphology on the surface and its preparation method and application |
-
1990
- 1990-11-05 JP JP29708690A patent/JP3086478B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021049900A1 (en) * | 2019-09-11 | 2021-03-18 | (주)엘지하우시스 | Thermoplastic polymer particles and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04170445A (en) | 1992-06-18 |
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