JPH01301717A - Production of fine spherical particle of acrylonitrile-based polymer - Google Patents
Production of fine spherical particle of acrylonitrile-based polymerInfo
- Publication number
- JPH01301717A JPH01301717A JP13205888A JP13205888A JPH01301717A JP H01301717 A JPH01301717 A JP H01301717A JP 13205888 A JP13205888 A JP 13205888A JP 13205888 A JP13205888 A JP 13205888A JP H01301717 A JPH01301717 A JP H01301717A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- acrylonitrile
- particles
- particle
- fluid nozzle
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000012798 spherical particle Substances 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 53
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 17
- 239000012530 fluid Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010419 fine particle Substances 0.000 abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 3
- 239000007921 spray Substances 0.000 abstract description 3
- 238000001694 spray drying Methods 0.000 abstract description 2
- 230000001112 coagulating effect Effects 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は重合体微粒子の製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing fine polymer particles.
本発明方法により得られる重合体微粒子は、戻素質小球
体（カーボンマイクロビーズ）製造用原料、液体クロマ
トグラフィー用充填剤、イオン交換樹脂用ビーズ、粉末
成形用材料、粉末塗装用材料、艶消し剤等の用途に用い
ることができる。The polymer fine particles obtained by the method of the present invention can be used as a raw material for producing return element small spheres (carbon microbeads), a filler for liquid chromatography, beads for ion exchange resins, materials for powder molding, materials for powder coating, and matting agents. It can be used for purposes such as
近年、プラスチックの粉末成形、粉末塗装が盛んになり
、そのだめ、プラスチック微粒子の需要が増大し、また
、種々の粒子径を有するプラスチック微粒子が要求され
ている。更に、塗装面の艶消し剤としても微粒子状重合
体が使用されるようになってきている。また、微粒子状
重合体は液体クロマトグラフィー用充填剤、あるいはイ
オン交換樹脂用粒子としても有用であり、かかる分野へ
の利用も期待されている。In recent years, powder molding and powder coating of plastics have become popular, and as a result, the demand for plastic fine particles has increased, and plastic fine particles having various particle sizes are also required. Furthermore, particulate polymers are also being used as matting agents for painted surfaces. The particulate polymer is also useful as a filler for liquid chromatography or as particles for ion exchange resins, and is expected to be used in such fields.
このように種々の用途に用いられる微粒子状重合体は、
一般にポリエチレン、ポリプロピレン、ポリスチレンを
始めとし、多種の合成重合体から製造されている。一方
、繊維製造用重合体として周知のアクリロニトリル系重
合体はポリオレフイン系重合体と比較して耐光性、耐候
性に優れ、また焼成して炭素質物質に容易に変換される
ことから、かかる重合体をｍ−た微小球体（マイクロビ
ーズ）の製造法の開発が行われている。Fine particulate polymers used for various purposes are as follows:
They are generally manufactured from a variety of synthetic polymers, including polyethylene, polypropylene, and polystyrene. On the other hand, acrylonitrile-based polymers, which are well-known as polymers for fiber manufacturing, have superior light resistance and weather resistance compared to polyolefin-based polymers, and are easily converted into carbonaceous materials by firing. A method for producing microspheres (microbeads) is being developed.
このよう々アクリロニトリル系重合体微粒子を得る方法
としては、例えば、油溶性高分子分散剤の存在下で溶液
重合を行い単量体よシ直接アクリロニトリル糸重合体微
粒子を得る力源特公昭４５−３４３９６号公報）、アク
リロニトリル系重合体を溶解しない溶剤中で重合し得た
重合体を物理的に分散処理したり（％公昭４９−３１７
５３号公報）、或は水の共存下でアクリロニトリル系重
合体を加熱溶融せしめた後、噴霧する方法（％公昭４２
−１７６４４号公報）等が提案されている。As a method for obtaining such acrylonitrile polymer fine particles, for example, the monomer is directly subjected to solution polymerization in the presence of an oil-soluble polymer dispersant to obtain acrylonitrile thread polymer fine particles. Publication No. 49-317), physical dispersion treatment of polymers polymerized in solvents that do not dissolve acrylonitrile polymers (% Publication No. 49-317)
53), or a method of heating and melting an acrylonitrile polymer in the coexistence of water and then spraying it (% Kosho 42)
-17644) etc. have been proposed.
しかしながら、これらの方法で得られるアクリロニトリ
ル系重合体微粒子はその形状が不規則であるだけでなく
、その粒子径分布が広いだめ用途によっては後処理を行
わなければならなかった。また、粒子表面に多くの凸凹
を有したてこほど状の物であり、粒子形状が均一で粒子
表面に凸凹のない、粒子径分布の狭いアクリロニトリル
系重合体微粒子を製造する方法は未だ見いださ力、てい
方いのが現状である。However, the acrylonitrile polymer fine particles obtained by these methods not only have an irregular shape but also have a wide particle size distribution, and therefore require post-treatment depending on the intended use. In addition, the particle surface is lever-shaped with many irregularities, and no method has yet been found to produce acrylonitrile polymer fine particles with a uniform particle shape, no irregularities on the particle surface, and a narrow particle size distribution. The current situation is that it is difficult to do so.
本発明の目的は、粒子径分布が狭くかつコントロールさ
れた粒子径を有するアクリロニトリル系重合体の真球状
微粒子を製造する方法を提供することにある。An object of the present invention is to provide a method for producing true spherical fine particles of an acrylonitrile polymer having a narrow and controlled particle size distribution.
〔問題点を解決しようとするだめの手段〕そこで本発明
者らは、このような現状に鑑み鋭意検討した結果、本発
明を完成するにいたった。即ち、本発明はアクリロニト
リル系重合体の有機溶剤溶液を２流体ノズルを用いて粒
子状に分割し、該分割した粒子を一般式Ｒ−ＯＨ（Ｒ：
水素まだは炭素数１〜３のアルキル基）で示される非溶
剤と接触させて重合体を凝固させ、該凝固した重合体微
粒子を含む分散液を、２流体ノズルを用いて噴霧乾燥し
体積平均粒子径（Ｄｖｏよ）が１〜１００μｍでかつ体
積平均粒子径と数平均粒子径（Ｄ ）の比が１〜２Ｏ
ｐ
の分布を有する真球状のアクリロニトリル系重合体微粒
子の製造方法にある。[Means to Solve the Problem] The inventors of the present invention conducted extensive studies in view of the current situation, and as a result, completed the present invention. That is, the present invention divides an organic solvent solution of an acrylonitrile polymer into particles using a two-fluid nozzle, and divides the divided particles into particles with the general formula R-OH (R:
The polymer is coagulated by contacting it with a non-solvent represented by hydrogen or an alkyl group having 1 to 3 carbon atoms, and the dispersion containing the coagulated polymer particles is spray-dried using a two-fluid nozzle to obtain a volume average The particle diameter (Dvo) is 1 to 100 μm and the ratio of volume average particle diameter to number average particle diameter (D) is 1 to 2O
The present invention provides a method for producing truly spherical acrylonitrile polymer fine particles having a distribution of p.
本発明を実施するに際して使用されるアクリロニトリル
系重合体はアクリロニトリルを５０重量％以上含有する
重合体である。アクリロニトリルと共重合することが可
能な他の単量体としては、メチルメタクリレート、エチ
ルメタクリレート、ブチルメタクリレート、ヘキシルメ
タクリレート、メチルアクリレート、エチルアクリレー
ト、ブチルアクリレート、プロピルアクリレートなどの
メタクリル酸、アクリル酸のエステル類、塩化ビニル、
臭化ビニル、塩化ビニリデン等のハロゲン化ビニル類、
メタクリル酸、アクリル酸、イタコン酸、クロトン酸、
ビニルスルホン酸、アリルヌルホン酸、メタリルスルホ
ン酸等の酸類及びそれらの塩類：或はマレイン酸イミド
、フェニルマレイミド、アクリルアミド、メタクリルア
ミド、スチレン、γ−メチルスチレンなどを挙げること
ができる。これらの単量体は単独で寸だけ２種以上を混
合して用いることができる。The acrylonitrile polymer used in carrying out the present invention is a polymer containing 50% by weight or more of acrylonitrile. Other monomers that can be copolymerized with acrylonitrile include esters of methacrylic acid and acrylic acid, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and propyl acrylate. , vinyl chloride,
Vinyl halides such as vinyl bromide and vinylidene chloride,
Methacrylic acid, acrylic acid, itaconic acid, crotonic acid,
Examples include acids such as vinyl sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, and salts thereof; or maleic acid imide, phenyl maleimide, acrylamide, methacrylamide, styrene, and γ-methylstyrene. These monomers can be used alone or in a mixture of two or more.
また、上記のアクリロニトリル系重合体を溶解する有機
溶剤としては、ジメチルホルムアミド、ジメチルアセト
アミド、ジメチルスルホキシド、α−ブチルラクトン、
エチレンカーボネイト等が挙げられる。In addition, examples of organic solvents that dissolve the acrylonitrile-based polymer include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, α-butyl lactone,
Examples include ethylene carbonate.
次に、本発明においては、上記アクリロニトリル系重合
体の有機溶剤溶液を２流体ノズル或はスプレィガンによ
って粒子状に分割し、該分割した粒子を一般式Ｒ−ＯＨ
（Ｒ：水素または炭素数１〜３のアルキル基）で示され
る非溶剤に接触させて重合体を凝固させる。これ以外の
非溶剤を用いると、粒子表面に多くの凸凹を有したでこ
ぼこ状の粒子しか得られない。また、重合体溶液を２流
体ノズル以外のノズルを用いて粒子状に分割した場合に
は分割した粒子の大きさが不均一となり、その後の乾燥
工程にまで粗大の粒子が混入する結果、得られるアクリ
ロニトリル系重合体は、その粒径分布が非常に広くなり
、例えば、静電記録紙用の絶縁層として用いた場合には
線切れが発生し、また、化粧品用微粒子として用いた場
合には、ざらつき感のある製品しか得ることはできなり
０
また、本発明において噴霧乾燥においても２流体ノズル
を使用することによって初めて粒子径分布の狭い真球状
のアクリロニトリル系重合体微粒子を製造することが可
能となったばかりで々く、ノズル詰まり等の発生も防止
でき生産性の向上をはかることが可能となった。Next, in the present invention, the organic solvent solution of the acrylonitrile polymer is divided into particles using a two-fluid nozzle or a spray gun, and the divided particles are expressed by the general formula R-OH.
The polymer is solidified by contacting with a non-solvent represented by (R: hydrogen or an alkyl group having 1 to 3 carbon atoms). If any other non-solvent is used, only uneven particles with many irregularities on the particle surface will be obtained. In addition, when a polymer solution is divided into particles using a nozzle other than a two-fluid nozzle, the sizes of the divided particles become non-uniform, and as a result, coarse particles are mixed into the subsequent drying process. Acrylonitrile polymers have a very wide particle size distribution, for example, when used as an insulating layer for electrostatic recording paper, line breakage occurs, and when used as fine particles for cosmetics, In addition, in the present invention, by using a two-fluid nozzle in spray drying, it is possible to produce perfectly spherical acrylonitrile polymer fine particles with a narrow particle size distribution for the first time. This has made it possible to prevent nozzle clogging and improve productivity.
以下、本発明を実施例で説明する。尚、実施例中チは重
量係を示す。The present invention will be explained below with reference to Examples. Incidentally, in the examples, ``chi'' indicates weight.
実施例１
水系懸濁重合法により得られたηｓｐ／ｃ−α５６（ｏ
、 ５ ％のジメチルホルムアミド溶液で測定）のポリ
アクリロニトリル重合体の２−５チジメチルホルムアミ
ド溶液を２流体ノズ）Ｖ （静東共立商会製 ＡＭ−４
５）を用いてメタノール中に噴霧し凝固させた後、同ノ
ズルを用いて噴霧乾燥した。得られた粒子は球状で、コ
ールタ−カウンターによる粒径分布の測定した結果、そ
の体積平均粒子径は＆６２μｍ、粒子径１０μｍ以上及
び０７４μｍ以下の粒子の含有率は００１％以下であっ
た。Example 1 ηsp/c-α56(o
A 2-5 tidimethylformamide solution of a polyacrylonitrile polymer (measured with a 5% dimethylformamide solution) was added using a two-fluid nozzle) V (AM-4 manufactured by Shizuto Kyoritsu Shokai).
5) was used to spray it into methanol and solidify it, and then spray-dried using the same nozzle. The obtained particles were spherical, and as a result of particle size distribution measurement using a Coulter counter, the volume average particle size was &62 μm, and the content of particles with particle sizes of 10 μm or more and 0.074 μm or less was 0.001% or less.
実施例２
実施例１で用込だポリアクリロニトリル重合体を数種の
濃度のジメチルホルムアミド溶液とし実施例１と同様に
粉末化した。その結果を以下の表１に示した。Example 2 The polyacrylonitrile polymer used in Example 1 was made into dimethylformamide solutions of several concentrations and powdered in the same manner as in Example 1. The results are shown in Table 1 below.
比較例１
実施例１と同様にしてメタノール中に噴霧凝固させたポ
リアクリロニトリル重合体粒子を、回転ディスクタイプ
の微粒化ノズルを用いて噴霧乾燥したところ、その形状
は偏平なもの（円盤状）となり、その体積平均粒子径も
５．７５μｍ、数平均粒子径２．５１μｒｎ （Ｄ ｖ
ｏ ｘ ／ Ｄ Ｉ）０７）−２，２９）、かつ粒子径
１０μｍ以上の粒子もａ２％存在する分布の広い粉末し
か得られなかった。Comparative Example 1 Polyacrylonitrile polymer particles spray-coagulated in methanol in the same manner as in Example 1 were spray-dried using a rotating disk type atomization nozzle, and the shape was flat (disk-like). , its volume average particle diameter is also 5.75 μm, and its number average particle diameter is 2.51 μrn (D v
ox/DI) 07)-2,29), and only a powder with a wide distribution in which particles with a particle diameter of 10 μm or more were present in a2% was obtained.
表 １
〔発明の効果〕
以上詳述したように、本発明の方法により粒度分布の狭
い真球状のアクυロニ） ＩＪ ／し系重合体が得られ
、その結果種々の分野でその使用が可能となり、その効
果は極めて太きｂものである。Table 1 [Effects of the Invention] As detailed above, the method of the present invention yields a truly spherical acrylonitrile (IJ)-based polymer with a narrow particle size distribution, and as a result, it can be used in various fields. Therefore, the effect is extremely large.
特許出願人 三菱レイヨン株式会社 代理人 弁理士 吉 沢 敏 夫Patent applicant: Mitsubishi Rayon Co., Ltd. Agent: Patent Attorney Toshio Yoshizawa
Claims (1)
ルを用いて粒子状に分割し、該分割した粒子を一般式Ｒ
−ＯＨ（Ｒ：水素または炭素数１〜３のアルキル基）で
示される非溶剤と接触させて重合体を凝固させ、該凝固
した重合体微粒子を含む分散液を、２流体ノズルを用い
て噴霧乾燥することにより得られる体積平均粒子径（Ｄ
＿ｖ＿ｏ＿ｌ）が１〜１００μｍでかつ体積平均粒子径
と数平均粒子径（Ｄ＿ｐ＿ｏ＿ｐ）の比が１〜２の分布
を有する真球状のアクリロニトリル系重合体微粒子の製
造方法。An organic solvent solution of an acrylonitrile polymer is divided into particles using a two-fluid nozzle, and the divided particles are divided into particles with the general formula R
The polymer is coagulated by contacting with a non-solvent represented by -OH (R: hydrogen or an alkyl group having 1 to 3 carbon atoms), and a dispersion containing the coagulated polymer particles is sprayed using a two-fluid nozzle. Volume average particle diameter obtained by drying (D
_v_o_l) is 1 to 100 μm and the ratio of volume average particle diameter to number average particle diameter (D_p_o_p) is 1 to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13205888A JPH01301717A (en) | 1988-05-30 | 1988-05-30 | Production of fine spherical particle of acrylonitrile-based polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13205888A JPH01301717A (en) | 1988-05-30 | 1988-05-30 | Production of fine spherical particle of acrylonitrile-based polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01301717A true JPH01301717A (en) | 1989-12-05 |
Family
ID=15072531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13205888A Pending JPH01301717A (en) | 1988-05-30 | 1988-05-30 | Production of fine spherical particle of acrylonitrile-based polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01301717A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012031291A (en) * | 2010-07-30 | 2012-02-16 | Toray Ind Inc | Resin fine particle and production method of the same |
| US9724302B2 (en) | 2010-04-09 | 2017-08-08 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| DE102016203349A1 (en) | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Production of Si / C composite particles |
-
1988
- 1988-05-30 JP JP13205888A patent/JPH01301717A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9724302B2 (en) | 2010-04-09 | 2017-08-08 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| US9730892B2 (en) | 2010-04-09 | 2017-08-15 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| US9737483B2 (en) | 2010-04-09 | 2017-08-22 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| US9737482B2 (en) | 2010-04-09 | 2017-08-22 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| US9757336B2 (en) | 2010-04-09 | 2017-09-12 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| US9808424B2 (en) | 2010-04-09 | 2017-11-07 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| US10045941B2 (en) | 2010-04-09 | 2018-08-14 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| US10398648B2 (en) | 2010-04-09 | 2019-09-03 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
| JP2012031291A (en) * | 2010-07-30 | 2012-02-16 | Toray Ind Inc | Resin fine particle and production method of the same |
| DE102016203349A1 (en) | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Production of Si / C composite particles |
| WO2017148871A1 (en) | 2016-03-01 | 2017-09-08 | Wacker Chemie Ag | Production of si/c composite particles |
| US11145849B2 (en) | 2016-03-01 | 2021-10-12 | Wacker Chemie Ag | Production of Si/C composite particles |
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