JPH04239031A - Production of polymer powder having increased particle diameter - Google Patents
Production of polymer powder having increased particle diameterInfo
- Publication number
- JPH04239031A JPH04239031A JP6074391A JP6074391A JPH04239031A JP H04239031 A JPH04239031 A JP H04239031A JP 6074391 A JP6074391 A JP 6074391A JP 6074391 A JP6074391 A JP 6074391A JP H04239031 A JPH04239031 A JP H04239031A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- polystyrene
- powder
- resin powder
- particle size
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 239000002245 particle Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920000642 polymer Polymers 0.000 title description 10
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 91
- 239000004793 Polystyrene Substances 0.000 claims abstract description 44
- 229920002223 polystyrene Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000010419 fine particle Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- CUTXCTMFSKCMJV-UHFFFAOYSA-N 3-chloro-5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound ClC1=C(O2)C(C)=CC2=C1 CUTXCTMFSKCMJV-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- -1 polyphenylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyethers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は粉体取扱い性の良い粒子
径の肥大化したポリフェニレンエーテルまたは変性ポリ
フェニレンエーテル樹脂粉粒体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polyphenylene ether or modified polyphenylene ether resin powder having an enlarged particle size that is easy to handle.
【０００２】0002
【従来の技術】ポリフェニレンエーテル樹脂は一般に有
機溶媒中でフェノール類を酸化重合することによって製
造されているが、重合体溶液からポリフェニレンエーテ
ルを回収するのに一般的にメタノール等のポリフェニレ
ンエーテルに対する貧溶媒と接触させて行っている。こ
の際、析出するポリフェニレンエーテル粒子は著しく微
細な粒子を含んでいる。[Prior Art] Polyphenylene ether resins are generally produced by oxidative polymerization of phenols in an organic solvent, but in order to recover polyphenylene ether from a polymer solution, a poor solvent for polyphenylene ether such as methanol is generally used. We are contacting them. At this time, the polyphenylene ether particles precipitated contain extremely fine particles.
【０００３】このことは粒子の濾別工程における濾別時
間の増大、乾燥工程、輸送工程における飛散等の問題、
あるいは成形時においてホッパーから供給される粒子の
噛み込み不良等の問題のため、多くのトラブルの原因と
なっている。このような微粉体に対する成形操作におい
てはバキュームホッパー、及びバキュームコンベアー等
の装置を組み合わせることにより解決されているが、経
済的に不利であり操作も繁雑になるといった問題があっ
た。[0003] This results in problems such as increased filtration time in the particle filtration process, scattering in the drying process and transport process, etc.
Alternatively, problems such as poor biting of particles supplied from a hopper during molding cause many troubles. Molding operations for such fine powders have been solved by combining devices such as vacuum hoppers and vacuum conveyors, but these have been disadvantageous economically and require complicated operations.
【０００４】一方、特公昭４５−５８７号公報などに明
示されているようにポリフェニレンエーテルの重合体溶
液にポリフェニレンエーテルの貧溶媒を接触させ重合体
を析出させる時の条件が析出する重合体の粒子径に大き
な影響を及ぼすことが既に知られている。しかしこの方
法も重合体溶液をその沸点近傍まで加熱することや、ポ
リフェニレンエーテルの貧溶媒であるメタノールの添加
を可及的速やかに行わなければならないことから操作が
困難かつ繁雑であつた。On the other hand, as disclosed in Japanese Patent Publication No. 45-587, the conditions for bringing a poor solvent of polyphenylene ether into contact with a polyphenylene ether polymer solution to precipitate the polymer are such that the particles of the polymer precipitate are It is already known that it has a large effect on the diameter. However, this method is also difficult and complicated to operate because the polymer solution must be heated to near its boiling point and methanol, which is a poor solvent for polyphenylene ether, must be added as quickly as possible.
【０００５】また特公昭５５−１７７７５号公報におい
ては有機溶媒を含むポリフェニレンエーテルの水分散系
において熱処理を行うことでポリフェニレンエーテル樹
脂粉粒体の粒子径を肥大化させる方法が明示されている
が、この方法では熱処理温度が４０℃〜１５０℃という
ように常温より比較的高温で行わなければならず比熱の
高い水を使用することによるエネルギーコストがかなり
かかるといった問題があった。Furthermore, Japanese Patent Publication No. 55-17775 clearly discloses a method of enlarging the particle size of polyphenylene ether resin powder by carrying out heat treatment in an aqueous dispersion system of polyphenylene ether containing an organic solvent. This method has the problem that the heat treatment must be carried out at a temperature of 40 DEG C. to 150 DEG C., which is relatively higher than room temperature, and the energy cost is considerable due to the use of water with a high specific heat.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、微細な粒子
を多量に含むポリフェニレンエーテルおよび変性ポリフ
ェニレンエーテル樹脂粉粒体の有機溶媒分散系から常温
で容易に適度に粒子径の肥大化したポリフェニレンエー
テル樹脂粉粒体を得ることができ、粉粒体取扱い性の改
良されたポリフェニレンエーテルおよび変性ポリフェニ
レンエーテル樹脂粉粒体を提供することを課題とするも
のである。[Problems to be Solved by the Invention] The present invention provides polyphenylene ether which can be easily and appropriately enlarged in particle size at room temperature from an organic solvent dispersion system of polyphenylene ether containing a large amount of fine particles and modified polyphenylene ether resin powder. It is an object of the present invention to provide polyphenylene ether and modified polyphenylene ether resin powder which can be obtained as resin powder and which has improved powder handling properties.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、粉体取扱
い性の良い粒子径の肥大したポリフェニレンエーテル樹
脂の製造方法について鋭意努力を重ねた結果、ポリフェ
ニレンエーテル粉粒体の有機溶媒分散系にポリスチレン
溶液を接触させることによりポリフェニレンエーテル樹
脂の粒子同志を凝集せしめ、肥大化した重合体粒子が得
られることを見い出した。[Means for Solving the Problems] As a result of intensive efforts by the present inventors to develop a method for producing a polyphenylene ether resin with an enlarged particle size that is easy to handle as a powder, the present inventors have developed an organic solvent dispersion system of polyphenylene ether powder particles. It has been discovered that by bringing a polystyrene solution into contact with a polyphenylene ether resin, particles of polyphenylene ether resin can be aggregated to form enlarged polymer particles.
【０００８】すなわち、本発明はポリフェニレンエーテ
ル樹脂粉粒体の有機溶媒分散系にポリスチレン溶液を接
触させることを特徴とする粒子径の肥大化したポリフェ
ニレンエーテルまたは変性ポリフェニレンエーテル樹脂
粉粒体の製造方法を提供するものである。本発明に用い
るポリフェニレンエーテルは一般式（１）で表される。That is, the present invention provides a method for producing polyphenylene ether or modified polyphenylene ether resin powder having an enlarged particle size, which comprises bringing a polystyrene solution into contact with an organic solvent dispersion of polyphenylene ether resin powder. This is what we provide. The polyphenylene ether used in the present invention is represented by general formula (1).
【０００９】[0009]
【化１】[Chemical formula 1]
【００１０】この一般構造をもつ典型的な例は、ポリ−
（２，６−ジメチル−１，４−フェニレン）−エーテル
、ポリ−（２−メチル−６−エチル−１，４−フェニレ
ン）−エーテル、ポリ−（２，６−ジエチル−１，４−
フェニレン）−エーテル、ポリ−（２−エチル−６−ｎ
−プロピル−１，４−フェニレン）−エーテル、ポリ−
（２−メチル−６−クロロ−１，４−フェニレン）−エ
ーテル、ポリ−（２−メチル−６−ブロモ−１，４−フ
ェニレン）−エーテル、ポリ−（２−メチル−６−イソ
プロピル−１，４−フェニレン）−エーテル、ポリ−（
２−メチル−６−ｎ−プロピル−１，４−フェニレン）
−エーテル、ポリ−（２−メチル−６−ｎ−ブチル−１
，４−フェニレン）−エーテル、ポリ−（２，６−ジ−
ｎ−プロピル−１，４−フェニレン）−エーテル、ポリ
−（２−エチル−６−クロロ−１，４−フェニレン）−
エーテルなどの単独重合体、あるいはランダム共重合体
、ブロック共重合体が挙げられるが、これらに限定され
るものではない。又、これらは少量のｏ−クレゾール、
ｍ−クレゾール、ｐ−クレゾール、２，３，６−トリメ
チルフェノールなどを共重合成分として含んでいても何
ら差し支えない。A typical example with this general structure is poly-
(2,6-dimethyl-1,4-phenylene)-ether, poly-(2-methyl-6-ethyl-1,4-phenylene)-ether, poly-(2,6-diethyl-1,4-
phenylene)-ether, poly-(2-ethyl-6-n
-propyl-1,4-phenylene)-ether, poly-
(2-methyl-6-chloro-1,4-phenylene)-ether, poly-(2-methyl-6-bromo-1,4-phenylene)-ether, poly-(2-methyl-6-isopropyl-1 ,4-phenylene)-ether, poly-(
2-methyl-6-n-propyl-1,4-phenylene)
-ether, poly-(2-methyl-6-n-butyl-1
,4-phenylene)-ether, poly-(2,6-di-
n-propyl-1,4-phenylene)-ether, poly-(2-ethyl-6-chloro-1,4-phenylene)-
Examples include, but are not limited to, homopolymers such as ether, random copolymers, and block copolymers. In addition, these contain a small amount of o-cresol,
There is no problem even if m-cresol, p-cresol, 2,3,6-trimethylphenol, etc. are included as a copolymerization component.
【００１１】変性ポリフェニレンエーテルとしては、例
えば、前述したポリフェニレンエーテルに、スチレン重
合体等、その他の重合体が、グラフトしているものある
いは、ポリフェニレンエーテルにマレイン酸や臭化アリ
ル等炭素−炭素２重結合を分子内に持つ化合物を付加せ
しめたもの等が挙げられる。Examples of modified polyphenylene ethers include polyphenylene ethers grafted with other polymers such as styrene polymers, or polyphenylene ethers with carbon-carbon double polymers such as maleic acid and allyl bromide. Examples include those to which a compound having a bond in the molecule is added.
【００１２】ポリフェニレンエーテル粉粒体を分散させ
る有機溶媒としては、ポリフェニレンエーテルの良溶媒
とポリフェニレンエーテルの貧溶媒とを混合して使用す
ることが望ましい。As the organic solvent for dispersing the polyphenylene ether powder, it is desirable to use a mixture of a good solvent for polyphenylene ether and a poor solvent for polyphenylene ether.
【００１３】ポリフェニレンエーテルの良溶媒としては
例えば、ベンゼン、トルエン、エチルベンゼン、キシレ
ン等の芳香族炭化水素、クロロホルム、１，２−ジクロ
ルエタン、クロルベンゼン、ジクロルベンゼンなどのハ
ロゲン化炭化水素、ニトロベンゼンのようなニトロ化合
物などが使用でき、またポリフェニレンエーテルの貧溶
媒としてはメタノール、エタノール、ｎ−プロパノール
、イソプロパノール、ｎ−ブタノール、ｓｅｃ−ブタノ
ール、ｔｅｒｔ−ブタノール等のアルコール類、アセト
ン、メチルエチルケトン等のケトン類、酢酸エチル、蟻
酸エチル等のエステル類、テトラヒドロフラン、ジエチ
ルエーテル等のエーテル類を使用する。これらのポリフ
ェニレンエーテルに対する良溶媒、貧溶媒の混合溶媒中
に微細な粒子を含むポリフェニレンエーテル粒子を分散
させる。この時混合溶媒の組成はかかるポリフェニレン
エーテル粒子が溶解してしまわないように調整する。
本発明に用いるポリスチレンは一般式（２）で表される
。Examples of good solvents for polyphenylene ether include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene, and nitrobenzene. Examples of poor solvents for polyphenylene ether include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and tert-butanol; ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate and ethyl formate, and ethers such as tetrahydrofuran and diethyl ether are used. Polyphenylene ether particles containing fine particles are dispersed in a mixed solvent of a good solvent and a poor solvent for these polyphenylene ethers. At this time, the composition of the mixed solvent is adjusted so that the polyphenylene ether particles are not dissolved. The polystyrene used in the present invention is represented by general formula (2).
【００１４】[0014]
【化２】[Case 2]
【００１５】但し、式中のＲ３ は、水素原子、アルキ
ル基、ハロゲン基、Ｒ４ は水素原子、アルキル基、ビ
ニル基であり、ｍは１〜５の整数でｍが２以上であれば
、Ｒ４ は互いに異なる基であっても良い。これらの例
としては、ポリスチレン、ポリ−α−メチルスチレン、
ポリクロロスチレンなどの単独重合体あるいはランダム
共重合体ブロック共重合体が挙げられる。However, R3 in the formula is a hydrogen atom, an alkyl group, or a halogen group, R4 is a hydrogen atom, an alkyl group, or a vinyl group, m is an integer from 1 to 5, and if m is 2 or more, R4 may be mutually different groups. Examples of these include polystyrene, poly-alpha-methylstyrene,
Examples include homopolymers such as polychlorostyrene, random copolymers, and block copolymers.
【００１６】本発明に於てはかかるポリスチレンが、酸
化防止剤、潤滑剤、耐磨耗剤など他の添加剤を含んでい
ても差し支えない。また、本発明に用いるポリスチレン
は、前述したポリスチレン系樹脂のみではなく、ゴム変
性ポリスチレン等の変性ポリスチレン、スチレン−ブタ
ジエン共重合体やそれらを水添させたもの、スチレン−
ブタジエン−アクリロニトリル共重合体なども用いるこ
とができる。さらに、使用するにあたっては、これらを
、単独で用いても良いし、２種以上組合せて用いること
もできる。In the present invention, the polystyrene may contain other additives such as antioxidants, lubricants, and anti-wear agents. In addition, the polystyrene used in the present invention is not limited to the above-mentioned polystyrene resin, but also modified polystyrene such as rubber modified polystyrene, styrene-butadiene copolymer, hydrogenated products thereof, and styrene-butadiene copolymer.
Butadiene-acrylonitrile copolymers and the like can also be used. Furthermore, when used, these may be used alone or in combination of two or more.
【００１７】ポリスチレンを溶解させるための溶媒は次
のようなものが使用できる。例えば、ベンゼン、トルエ
ン、エチルベンゼン、キシレン等の芳香族炭化水素、ク
ロロホルム、１，２−ジクロルエタン、クロルベンゼン
、ジクロルベンゼンなどのハロゲン化炭化水素、ニトロ
ベンゼンのようなニトロ化合物などが挙げられる。また
ポリスチレン溶液中には少量のポリスチレンに対する貧
溶媒が混入していても良い。The following solvents can be used to dissolve polystyrene. Examples include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene, and nitro compounds such as nitrobenzene. Further, a small amount of a poor solvent for polystyrene may be mixed in the polystyrene solution.
【００１８】かかるポリスチレンの溶液を先のポリフェ
ニレンエーテル粉粒体を分散させるための混合溶媒中に
添加した際、ポリスチレンが析出するような組成になる
ようポリフェニレンエーテル粉粒体を分散させるための
混合溶媒の組成を調整する。このように調整したポリフ
ェニレンエーテル粉粒体の分散系にポリスチレンの溶液
を接触せしめることによって簡単にポリフェニレンエー
テルの微粒子が肥大化する効果が得られる。[0018] A mixed solvent for dispersing the polyphenylene ether powder so as to have a composition such that polystyrene precipitates when the polystyrene solution is added to the mixed solvent for dispersing the polyphenylene ether powder. Adjust the composition of By bringing a polystyrene solution into contact with the polyphenylene ether powder dispersion prepared in this manner, the effect of enlarging the polyphenylene ether fine particles can be easily obtained.
【００１９】ポリフェニレンエーテル粉粒体の分散系に
接触せしめるポリスチレンの溶液の濃度は０．１〜３０
ｗｔ％であることが好ましく、より好ましくは２〜２０
ｗｔ％であることが望ましい。またポリスチレンのポリ
フェニレンエーテルに対する添加量はポリフェニレンエ
ーテル１００重量部に対して０．１〜２０重量部が好ま
しく、より好ましくは０．５〜１０重量部が望ましい。The concentration of the polystyrene solution brought into contact with the dispersion of polyphenylene ether powder is 0.1 to 30.
It is preferably wt%, more preferably 2 to 20
It is desirable that it is wt%. The amount of polystyrene added to polyphenylene ether is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of polyphenylene ether.
【００２０】かかるポリスチレンの溶液を先のポリフェ
ニレンエーテル粉粒体分散系に接触せしめる際、バッチ
方式で行う場合にはポリフェニレンエーテル粉粒体分散
系を撹拌槽に入れた後、ポリスチレンの溶液を接触せし
めても良く、ポリフェニレンエーテル粉粒体分散系とポ
リスチレンの溶液を同時に撹拌槽に入れ接触せしめても
良く、ポリスチレンの溶液を撹拌槽に入れた後、ポリフ
ェニレンエーテル粉粒体分散系に接触せしめても良い。
接触せしめる温度は０℃〜６０℃の範囲で行うことが操
作上好ましい。[0020] When bringing the polystyrene solution into contact with the polyphenylene ether powder dispersion system, if a batch method is used, the polyphenylene ether powder dispersion system is placed in a stirring tank and then brought into contact with the polystyrene solution. Alternatively, the polyphenylene ether powder dispersion system and the polystyrene solution may be placed in a stirring tank at the same time and brought into contact with each other, or the polystyrene solution may be placed in a stirring tank and then brought into contact with the polyphenylene ether powder dispersion system. good. For operational reasons, it is preferable that the temperature of contact be in the range of 0°C to 60°C.
【００２１】また本発明の製造方法は撹拌機のついた撹
拌槽中で行うことが望ましいが、場合によってはマグネ
チックスターラーによっても、また振とう機による接触
でも何ら差し支えない。接触に要する時間は１分〜３０
分で充分ある。[0021] The production method of the present invention is preferably carried out in a stirring tank equipped with a stirrer, but depending on the case, contact with a magnetic stirrer or a shaker may be used without any problem. The time required for contact is 1 minute to 30 minutes.
A minute is enough.
【００２２】またポリフェニレンエーテルの連続製造法
においては重合工程、触媒や副生物の除去等の洗浄工程
などどのような製造工程においても、ポリフェニレンエ
ーテル粉粒体が有機溶媒分散系として存在していればそ
こにポリスチレン溶液と接触せしめることができる。ま
た別個にポリフェニレンエーテル粉粒体の粒子を凝集さ
せる工程を設けても良い。例えば、重合工程の直後にポ
リスチレン溶液を加える場合には図１のようにポリフェ
ニレンエーテルの重合溶液から粒子を析出させる析出槽
Ｂにポリスチレンの溶液を連続的に接触させる方法（１
）または別個に混合槽Ｃを設けてこれにポリスチレンの
溶液を連続的に接触させる方法（２）の様な方法がとら
れる。しかし、本発明はこれらの方法に限定されるもの
ではない。上記の方法（１）を使用するにあたっては混
合槽Ｃは必ずしも必要では無い。In addition, in the continuous production method of polyphenylene ether, if polyphenylene ether powder is present as an organic solvent dispersion system in any production process such as the polymerization process and the cleaning process such as the removal of catalysts and by-products, It can be brought into contact with a polystyrene solution. Further, a separate step of aggregating the particles of polyphenylene ether powder may be provided. For example, when adding a polystyrene solution immediately after the polymerization step, as shown in Figure 1, there is a method (1
) or method (2), in which a separate mixing tank C is provided and the polystyrene solution is brought into continuous contact with the mixing tank C, may be used. However, the present invention is not limited to these methods. When using the above method (1), the mixing tank C is not necessarily required.
【００２３】[0023]
【実施例】以下、実施例によって本発明を説明するが本
発明はこれらの例によって何ら制限されるものではない
。なお、ポリフェニレンエーテルとしては、ポリ−（２
，６−ジメチル−１，４−フェニレン）−エーテルを用
いて実施した。またポリフェニレンエーテルの粒径分布
はレーザー式粒径分布測定装置によって測定した。[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, as polyphenylene ether, poly-(2
,6-dimethyl-1,4-phenylene)-ether. Further, the particle size distribution of polyphenylene ether was measured using a laser particle size distribution measuring device.
【００２４】実施例１
１０μｍ以下の粒径の微粒子を１０ ｖｏｌ％含有する
平均粒径３５μｍのポリフェニレンエーテル樹脂粉粒体
（ηｓｐ／Ｃ＝０．５２）をキシレン６０重量部、ブタ
ノール２０重量部、メタノール２０重量部からなる混合
溶媒に分散させた。この分散系におけるポリフェニレン
エーテル樹脂粉粒体の濃度は２２ｗｔ％である。これに
重量平均重合度約３０万のポリスチレン（旭化成工業株
式会社製スタイロンＧＰ６８５）をキシレンに溶解させ
た溶液（ポリスチレン濃度１０ｗｔ％）を先のポリフェ
ニレンエーテル樹脂粉粒体分散系にポリスチレンの量が
ポリフェニレンエーテル１００重量部に対し５．０重量
部になるように混合し撹拌機付きの撹拌槽中、５００ｒ
ｐｍ で３０分間撹拌処理した。処理後のポリフェニレ
ンエーテル粉粒体の平均粒径は６０μｍで１０μｍ以下
の微粒子の割合は２．５ ｖｏｌ％になった。Example 1 Polyphenylene ether resin powder (ηsp/C=0.52) with an average particle size of 35 μm containing 10 vol% of fine particles with a particle size of 10 μm or less was mixed with 60 parts by weight of xylene, 20 parts by weight of butanol, It was dispersed in a mixed solvent consisting of 20 parts by weight of methanol. The concentration of polyphenylene ether resin powder in this dispersion system is 22 wt%. A solution (polystyrene concentration 10 wt%) in which polystyrene with a weight average degree of polymerization of about 300,000 (Styron GP685 manufactured by Asahi Kasei Corporation) was dissolved in xylene was added to the above polyphenylene ether resin powder dispersion system so that the amount of polystyrene was equal to that of polyphenylene. Mix 100 parts by weight of ether to 5.0 parts by weight, and mix in a stirring tank with a stirrer for 500 r.
The mixture was stirred at pm for 30 minutes. The average particle diameter of the polyphenylene ether powder after treatment was 60 μm, and the proportion of fine particles of 10 μm or less was 2.5 vol%.
【００２５】比較例１
ポリスチレンの溶液の代りにポリスチレンの入っていな
い溶媒のみを実施例１に相当する量混合した以外は実施
例１と全く同様の方法で処理した。処理後のポリフェニ
レンエーテル粉粒体の平均粒径は３５μｍ、１０μｍ以
下の微粒子の割合は１０ ｖｏｌ％でもとのポリフェニ
レンエーテル粉粒体となんら変化なかった。Comparative Example 1 The process was carried out in exactly the same manner as in Example 1, except that instead of the polystyrene solution, only a polystyrene-free solvent was mixed in an amount corresponding to Example 1. The average particle size of the polyphenylene ether powder after treatment was 35 μm, and the proportion of fine particles of 10 μm or less was 10 vol%, which was no different from the original polyphenylene ether powder.
【００２６】実施例２
図１のポリフェニレンエーテルの連続重合法を使用して
前記の方法（２）に従い重量平均重合度約３０万のポリ
スチレン（旭化成工業株式会社製スタイロンＧＰ６８５
）をキシレンに溶解させた溶液（ポリスチレン濃度１０
ｗｔ％）を混合槽Ｃにおけるポリフェニレンエーテル１
００重量部に対しポリスチレンが５．０重量部になるよ
うに混合槽Ｃへ連続的に混合した。混合槽Ｃにおけるポ
リフェニレンエーテル粉粒体は定常的に２０ｗｔ％であ
る。析出槽Ｂから流出するポリフェニレンエーテル粉粒
体の平均粒径は２３μｍ、１０μｍ以下の微粒子の割合
は１８ｖｏｌ ％であったが、混合槽Ｃから流出するポ
リフェニレンエーテル粉粒体の平均粒径は４１５μｍ、
１０μｍ以下の微粒子の割合は０．０１ ｖｏｌ％以下
になった。Example 2 Using the continuous polymerization method of polyphenylene ether shown in FIG.
) dissolved in xylene (polystyrene concentration 10
wt%) to polyphenylene ether 1 in mixing tank C.
Polystyrene was continuously mixed into mixing tank C so that the amount of polystyrene was 5.0 parts by weight per 00 parts by weight. The polyphenylene ether powder in mixing tank C is constantly 20 wt%. The average particle size of the polyphenylene ether powder flowing out from precipitation tank B was 23 μm, and the proportion of fine particles of 10 μm or less was 18 vol %, but the average particle size of the polyphenylene ether powder flowing out from mixing tank C was 415 μm.
The proportion of fine particles of 10 μm or less was 0.01 vol% or less.
【００２７】比較例２
実施例２でポリスチレンの溶液の代わりにポリスチレン
の入っていない溶媒のみを実施例２に相当する量連続的
に混合槽Ｃに混合した以外は実施例２と全く同様の方法
で処理した。混合槽Ｃから流出するポリフェニレンエー
テル粉粒体の平均粒径は２３μｍ、１０μｍ以下の微粒
子の割合は１８ ｖｏｌ％であった。Comparative Example 2 Completely the same method as in Example 2, except that instead of the polystyrene solution in Example 2, only a polystyrene-free solvent was continuously mixed in the mixing tank C in an amount corresponding to Example 2. Processed with. The average particle size of the polyphenylene ether powder flowing out from mixing tank C was 23 μm, and the proportion of fine particles of 10 μm or less was 18 vol%.
【００２８】実施例３
重量平均重合度約１０万のポリスチレンを用いた以外は
実施例１と全く同様の方法で処理した。処理後のポリフ
ェニレンエーテル粉粒体の平均粒径は５８μｍ、１０μ
ｍ以下の微粒子の割合は２．３ ｖｏｌ％であった。Example 3 The process was carried out in exactly the same manner as in Example 1, except that polystyrene having a weight average degree of polymerization of about 100,000 was used. The average particle size of the polyphenylene ether powder after treatment is 58 μm and 10 μm.
The proportion of fine particles with a diameter of m or less was 2.3 vol%.
【００２９】実施例４
重量平均重合度約５０万のポリスチレンを用いた以外は
実施例１と全く同様の方法で処理した。処理後のポリフ
ェニレンエーテル粉粒体の平均粒径は６３μｍ、１０μ
ｍ以下の微粒子の割合は２．０ ｖｏｌ％であった。Example 4 The process was carried out in exactly the same manner as in Example 1 except that polystyrene having a weight average degree of polymerization of about 500,000 was used. The average particle size of the polyphenylene ether powder after treatment is 63 μm and 10 μm.
The proportion of fine particles with a diameter of m or less was 2.0 vol%.
【００３０】実施例５
重量平均重合度約３０万のポリスチレン（旭化成工業株
式会社製スタイロンＧＰ６８５）をキシレンに溶解させ
た溶液（ポリスチレン濃度１０ｗｔ％）をポリフェニレ
ンエーテル樹脂粉粒体分散系にポリスチレンの量がポリ
フェニレンエーテル１００重量部に対し１．０重量部に
なるように混合した以外は実施例１と全く同様の方法で
処理した。処理後のポリフェニレンエーテル粉粒体の平
均粒径は４０μｍで１０μｍ以下の微粒子の割合は３．
０ ｖｏｌ％であった。Example 5 A solution (polystyrene concentration 10 wt%) in which polystyrene with a weight average degree of polymerization of about 300,000 (Styron GP685 manufactured by Asahi Kasei Corporation) was dissolved in xylene was added to a polyphenylene ether resin powder dispersion system in an amount of polystyrene. The process was carried out in exactly the same manner as in Example 1, except that the mixture was mixed in an amount of 1.0 parts by weight with respect to 100 parts by weight of polyphenylene ether. The average particle diameter of the polyphenylene ether powder after treatment was 40 μm, and the proportion of fine particles of 10 μm or less was 3.
It was 0 vol%.
【００３１】実施例６
重量平均重合度約３０万のポリスチレン（旭化成工業株
式会社製スタイロンＧＰ６８５）をキシレンに溶解させ
た溶液（ポリスチレン濃度１０ｗｔ％）をポリフェニレ
ンエーテル樹脂粉粒体分散系にポリスチレンの量がポリ
フェニレンエーテル１００重量部に対し１０重量部にな
るように混合した以外は実施例１と全く同様の方法で処
理した。処理後のポリフェニレンエーテル粉粒体の平均
粒径は９５μｍで１０μｍ以下の微粒子の割合は０．０
５ ｖｏｌ％になった。Example 6 A solution (polystyrene concentration 10 wt%) in which polystyrene with a weight average degree of polymerization of approximately 300,000 (Styron GP685 manufactured by Asahi Kasei Corporation) was dissolved in xylene was added to a polyphenylene ether resin powder dispersion system in an amount of polystyrene. The process was carried out in exactly the same manner as in Example 1, except that 10 parts by weight of polyphenylene ether was mixed with 100 parts by weight of polyphenylene ether. The average particle size of the polyphenylene ether powder after treatment is 95 μm, and the proportion of fine particles of 10 μm or less is 0.0
It became 5 vol%.
【００３２】実施例７
重量平均重合度約３０万のポリスチレン（旭化成工業株
式会社製スタイロンＧＰ６８５）をキシレンに溶解させ
た溶液（ポリスチレン濃度５．０ｗｔ％）をポリフェニ
レンエーテル樹脂粉粒体分散系にポリスチレンの量がポ
リフェニレンエーテル１００重量部に対し３．０重量部
になるように混合した以外は実施例１と全く同様の方法
で処理した。処理後のポリフェニレンエーテル粉粒体の
平均粒径は４５μｍで１０μｍ以下の微粒子の割合は２
．９ ｖｏｌ％になった。これらの結果を表１にまとめ
て示す。Example 7 A solution (polystyrene concentration 5.0 wt%) in which polystyrene with a weight average degree of polymerization of approximately 300,000 (Stylon GP685 manufactured by Asahi Kasei Corporation) was dissolved in xylene was added to a polyphenylene ether resin powder dispersion system. The process was carried out in exactly the same manner as in Example 1, except that the amount of 3.0 parts by weight was mixed with respect to 100 parts by weight of polyphenylene ether. The average particle size of the polyphenylene ether powder after treatment is 45 μm, and the proportion of fine particles of 10 μm or less is 2.
．． It became 9 vol%. These results are summarized in Table 1.
【００３３】[0033]
【表１】[Table 1]
【００３４】[0034]
【発明の効果】本発明は、従来取扱いが難しく、多くの
トラブルの原因となっていた微粒子状のポリフェニレン
エーテルもしくは変性ポリフェニレンエーテル樹脂の粒
子径を肥大化することに成功したものであり、その結果
、該樹脂粉粒体の取扱い性が大幅に向上したという効果
を有する。[Effects of the Invention] The present invention has succeeded in enlarging the particle size of fine particulate polyphenylene ether or modified polyphenylene ether resin, which was conventionally difficult to handle and caused many troubles. This has the effect of greatly improving the handling properties of the resin powder.
【図１】ポリフェニレンエーテルの連続製造法でポリス
チレン溶液を接触せしめることによりポリフェニレンエ
ーテル樹脂粉粒体を凝集する方法を示す概略工程図であ
る。FIG. 1 is a schematic process diagram showing a method for agglomerating polyphenylene ether resin powder by contacting with a polystyrene solution in a continuous polyphenylene ether production method.
Ａ ポリフェニレンエーテ
ルに対する貧溶媒の添加経路A Addition route of poor solvent to polyphenylene ether
Claims (2)
有機溶媒分散系にポリスチレン溶液を接触させることを
特徴とする粒子径の肥大化したポリフェニレンエーテル
または変性ポリフェニレンエーテル樹脂粉粒体の製造方
法。1. A method for producing polyphenylene ether or modified polyphenylene ether resin powder with enlarged particle size, which comprises bringing a polystyrene solution into contact with an organic solvent dispersion of polyphenylene ether resin powder.
分散させる有機溶媒がポリフェニレンエーテルの良溶媒
とポリフェニレンエーテルの貧溶媒の混合溶媒からなる
請求項１記載の製造方法。2. The manufacturing method according to claim 1, wherein the organic solvent in which the polyphenylene ether resin powder is dispersed comprises a mixed solvent of a good solvent for polyphenylene ether and a poor solvent for polyphenylene ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6074391A JP3006116B2 (en) | 1991-01-10 | 1991-01-10 | Method for producing polymer powder having enlarged particle diameter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6074391A JP3006116B2 (en) | 1991-01-10 | 1991-01-10 | Method for producing polymer powder having enlarged particle diameter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04239031A true JPH04239031A (en) | 1992-08-26 |
| JP3006116B2 JP3006116B2 (en) | 2000-02-07 |
Family
ID=13151051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6074391A Expired - Fee Related JP3006116B2 (en) | 1991-01-10 | 1991-01-10 | Method for producing polymer powder having enlarged particle diameter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3006116B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017501285A (en) * | 2014-01-03 | 2017-01-12 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Dust-free poly (phenylene ether) particles |
-
1991
- 1991-01-10 JP JP6074391A patent/JP3006116B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017501285A (en) * | 2014-01-03 | 2017-01-12 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Dust-free poly (phenylene ether) particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3006116B2 (en) | 2000-02-07 |
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