JPH0236228A - Purification of aromatic polyether polymer - Google Patents
Purification of aromatic polyether polymerInfo
- Publication number
- JPH0236228A JPH0236228A JP18774388A JP18774388A JPH0236228A JP H0236228 A JPH0236228 A JP H0236228A JP 18774388 A JP18774388 A JP 18774388A JP 18774388 A JP18774388 A JP 18774388A JP H0236228 A JPH0236228 A JP H0236228A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- polymer
- aromatic polyether
- polyether polymer
- mixture
- 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
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 35
- 229920000570 polyether Polymers 0.000 title claims abstract description 32
- 238000000746 purification Methods 0.000 title description 10
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000006227 byproduct Substances 0.000 claims abstract description 16
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229920002959 polymer blend Polymers 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 28
- 238000001556 precipitation Methods 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000013557 residual solvent Substances 0.000 description 7
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（ａ）発明の目的
本発明は、芳香族ポリエーテル重合体の精製方法、特に
、芳香族ポリエーテル重合体混合物から芳香族ポリエー
テル重合体を効率的に分離し、重合体中の反応溶媒残留
量と副生酸物残留量が少ない芳香族ポリエーテル重合体
を得る精製方法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Object of the Invention The present invention provides a method for purifying an aromatic polyether polymer, in particular, a method for efficiently separating an aromatic polyether polymer from an aromatic polyether polymer mixture; The present invention relates to a purification method for obtaining an aromatic polyether polymer with a small amount of residual reaction solvent and by-product acid in the polymer.
（産業上の利用分野）
本発明の精製方法は、耐熱性・難燃性が良好で、かつ機
械的性質・電気的性質が優れた電気・電子機器部品・航
空機部品・自動車部品・自動車部品・衛生食品機器部品
などに広く活用される芳香族ポリエーテル樹脂を得るの
に有利に使用される。(Industrial Application Field) The refining method of the present invention is applicable to electric/electronic equipment parts, aircraft parts, automobile parts, automobile parts, etc., which have good heat resistance, flame retardance, and excellent mechanical and electrical properties. It is advantageously used to obtain aromatic polyether resins that are widely used in sanitary food equipment parts, etc.
（従来の技術）
従来、芳香族ポリエーテル重合体の代表的な製造方法と
して、二価フェノールのジアルカリ金属塩と芳香族シバ
ライド類とを反応させる方法がよく知られている。この
際、極性の不活性溶媒を反応媒体として使用することに
より、比較的低温度で反応を実施し、重合体と溶媒とを
効率よく分離することが、芳香族ポリエーテル重合体を
工業的に製造するにあたって重要となる。(Prior Art) Conventionally, a method of reacting a dialkali metal salt of a dihydric phenol with an aromatic cybaride is well known as a typical method for producing an aromatic polyether polymer. At this time, by using a polar inert solvent as a reaction medium, the reaction can be carried out at a relatively low temperature and the polymer and solvent can be efficiently separated. This is important in manufacturing.
通常、二価フェノールのジアルカリ金属塩と芳香族シバ
ライド類とを極性溶媒中で重縮合せしめることによって
得られる重合体混合物は、生成重合体・副生塩及び反応
溶媒から成っている。このような重合体混合物から重合
体を分離する方法として種々の方法が提案されている。Usually, a polymer mixture obtained by polycondensing a dialkali metal salt of a dihydric phenol and an aromatic cybaride in a polar solvent consists of a produced polymer, a by-product salt, and a reaction solvent. Various methods have been proposed for separating polymers from such polymer mixtures.
特公昭５２−３９０８０号公報では、不活性高融点溶媒
を用い、溶媒の融点以下に冷却、固化、粉砕した後、メ
タノール、水等で抽出する方法が提案されている。Japanese Patent Publication No. 52-39080 proposes a method in which an inert high-melting point solvent is used, the mixture is cooled to below the melting point of the solvent, solidified, pulverized, and then extracted with methanol, water, or the like.
特公昭４９−１１０７９１号公報では、非溶媒上に噴霧
する方法。特開昭５１−１３４７９９号公報では重合体
溶液を高圧帯域から低圧帯域ヘフラッシュし、溶媒を除
去する方法が提案されている。これらの方法では、大部
分の溶媒は除去できたとしても、かなりの量の高極性溶
媒の残存は避けられないが、凝固した固体から溶媒を抽
出するために、溶媒による多数回の洗浄を要し、多量の
非溶媒が必要である。また、得られた重合体の見かけの
比重（嵩密度）が極めて小さい状態で回収する結果とな
り、嵩密度の低下は、重合体を乾燥したり、ペレット化
する際の容積効率の低下、さらには作業性の悪化をまね
くことから好ましくない。Japanese Patent Publication No. 49-110791 discloses a method of spraying onto a non-solvent. JP-A-51-134799 proposes a method in which a polymer solution is flushed from a high pressure zone to a low pressure zone to remove the solvent. In these methods, even if most of the solvent can be removed, a significant amount of highly polar solvent remains, but many washes with solvent are required to extract the solvent from the solidified solid. However, a large amount of non-solvent is required. In addition, the resulting polymer is recovered with an extremely low apparent specific gravity (bulk density), and a decrease in bulk density leads to a decrease in volumetric efficiency when drying or pelletizing the polymer, and even This is not preferable because it leads to deterioration of workability.
（発明が解決しようとする課題）
本発明の芳香族ポリエーテル重合体の精製方法は、芳香
族ポリエーテル重合体の反応溶媒及び副生塩の残存量が
少なく、作業性良好な重合体を得ることができる効率的
な精製法を提供しようとするものである。(Problems to be Solved by the Invention) The method for purifying an aromatic polyether polymer of the present invention provides a polymer with a small amount of residual reaction solvent and by-product salt of the aromatic polyether polymer and good workability. The purpose of this study is to provide an efficient purification method.
（ｂ）発明の構成
（課題を解決するための手段）
本発明の芳香族ポリエーテル重合体の精製方法は、生成
重合体・副生成物及び極性溶媒等から成る重合体混合物
から、芳香族ポリエーテル重合体を単離するにあたり、
必要に応じて副生成物等を除去した後、芳香族ポリエー
テル重合体に対して非溶媒である揮発性溶媒中に芳香族
ポリエーテル重合体混合物を添加、析出と同時に機械的
に粉砕することにより粒状化した後、非溶媒（粉砕特使
用した非溶媒と異なる非溶媒でもよいが、回収の容易さ
から同一溶媒を用いるのが好ましい。）で析出すること
を特徴とする精製方法である。さらに、芳香族ポリエー
テル重合体混合物を６０重量％〜４００重量％（芳香族
ポリエーテル重合体混合物に対して）の非溶媒中に添加
することを特徴とする精製方法である。即ち、重合体中
の反応溶媒残留量と副生酸物残留量を極力少なくするた
めの手段として、粉砕時において、粒状化した重合体の
多孔質表面が塞がれないように、融着（ブロッキング）
しない条件下で行うのが、効率的に精製するための重要
な点である。具体的には、反応溶媒の種類・濃度・非溶
媒の種類、処理温度等により異なるが、芳香族ポリエー
テル重合体混合物に対して６０重量％〜４００重量％の
非溶媒中に芳香族ポリエーテル重合体混合物を添加する
ことが重要である。６０重量％以下では、粒状化した重
合体の融着が部分的に生じ、結果として、後処理工程に
おいて、重合体混合物中からの溶媒の除去効率が悪くな
る。非溶媒で反応溶媒等を抽出する場合、多数回の洗浄
を要し、多量の非溶媒が必要となる。また、４００重量
％以上では、使用する非溶媒の量が増大し、粉砕時の装
置容量のアップにつながり、特段の効果は、期待できな
いことから、経済的でない。ここで、副生成物とは、例
えば、ジハロゲン化アルカリ金属塩（ＫＣＩ 、 Ｎａ
Ｃ１等）である。反応溶媒としては、ジメチルスルホキ
シド、テトラメチレンスルホン、ジフェニルスルホン、
１，３−ジメチル−２−イミダゾリジノン、Ｎ、Ｎ−ジ
メチルホルムアミド、 Ｎ、Ｎ−ジメチルアセトアミド
、ヘキサメチルホスホロトリアミド、Ｎ−メチル−２−
ピロリドン、ジメチルスルホン、ジエチルスルホキシド
等が挙げられる。(b) Structure of the Invention (Means for Solving the Problems) The method for purifying an aromatic polyether polymer of the present invention is to purify an aromatic polyether polymer from a polymer mixture consisting of a produced polymer, a by-product, a polar solvent, etc. In isolating the ether polymer,
After removing by-products as necessary, the aromatic polyether polymer mixture is added to a volatile solvent that is a non-solvent for the aromatic polyether polymer, and mechanically pulverized at the same time as precipitation. This is a purification method characterized by precipitating with a non-solvent (a different non-solvent than the non-solvent used for pulverization may be used, but it is preferable to use the same solvent for ease of recovery). Furthermore, the purification method is characterized in that the aromatic polyether polymer mixture is added to a non-solvent in an amount of 60% to 400% by weight (based on the aromatic polyether polymer mixture). In other words, as a means to minimize the residual amount of reaction solvent and by-product acid in the polymer, fusion bonding ( blocking)
An important point for efficient purification is to perform the purification under conditions that do not Specifically, it varies depending on the type and concentration of the reaction solvent, the type of nonsolvent, the treatment temperature, etc., but the amount of aromatic polyether in the nonsolvent is 60% to 400% by weight based on the aromatic polyether polymer mixture. It is important to add the polymer mixture. When the amount is less than 60% by weight, the granulated polymer partially fuses, resulting in poor removal efficiency of the solvent from the polymer mixture in the post-treatment step. When extracting the reaction solvent etc. with a non-solvent, multiple washings are required and a large amount of non-solvent is required. Moreover, if it exceeds 400% by weight, the amount of non-solvent used increases, which leads to an increase in the capacity of the equipment during pulverization, and no particular effect can be expected, which is not economical. Here, by-products are, for example, dihalogenated alkali metal salts (KCI, Na
C1 etc.). As a reaction solvent, dimethyl sulfoxide, tetramethylene sulfone, diphenyl sulfone,
1,3-dimethyl-2-imidazolidinone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphorotriamide, N-methyl-2-
Examples include pyrrolidone, dimethylsulfone, diethylsulfoxide, and the like.
本発明の精製方法に適用される芳香族ポリエーテル重合
体とは、一般に、
（式中２は、直接結合又は１〜５個の炭素原子を有する
アルキレン又はアルキリデン基、又は５〜１５個の炭素
原子を有するシクロアルキレン又はシクロアルキリデン
基、或いは−ｏ＋、−ＣＯ−ｓｏ２−、−ｓ−のいずれ
かの基を表す。Ｒ１、Ｒ２、Ｒ３。The aromatic polyether polymer applied to the purification method of the present invention generally refers to the following: (wherein 2 is a direct bond or an alkylene or alkylidene group having 1 to 5 carbon atoms, or 5 to 15 carbon atoms) Represents a cycloalkylene or cycloalkylidene group having an atom, or a group of -o+, -CO-so2-, -s-.R1, R2, R3.
Ｒ４は−ＣＨ３−、−Ｃ２Ｈ５−、−ＣＨ（ＣＨ３）２
− 。R4 is -CH3-, -C2H5-, -CH(CH3)2
−.
ＯＣＨ３、０Ｃ２Ｈ５−の基の中から選ばれ、Ｒ１とＲ
２及びＲ３とＲ４は同一でも異なっていてもよい。selected from OCH3, 0C2H5-, R1 and R
2 and R3 and R4 may be the same or different.
ｎｌ ｌ ｎ２１ ｎ３ ＋ ｎ４は０〜４の整数を表
す。２′は一５ｏ２−又は−ＣＯ−である。）の繰り返
し単位を有するものである。nl l n21 n3 + n4 represents an integer from 0 to 4. 2' is -5o2- or -CO-. ) has a repeating unit.
一例として、式
の繰り返し単位を持ち、別の例としては式の繰り返し単
位を持つものである。One example is having a repeating unit of the formula, and another example is having a repeating unit of the formula.
また、本発明に使用される非溶媒としては、重合体を溶
解しないもので、水の他にヘキサ、ン、トルエン等の炭
化水素、メタノール、エタノール、プロパツール 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 メチルイソブチルケトンの如きジアルキルケトン等
が挙げられる。In addition, non-solvents used in the present invention are those that do not dissolve the polymer, such as water, hydrocarbons such as hexane, alcohol, toluene, alcohols such as methanol, ethanol, propatool butanol, acetone, methyl ethyl ketone, methyl, etc. Examples include dialkyl ketones such as isobutyl ketone.
本発明で使用される重合体混合物（樹脂溶液）の重合体
濃度は１０〜７０重量％、好ましくは、１５〜５０重量
％であることが必要である。１０重量％以下では、微粉
末化するか、もしくは均一な粒径のものが得られ難い。The polymer concentration of the polymer mixture (resin solution) used in the present invention needs to be 10 to 70% by weight, preferably 15 to 50% by weight. If it is less than 10% by weight, it becomes fine powder or it is difficult to obtain particles with uniform particle size.
７０重量％以上では析出の際に析出粒子表面化部分が迅
速に固化してしまう結果、析出粒子内部の析出が遅くな
る傾向がある。また、析出・粉砕処理における装置とし
ては、プロペラ又は、タービンブレードのような高速回
転による高ぜん断分散装置が使用可能であるが短時間で
析出と同時に粉砕する方法として、ニーダ−、ラインミ
キサー等の混線タイプ、ボールミル、ロッドミル等の粉
砕タイプ等が好ましい。これらの組み合せによる方法を
用いてもよい。得られる重合体の粒子径は３００〜５０
０ｐｍ程度が望ましいものである。処理温度としては、
通常室温下で処理するのが好ましいが、必要に応じて加
温することも可能である。ただし、粒状化した重合体が
融着を生じない範囲で行う必要がある。If the content is 70% by weight or more, the surface portion of the precipitated particles will solidify rapidly during precipitation, resulting in a tendency for the precipitation inside the precipitated particles to slow down. In addition, as a device for the precipitation/pulverization process, a high-shear dispersion device with high-speed rotation such as a propeller or turbine blade can be used, but as a method for simultaneously precipitating and pulverizing in a short time, a kneader, line mixer, etc. A mixed wire type, a pulverizing type such as a ball mill, a rod mill, etc. are preferable. A combination of these methods may also be used. The particle size of the obtained polymer is 300-50
Approximately 0 pm is desirable. As for the processing temperature,
Although it is usually preferable to carry out the treatment at room temperature, it is also possible to heat the treatment if necessary. However, it is necessary to carry out this process within a range that does not cause fusion of the granulated polymer.
（実施例）
以下、実施例により説明する。実施例中もしくは比較例
中の測定は、次の方法により実施した。(Example) Examples will be described below. Measurements in Examples and Comparative Examples were carried out by the following method.
重合体中の溶媒残留量は、ガスクロマトグラフにより、
アルカリ金属イオンの定量は原子吸光分析法によった。The amount of solvent remaining in the polymer is determined by gas chromatography.
Alkali metal ions were determined by atomic absorption spectrometry.
尚、ここで使用する比率、倍率は特記せぬかぎり重量基
準である。Note that the ratios and magnifications used here are based on weight unless otherwise specified.
実施例１
撹拌機、コンデンサー及び窒素供給口を備えた三ツロフ
ラスコ（容量１１）中に４，４′−ジヒドロキシジフェ
ニルスルホン（６９，８７ｇ） 、 ４．４’−ジクロ
ロジフェニルスルホン（８２，１５ｇ）及び炭酸ナトリ
ウム（３１，３２ｇ）を併給した。更に、反応溶媒とし
て、テトラメチレンスルホン（２００，９８ｇ）を添加
、撹拌し、窒素流下で２３５°Ｃに加熱した。６時間後
、生成した粘調な溶液にテトラメチレンスルホン（３７
６，２０ｇ）を加え、ガス状メチルクロリドを１時間通
した。濾過により、副生塩を除去した後、事前にメタノ
ール（反応粗液に対して３倍量）を仕込んだミキサー内
に添加、高速撹拌で粉砕、スリラー化した後、洗浄を４
回繰り返し行った。処理後の固形分を１４５°Ｃで熱風
乾燥した。得られた重合体の残留溶媒濃度は０．１０重
量％であった。ナトリウム含量は５０ｐｐｍであった。Example 1 4,4'-dihydroxydiphenylsulfone (69,87g), 4,4'-dichlorodiphenylsulfone (82,15g) and Sodium carbonate (31.32 g) was co-fed. Furthermore, tetramethylene sulfone (200.98 g) was added as a reaction solvent, stirred, and heated to 235° C. under nitrogen flow. After 6 hours, tetramethylene sulfone (37
6.20 g) was added and gaseous methyl chloride was passed through for 1 hour. After removing the by-product salts by filtration, it was added to a mixer containing methanol (3 times the volume of the reaction crude liquid), pulverized with high-speed stirring, turned into a thriller, and washed for 4 times.
I did it repeatedly. The solid content after treatment was dried with hot air at 145°C. The residual solvent concentration of the obtained polymer was 0.10% by weight. Sodium content was 50 ppm.
実施例２
撹拌機、コンデンサー及び窒素供給口を備えた三ツロフ
ラスコ（容量１１）中に２，２−ビス−（４−ヒドロキ
シフェニル）プロパン（６８，５６ｇ）、４，４′−ジ
クロロジフェニルスルホン（８７，９０ｇ）及び炭酸ナ
トリウム（８３，ＯＯｇ）を挿入した。さらに、反応溶
媒としてジメチルアセトアミド（４５０，ＯＯｇ）を添
加、撹拌し、窒素流下で１６５°Ｃに加熱した。８時間
後、生成した粘調な溶液にジメチルアセトアミド（２０
２，９ｇ）を加え、ガス状メチルクロリドを１時間通し
た。濾過により、副生塩を除去した後、メタノール（反
応粗液に対して３倍量）を仕込んだミキサー内に添加、
高速撹拌で粉砕、スリラー化した後、洗浄を４回繰り返
した。処理後の固形分を１４０°Ｃで熱風乾燥した。得
られた重合体の残留溶媒濃度は０．０５重量％であった
。カリウム含量は３０ｐｐｍであった。Example 2 2,2-bis-(4-hydroxyphenyl)propane (68,56 g), 4,4'-dichlorodiphenylsulfone ( 87.90 g) and sodium carbonate (83.00 g). Furthermore, dimethylacetamide (450, OOg) was added as a reaction solvent, stirred, and heated to 165°C under a nitrogen flow. After 8 hours, dimethylacetamide (20
2.9 g) was added and gaseous methyl chloride was passed through for 1 hour. After removing by-product salts by filtration, add methanol (3 times the volume to the reaction crude liquid) into a mixer.
After pulverizing and turning into a thriller by high-speed stirring, washing was repeated four times. The solid content after the treatment was dried with hot air at 140°C. The residual solvent concentration of the obtained polymer was 0.05% by weight. Potassium content was 30 ppm.
比較例１
実施例１と同様な方法で反応を行って得られた反応溶液
を、濾過により、副生塩を除去した後、メタノール（反
応粗液に対して０．５倍量）を仕込んだミキサー内に添
加、高速撹拌で粉砕、スリラー化した後、洗浄を４回繰
り返した。処理後の固形分を１４５°Ｃで熱風乾燥した
。得られた重合体は不均一な形状で一部塊状のものがあ
った。残留溶媒濃度は０．５３重量％、ナトリウム含量
は１１００ｐｐであった。また、洗浄をさらに４回、計
８回行って、残留溶媒濃度を測定したところ、０．１重
量％まで低下させるに至らなかった。Comparative Example 1 A reaction solution obtained by carrying out a reaction in the same manner as in Example 1 was filtered to remove by-product salts, and then methanol (0.5 times the amount of the crude reaction solution) was added. The mixture was added to a mixer, pulverized by high-speed stirring, and turned into a thriller, followed by washing four times. The solid content after treatment was dried with hot air at 145°C. The obtained polymer had a non-uniform shape and some lumps. The residual solvent concentration was 0.53% by weight, and the sodium content was 1100 pp. Further, when washing was carried out four more times, a total of eight times, and the residual solvent concentration was measured, it was not found that the concentration could not be lowered to 0.1% by weight.
比較例２
実施例２と同様な方法で反応を行って得られた反応溶媒
を濾過により、副生塩を除去した後、メタノール（反応
粗液に対して０，５倍量）を仕込んだミキサー内に添加
、高速撹拌で粉砕、スリラー化した後、洗浄を４回繰り
返した。処理後の固形分を１４０°Ｃで熱風乾燥した。Comparative Example 2 A reaction solvent obtained by carrying out a reaction in the same manner as in Example 2 was filtered to remove by-product salts, and then methanol (0.5 times the amount of the reaction crude liquid) was charged into a mixer. The mixture was added to the liquid, pulverized with high-speed stirring, turned into a thriller, and washed four times. The solid content after the treatment was dried with hot air at 140°C.
得られた重合体の残留溶媒濃度は０．３８重量％であっ
た。カリウム含量は１２０ｐｐｍであった。さらに洗浄
を５回、計９回繰り返した後、残留溶媒濃度はようや＜
０．０５重量％まで低下させることができた。The residual solvent concentration of the obtained polymer was 0.38% by weight. Potassium content was 120 ppm. After repeating the washing 5 times for a total of 9 times, the residual solvent concentration decreased to <
The content could be reduced to 0.05% by weight.
比較例３
撹拌機、コンデンサー及び窒素供給口を備えた三ツロフ
ラスコ（容量１１）中に４，４′−ジヒドロキシジフェ
ニルスルホン（６９，８７ｇ） 、 ４．４−ジクロロ
ジフェニルスルホン（８２，１５ｇ）及び炭酸ナトリウ
ム（３９，３０ｇ）を供給した。更に反応溶媒としてジ
フェニルスルホン（２００，９８ｇ）を添加、撹拌し、
窒素流下で２６５°Ｃに加熱した。７時間後、生成した
粘調な溶液に、更にジフェニルスルホン（３７６，２０
ｇ）を加え、ガス状メチルクロリドを１時間通した。濾
過により副生塩を除去した後、冷却固化させ、ミキサー
で粉砕した。メタノール（反応粗液に対して３倍量）で
８回繰り返し洗浄を行い処理後の固形分を１４５°Ｃで
熱風乾燥した。得られた重合体の残留溶媒濃度は０．３
０重量％であった。ナトリウム含量は１１００ｐｐであ
った。Comparative Example 3 4,4'-dihydroxydiphenylsulfone (69,87g), 4,4-dichlorodiphenylsulfone (82,15g) and carbonic acid were placed in a three-turn flask (capacity 11) equipped with a stirrer, condenser and nitrogen inlet. Sodium (39.30g) was fed. Furthermore, diphenylsulfone (200.98 g) was added as a reaction solvent and stirred,
Heated to 265°C under nitrogen flow. After 7 hours, diphenylsulfone (376,20
g) was added and gaseous methyl chloride was passed through for 1 hour. After removing by-product salts by filtration, the mixture was solidified by cooling and pulverized with a mixer. Washing was repeated 8 times with methanol (3 times the volume of the reaction crude liquid), and the solid content after the treatment was dried with hot air at 145°C. The residual solvent concentration of the obtained polymer was 0.3
It was 0% by weight. The sodium content was 1100 pp.
（発明の効果）
本発明の芳香族ポリエーテル重合体の精製方法は、芳香
族ポリエーテル重合体に対して非溶媒である溶媒を一定
量使用して、芳香族ポリエーテル重合体混合物から副生
成物及び反応溶媒を効率的に除去する格別に優れた精製
方法であり、得られる芳香族ポリエーテル重合体は残留
塩及び残留反応溶媒量の極めて少ないものである。(Effect of the invention) The aromatic polyether polymer purification method of the present invention uses a certain amount of a solvent that is a non-solvent for the aromatic polyether polymer to produce by-products from the aromatic polyether polymer mixture. This is an exceptionally excellent purification method that efficiently removes compounds and reaction solvents, and the resulting aromatic polyether polymer has extremely low amounts of residual salts and residual reaction solvents.
Claims (1)
び反応溶媒を除去するにあたり、芳香族ポリエーテル重
合体に対して非溶媒である揮発性溶媒の中に芳香族ポリ
エーテル重合体混合物を添加し、芳香族ポリエーテル重
合体を析出させると同時に粉砕し、粒状化した後、非溶
媒で抽出することを特徴とする芳香族ポリエーテル重合
体の精製方法。 ２、芳香族ポリエーテル重合体混合物を、６０重量％〜
４００重量％（芳香族ポリエーテル重合体混合物に対し
て）の非溶媒中に添加することを特徴とする特許請求の
範囲第１項に記載の製法。[Claims] 1. When removing by-products and reaction solvents from an aromatic polyether polymer mixture, an aromatic polyether polymer is added to a volatile solvent that is a non-solvent for the aromatic polyether polymer. A method for purifying an aromatic polyether polymer, which comprises adding an ether polymer mixture, precipitating the aromatic polyether polymer, simultaneously crushing and granulating it, and then extracting with a non-solvent. 2. 60% by weight of aromatic polyether polymer mixture
The method according to claim 1, characterized in that it is added to 400% by weight (based on the aromatic polyether polymer mixture) of a non-solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18774388A JPH0236228A (en) | 1988-07-27 | 1988-07-27 | Purification of aromatic polyether polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18774388A JPH0236228A (en) | 1988-07-27 | 1988-07-27 | Purification of aromatic polyether polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0236228A true JPH0236228A (en) | 1990-02-06 |
Family
ID=16211420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18774388A Pending JPH0236228A (en) | 1988-07-27 | 1988-07-27 | Purification of aromatic polyether polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0236228A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001083586A1 (en) * | 2000-04-28 | 2001-11-08 | Mitsubishi Gas Chemical Company, Inc. | Method of precipitating polyphenylene ether |
| JP2008527124A (en) * | 2005-01-14 | 2008-07-24 | エボニック デグサ ゲーエムベーハー | Process for producing polyarylene ether ketone |
-
1988
- 1988-07-27 JP JP18774388A patent/JPH0236228A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001083586A1 (en) * | 2000-04-28 | 2001-11-08 | Mitsubishi Gas Chemical Company, Inc. | Method of precipitating polyphenylene ether |
| US6627727B1 (en) | 2000-04-28 | 2003-09-30 | Mitsubishi Gas Chemical Co | Method of precipitating polyphenylene ether |
| JP2008527124A (en) * | 2005-01-14 | 2008-07-24 | エボニック デグサ ゲーエムベーハー | Process for producing polyarylene ether ketone |
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