CN1133857A - 聚芳硫醚的表面氧化方法 - Google Patents
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Abstract
在聚芳硫醚的表面氧化方法中把所要氧化材料的表面同一种含臭氧的气体或一种液体进行接触。
根据此方法制备的材料能用于飞机制造，汽车制造以及化学仪器制造上。
Description
本发明涉及一种借助臭氧对聚芳硫醚形成的模制件，粒状物或粉末进行表面氧化以提高其耐热性和耐化学性的方法。
聚芳硫醚为人所熟知。除有良好的耐热性外它还有良好的耐化学性。然而在许多应用上需要更好的耐热性和更好的耐化学性。例如这可通过把聚芳硫—聚合物链氧化成聚芳亚砜或聚芳砜(DE—A4314735，DE—A4314736，DE—A4314737)来实现。然而其缺点是这类聚合物用传统方法通过注塑或挤出通常不能进行热塑性加工。
在许多应用上只氧化模体的表面就行了。已知可借助过氧化氢和醋酸或二氯甲烷和间氯苯甲酸进行表面氧化(A.Kaul和K.Udip-i；Macromolecules 1989，22，1201—1207)，通常借助试剂的聚芳硫的表面氧化在US—A4,251,575；US—A0,051,691；US—A4,377,660中进行了描述。此外已知可借助等离子体处理对超薄膜进行表面氧化(JP88—200838)。
借助试剂的表面氧化费时并且需要特殊的反应容器。此外氧化后须对试剂进行处理。等离子体处理需要很高的仪器化费。
本发明的目的是，克服上述的缺点。
通过使用臭氧作氧化剂已达到了该目的。
本发明涉及一种对聚芳硫醚进行表面氧化的方法，在该方法中把要氧化的材料的表面同含臭氧的气流或溶有臭氧的液体进行接触。所用材料例如是模制件，粒状物或粉末。此时在固体物质的表面发生了聚芳硫醚的氧化。根据臭氧浓度聚芳硫醚的硫桥被氧化成亚砜和/或砜。在此较高的氧化程度会有较高的耐热性和耐化学性。
这种方法是一种简单，快速和经济的对聚芳硫醚表面氧化的方法。
表面氧化能在气体，优选在臭氧/氧气(O3/O2)混合物或臭氧/空气混合物中以及在液体中，特别是具有溶于水或不同浓度(优选10—100％)醋酸中的臭氧的液体中进行。
用各种臭氧浓度都能进行表面氧化，特别合适的是1g/m3—200g/m3的臭氧浓度。臭氧浓度＜1g/m3时花费时间太长。而臭氧浓度＞200g/m3臭氧会有自爆的危险。
可使用的聚合物是线性和/或支链形的具有式(1)重复单元的聚芳体系，该重复单元至少含有一个硫醚基。-[(Ar1)n-X]m-[(Ar2)i-Y]j-[(Ar3)k-Z]l-[(Ar4)o-W]p-(1)
其中Ar1，Ar2，Ar3，Ar4，W，X，Y和Z互相独立，相同或不同。角标n，m，i，j，k，l，o和p互相独立是0或整数1，2，3或4，其中它们的和必须至少为2。Ar1，Ar2，Ar3，和Ar4在式(1)中代表具有6—18个碳原子的亚芳基体系。W，X，Y和Z是二元连结基团，选自-SO2--，-S-，-SO-，-CO-，-CO2-，具有1-6，优选1-4个C原子的烷撑或烷叉。
合适的聚合物例如是具有式(II)-(VI)的重复单元的聚芳硫醚，其合成介绍在Chimia28(1974)，567中：
以及具有式(VII)的重复单元的聚芳硫醚(US—A-4,016,145)。
优选的聚芳硫醚是具有式(VIII)的重复单元的聚苯硫(PPS)(参看Uuman′s Encyclopedia of Industrial Chemistry，卷A21，Weinbeim—New York1992，463页)。
通常适合于本发明的聚芳硫醚，其平均分子量(用GPC测定)在4000—200000，优选10000—150000，特别优选25000—100000。
聚芳硫醚也能含有粉末状增强剂，诸如白垩，滑石，陶土，云母，和/或纤维状增强剂，诸如玻璃纤维和碳纤维，晶须(Whiskers)，以及其它的普通添加剂和加工助剂，例如润滑剂、分离剂、抗氧剂、UV-稳定剂。这类成分应用在飞机和汽车制造上以及化学仪器制造上。
实施例：1.模制件的表面氧化通常试验条件：
—用市场上常见的臭氧发生器(Fischer 503，Fa，FischerLabortechnik，Meckenheim，德国)经过静电放电由干燥氧气制备臭氧。在臭氧分析仪Fischer Ozotron23上进行臭氧分析(反应器进口/出口)。
—材料试样放在两边可用玻璃料封住的玻璃管中。随后用含臭氧的氧气流过玻璃管。
—材料试样的表面分析在ESCA(化学分析电子光谱)上进行。
分子量Mw为90000g/mol的聚苯硫用作聚芳硫。
| 实施例 | 1a | 1b |
| PPS管(直径：80mm，壁厚：3mm) | PPS棒(80*10*4mm) | |
| PPS重量(g) | 3 | 4 |
| 入口臭氧〔mg/m3〕 | 40000 | 35000 |
| 出口臭氧[mg/m3] | 39300 | 34400 |
| 吸收臭氧〔g〕 | 0.07 | 0.09 |
| 体积流速[m3/h] | 0.05 | 0.05 |
| 温度[℃] | 25 | 25 |
| 试验时间[h] | 2 | 3 |
| 臭氧处理前的表面组成〔原子％〕 | 100％PPS0％PPSO0％PPSO2 | 100％PPS0％PPSO0％PPSO2 |
| 臭氧处理后的表面组成〔原子％〕 | 19.7％PPS26.5％PPSO53.9％PPSO2 | 14.3％PPS29.0％PPSO56.7％PPSO2 |
2.表面氧化的模体的性质
把在未处理状态和表面氧化状态中的实施例1b的PPS棒在下列化学品中进行处理：
| 末处理 | 表面氧化 | |
| 在180℃硫酸(20％)中达96h | - | + |
| 在23℃硝酸(86％)中达1h | - | + |
| 在150℃甲苯中达24h | - | + |
| 在180℃乙二醇(50％)中达96h | - | + |
+：有耐蚀性，重量增加＜3％或重量损失＜0.5％和/或抗拉强度降低＜15％
/：部分耐蚀性，重量增加3—8％或重量损失0.5—3％和/或抗拉强度降低15—30％
-：无耐蚀性，重量增加＞8％或重量损失＞3％和/或抗拉强度降低＞30％
此外在未处理状态或表面氧化状态的实施例1b的PPS棒进行短暂的加热，如焊接过程中一般所发生的。
参数：每小时30次，在260℃达5秒。
我们发现，未处理的PPS棒在表面熔化，而表面氧化过的PPS没有变化。
3.粒状物和粉末的氧化通常试验条件：
—用市场上常见的臭氧发生器(Fischer 503，Fa，Fischer)经过静电放电由干燥氧气制备臭氧。
—把PPS粒状物(1mm粒度，筛份)放在双层外壳玻璃反应器中(1.5l)并用螺旋搅拌器在干燥状态彻底混合，接着经底部阀门把臭氧引到反应器中。冷却反应器外壳到5℃。
—在同样的反应器中把PPS粉末(20μm粒度)悬浮在50％的水性醋酸中并用一板状搅拌器充分搅拌，接着经底部阀门把臭氧引入到反应器中。冷却反应器外壳到5℃。用市场上常见的分析仪器(Fischer Ozotron23，Fa，Fischer)测定入口和出口的臭氧浓度。
用ESCA进行材料试样的表面分析。当为粒状物时一方面测定1mm粒子的纯表面氧化作用，另一方面通过把粒子精细研磨并随后测定来确定总氧化度。
| 实施例 | 3a | 3b |
| PPS-粒状物(1mm) | PPS-粉末(0.02mm) | |
| 悬浮介质/溶液 | - | 50％醋酸水溶液 |
| 转速(转/分) | 200 | 500 |
| PPS重量(g) | 400 | 216 |
| 入口臭氧[mg/m3](平均值) | 52000 | 55000 |
| 出口臭氧[mg/m3](平均值) | 3000 | 15000 |
| 体积流速(m3/h) | 0.1 | 0.05 |
| 吸收臭氧〔g〕 | 130 | 52 |
| 温度[℃] | 10-20 | 5-10 |
| 试验时间[h] | 2 | 3 |
| 臭氧处理前的表面组成〔原子％〕 | 100％PPS0％PPSO0％PPSO2 | 100％PPS0％PPSO0％PPSO2 |
| 臭氧处理后的表面组成(原子％) | 22.1％PPS27.7％PPSO50.2％PPSO2 | 10.5％PPS74.4％PPSO15.1％PPSO2 |
Claims (9)
1.聚芳硫醚的表面氧化方法，其特征是，所要氧化的表面同含臭氧的气流或溶有臭氧的液体进行接触。
2.根据权利要求1的方法，其特征是，使用臭氧/氧气或臭氧/空气的混合物。
3.根据权利要求1的方法，其特征是，把臭氧溶于水或醋酸中。
4.根据权利要求1—3的一项或多项的方法，其特征是，臭氧浓度为1g/m3—200g/m3。
5.根据权利要求1—4的一项或多项的方法，其特征是，聚芳硫醚的硫桥被氧化成亚砜和/或砜。
6.根据权利要求1—5的一项或多项的方法，其特征是，使用线形和/或支链形的具有式(1)重复单元的聚芳体系，该重复单元至少含有一个硫醚基。-[(Ar1)n-X]m-[(Ar2)i-Y]j-[(Ar3)k-Z]l-[(Ar4)o-W]p-(1)
其中Ar1，Ar2，Ar3，Ar4，W，X，Y和Z互相独立，相同或不同。每标n，m，i，j，k，l，o和p互相独立是0或整数1，2，3或4，其中它们的和必须至少为2。Ar1，Ar2，Ar3，和Ar4在式(1)中代表具有6—18个碳原子的亚芳基体系。W，X，Y和Z是二元连结基团，选自-SO2-，-S-，-SO-，-CO-，-CO2-，具有1—6，优选1—4个C原子的烷撑或烷叉。
7.根据权利要求6的方法，其特征是，使用聚苯硫。
8.根据权利要求1—7的一项或多项的方法，其特征是，聚芳硫醚的平均分子量(以GPC测定)为4000—200000，优选10000—150000，特别地25000—100000。
9.按照根据权利要求1—8的方法制备的材料用于飞机和汽车制造以及化学仪器制造。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4444442A DE4444442A1 (de) | 1994-12-14 | 1994-12-14 | Verfahren zur Oberflächenoxidation von Polyarylenthioethern |
| DEP4444442.7 | 1994-12-14 |
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| CN1133857A true CN1133857A (zh) | 1996-10-23 |
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| CN95120836A Pending CN1133857A (zh) | 1994-12-14 | 1995-12-12 | 聚芳硫醚的表面氧化方法 |
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| US (1) | US5691427A (zh) |
| EP (1) | EP0717067A1 (zh) |
| JP (1) | JPH08231739A (zh) |
| KR (1) | KR960022718A (zh) |
| CN (1) | CN1133857A (zh) |
| DE (1) | DE4444442A1 (zh) |
| TW (1) | TW355714B (zh) |
Cited By (1)
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| CN111349240A (zh) * | 2018-12-24 | 2020-06-30 | 上海钱丰纺织品有限公司 | 一种高玻璃化温度的改性聚苯硫醚及其制备方法 |
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|---|---|---|---|---|
| DE19612112C2 (de) * | 1996-03-27 | 1999-05-20 | Braun Gmbh | Ventilkörper von Dampfbügeleisen und Verfahren zu seiner Herstellung |
| IT1291669B1 (it) * | 1997-04-24 | 1999-01-19 | Tecno Coating Eng Srl | Metodo ed apparato per ossidare la superficie interna di un tubolare estruso,durante l'estrusione |
| EP0892359A1 (en) * | 1997-07-18 | 1999-01-20 | Datalogic S.P.A. | Portable code reading device |
| DE19751239A1 (de) * | 1997-11-19 | 1999-05-20 | Ticona Gmbh | Oxidation von Polyarylensulfiden |
| DE19916495A1 (de) * | 1999-04-12 | 2000-10-19 | Ticona Gmbh | Verfahren zur Oxidation von Polyarylensulfid zu Polyarylensulfoxid mittels Salpetersäure |
| DE10024172A1 (de) * | 2000-05-12 | 2001-11-15 | Volkswagen Ag | Kunststofferzeugnis mit verringerter Durchlässigkeit für unpolare Stoffe und Verfahren zur Herstellung |
| TWI558876B (zh) * | 2010-07-05 | 2016-11-21 | 大陽日酸股份有限公司 | 表面氧化處理方法及表面氧化處理裝置 |
| EP3959256A1 (en) * | 2019-04-26 | 2022-03-02 | Solvay Specialty Polymers USA, LLC. | Powdered material (p) containing poly(arylene sulfide) (pas) polymer and its use for additive manufacturing |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793256A (en) * | 1972-08-30 | 1974-02-19 | Phillips Petroleum Co | Controlled curing pf poly(arylene sulfide)resins |
| US4383080A (en) * | 1982-04-05 | 1983-05-10 | Phillips Petroleum Company | Process for curing poly(arylene sulfides) |
| JPH0621168B2 (ja) * | 1985-08-27 | 1994-03-23 | 呉羽化学工業株式会社 | 溶融結晶化温度の高いポリアリ−レンチオエ−テルの製造法 |
| JP3230258B2 (ja) * | 1991-11-18 | 2001-11-19 | 東ソー株式会社 | ポリフェニレンスルフィドの硬化方法 |
| DE4314737A1 (de) * | 1993-05-04 | 1994-11-10 | Hoechst Ag | Zweistufige Oxidation von Polyarylensulfiden |
| DE4314734A1 (de) * | 1993-05-04 | 1994-11-10 | Hoechst Ag | Filtermaterial und Verfahren zur Entfernung von Ozon aus Gasen und Flüssigkeiten |
| DE4314736A1 (de) * | 1993-05-04 | 1994-11-10 | Hoechst Ag | Oxidation von Polyarylensulfiden |
-
1994
- 1994-12-14 DE DE4444442A patent/DE4444442A1/de not_active Withdrawn
-
1995
- 1995-11-20 TW TW084112329A patent/TW355714B/zh active
- 1995-12-04 EP EP95119060A patent/EP0717067A1/de not_active Withdrawn
- 1995-12-12 CN CN95120836A patent/CN1133857A/zh active Pending
- 1995-12-13 KR KR1019950049105A patent/KR960022718A/ko not_active Application Discontinuation
- 1995-12-13 US US08/571,751 patent/US5691427A/en not_active Expired - Fee Related
- 1995-12-13 JP JP7324694A patent/JPH08231739A/ja active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349240A (zh) * | 2018-12-24 | 2020-06-30 | 上海钱丰纺织品有限公司 | 一种高玻璃化温度的改性聚苯硫醚及其制备方法 |
| CN111349240B (zh) * | 2018-12-24 | 2023-01-03 | 上海钱丰纺织品有限公司 | 一种高玻璃化温度的改性聚苯硫醚及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW355714B (en) | 1999-04-11 |
| US5691427A (en) | 1997-11-25 |
| DE4444442A1 (de) | 1996-06-27 |
| KR960022718A (ko) | 1996-07-18 |
| JPH08231739A (ja) | 1996-09-10 |
| EP0717067A1 (de) | 1996-06-19 |
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