CN101370856B - 用于制备氟聚合物粉末材料的方法 - Google Patents
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Abstract
公开了一种用于制备氟聚合物粉末材料的方法，将在液体载体，优选水，中的固体氟聚合物颗粒悬浮液冷冻，然后通过在负压下升华除去冷冻载体以产生氟化合物颗粒的干燥粉末。
Description
本发明涉及一种用于制备氟聚合物粉末材料的方法。
氟聚合物为主要包括乙烯类重复单元的长链聚合物，其中部分或所有的氢原子被氟代替。实例包括聚四氟乙烯、全氟甲基乙烯基醚(MFA)、氟乙烯丙烯(FEP)、全氟烷氧基(PFA)、聚氯三氟乙烯和聚氟乙烯。它们是在所有的聚合物中最化学惰性的之一并且具有独特的耐酸、耐碱和耐溶剂特性。它们具有独特的低摩擦特性并且具有耐极端温度的性质。因此，氟聚合物在必需抗极端环境时，用于各种广泛的应用。目前的应用包括在化工厂、半导体设备、汽车部件和结构包层中形成管道和填充材料。
几种应用方法的其中之一需要氟聚合物的粉末形式。这里氟聚合物一般用于粉末静电喷雾的表面。应用包括家用厨具的涂层以增加不粘性和耐磨性，和汽车部件的涂层以增加耐环境气候性。
目前，有两种方法用于产生氟聚合物的粉末形式。喷雾干燥法包括氟聚合物进料水分散体泵入雾化系统，其一般位于干燥室的上部。液体雾化成热气体料流以蒸发水分并且产生干燥粉体。这种方法具有几种局限。水分散体泵送入雾化系统的要求限制了这种方法用于可泵送的材料，并且喷雾干燥聚集体彼此紧密地结合并且抗随后的解聚。另外，由于雾化可能导致氟聚合物的纤丝化，导致难以处理处理的“棉花糖”材料，只有非可纤丝化的材料可以处理。
另外的方法包括在水分散体中颗粒的聚集。通过使用高机械剪切、加入酸或加入凝胶剂并且随后用水不可混溶的有机液体处理促进聚集。聚集颗粒通过过滤和随后干燥，一般使用盘、带或快速干燥器可以从残留的液体中分离出来。由于易于处理聚集颗粒一般表面硬化。然而，聚集体的形成导致颗粒度太大，不利于在传统的粉末喷雾应用技术中使用。传统地用于调节颗粒度分布的研磨可以引起颗粒的纤丝化以产生难以处理的材料。表面硬化的材料也产生抗随后的解聚的紧密聚集体。
本发明的目的是提供用于制备氟聚合物粉末材料的方法，其中氟聚合物颗粒不紧密团聚，并且其中粉末材料可以从固体氟聚合物颗粒的液体悬浮液中产生，由于其可纤丝化性质的限制在正常的条件下不可泵送。
根据本发明，提供了一种用于制备氟聚合物粉末材料的方法，该方法包括在液体载体中冷冻固体氟聚合物悬浮液并且随后通过冷冻载体的升华方式分离出氟聚合物颗粒以产生干燥粉末。
本方法特别适宜于如下聚合物的处理：聚四氟乙烯、全氟甲基乙烯醚(MFA)、氟乙烯丙烯(FEP)、全氟烷氧基(PFA)。
优选地，氟聚合物粉末材料具有充分小的颗粒度以允许通过传统的粉末喷雾应用技术应用。产生的聚集体(具有大约0.2μm的初级颗粒度)可具有从1到100μm的平均直径，更优选地从20到30μm。
优选地，在液体载体中的固体氟聚合物颗粒的悬浮液在低于0℃温度的冷冻器中冷冻。更优选地，悬浮液在-60℃到-20℃范围的温度下冷冻。一般地，冷冻可以在6小时到24小时内完成。
优选地，在冷冻前，在液体载体中的固体氟聚合物颗粒的悬浮液倒入、舀入或转移入盘中。优选地，然后含固体氟聚合物颗粒悬浮液的盘放入冷冻器并且在盘内冷冻。
优选地，液体载体是基于有或没有表面活性剂和有或没有中间溶剂(bridging solvent)(用于帮助分散/溶解额外的树脂的有机溶剂)的水。如果使用中间溶剂，它们应该在足够低的浓度下并且具有足够高的熔点以不抑制冷冻。
优选地，使用低于大气压的压力或真空实施升华。降低的压力的使用引起载体从冷冻状态直接到气体状态的升华，避免固体到液体和液体到气体的转变。优选地，通过真空泵产生降低的压力。优选地，降低的压力在0.01atm到0.99atm的范围，更优选地0.04atm到0.08atm。一般，升华可以在12小时到48小时内完成。
对有些氟聚合物，该方法在在实践中低于氟聚合物的玻璃化转变温度的温度下实施。聚合物的玻璃化转变温度，Tg，是其从玻璃化成橡胶态的温度。Tg的测量值依赖于聚合物的分子量、其热力学历史和使用年限(age)、和加热与冷却的速度。PTFE的典型值为大约130℃，PFA大约75℃，FEP大约-208℃，PVDF大约-45℃。
控制温度以帮助升华过程并且避免载体液体的熔化。有利的巧合是这些控制也维持温度低于某些列出材料的Tg值。因此，本方法可以在室温下实施。另外，为了降低完成过程花费的时间，本方法可以在室温以上的温度实施。
在冷冻前、升华发生后或在本发明过程中的任何点可以改性氟聚合物颗粒。这些改性可能包括加入填充剂、研磨或辐照氟聚合物。填充剂的加入将在干燥前实施以提高混合物稳定性；研磨将在干燥后实施。
辐照氟聚合物将在研磨后实施以帮助控制颗粒度。
在液体阶段加入填充剂允许填充剂颗粒在氟聚合物颗粒间充分分散，因此使完成的粉末涂层具有所需的性质。作为粉末涂层材料，后研磨或辐照冷冻-干燥氟聚合物材料也可以提高其稳定性。
填充剂包括那些提高或改性氟聚合物特别物理性质的材料。例如，填充剂可以改变氟聚合物的颜色、粘附性、硬度或抗腐蚀性。填充剂的实例包括温度稳定颜料、粘合剂、玻璃珠、青铜粉和钨。其它特别的填充剂包括碳化硅、聚苯硫(PPS)、磷酸锌、聚酰胺酰亚胺(PAI)、聚醚酰亚胺(PEI)、聚醚醚酮(PEEK)和其它工程聚合物。
本方法可另外包括氟聚合物颗粒的研磨。研磨调整氟聚合物的颗粒度分布，例如降低平均颗粒度以产生更细的粉末。一般研磨传统地要在针或喷射磨中实施。
本方法可能另外包括氟聚合物颗粒的辐照，一般以粉末但也可选择在悬浮液中。辐照调整氟聚合物的熔融特性，例如以降低熔融温度/玻璃化转变温度并且增加熔体流速。
本发明的方法不会导致颗粒的紧密团聚，相反产生细粉末，其适宜用于在传统的粉末喷雾应用技术中应用或用于在水溶液或有机介质中再分散。易碎的粉末可以很容易地打碎用于颗粒度改性。
本发明的方法可以在氟聚合物的玻璃化转变温度以下的温度实施，与公知的包括喷雾干燥和聚集的方法不同(其需要温度大大高于100℃)。使用室温温度允许更大的能量效率，尽管可以使用高于室温但是低于玻璃化转变温度的温度以增加升华过程的速度。也可以使用高于室温的温度以帮助二级干燥，分离任何残留的痕量液体载体。
本发明的方法可以用于制备为可纤丝化的或非可纤丝化的氟聚合物的氟聚合物粉末材料。可纤丝化材料为那些经受剪切力时形成纤维的材料。公知的方法，其包括喷雾干燥和聚集，都使固体氟聚合物颗粒经受剪切力，其可以导致难以处理材料的产生。本发明在任何阶段不包括剪切力并且因此适宜用于可纤丝化的氟聚合物。
本发明的方法可用于从在液体载体中的固体氟聚合物颗粒的可泵送的或非可泵送的悬浮液制备氟聚合物粉末材料。由于高粘度或剪切敏感性该悬浮液可能为非可泵送的，并且实例包括高分子质量的PTFE或不稳定化的PFA、MFA和FEP分散体。本方法不包括任何悬浮液必须被泵送的步骤。相反，悬浮液可以被注入或舀入盘用于冷冻，并且固态的冷冻的块可以转移到真空室。
本发明可以用各种方式实施实现并且现在通过实施例的方式描述某些实施方案。
发明详述
在典型的过程中，依赖于聚合物的性质，具有大约0.2μm颗粒度的氟聚合物(改性的或未改性的)在水中通过与任选的表面活性剂和/或中间溶剂混合形成分散体。分散体注入盘，一般深度达1到1.5cm。然后在介于-60℃到-20℃的温度冷冻负载的盘。当冷冻后，盘装入真空室并且压力降低至0.01到0.99大气压，更一般地0.04到0.08大气压。在这些条件下发生液体载体的升华。在避免冷冻载体材料熔化的同时，可以使用另外的加热以帮助升华过程，并且帮助二级干燥。
随后的过程步骤可能包括研磨、辐照和压缩改性的粉末性质并且根据特殊的需要定制。
如下描述了使用和处理的特别分散体。
氟聚合物
PFA在水中的分散体具有23-27重量％的固体含量和在372℃下测得的7.2g/10分钟的熔体流速。
FEP在水中的分散体具有23-27重量％的固体含量和在372℃下测得的6.5g/10分钟的熔体流速。
MFA在水中的分散体具有28-32重量％的固体含量和在372℃下测得的5.4g/10分钟的熔体流速。
PTFE在水中的分散体具有30-60重量％的固体含量和在372℃下测得的1-10g/10分钟的熔体流速。
其它成分
在分散体中提到的可能包括的其它成分，包括：由CARBOREX提供的碳化硅，平均颗粒度3微米。
RYTON提供的聚苯硫(PPS)
BAYFEROX提供的红色120铁氧化物颜料
FERRO提供的PK 6075赭色颜料
JOHNSON提供的34E23黑色金属颜料
Claims (12)
1.一种用于制备改性氟聚合物粉末材料的方法，其包括冷冻在液体载体中的固体氟聚合物颗粒和一种或多种填充剂的悬浮液并且升华冷冻的载体以分离干燥的改性氟聚合物粉末。
2.如权利要求1所述的方法，其中所述的升华通过低于大气压的方式实现。
3.如权利要求2所述的方法，其中所述的降低的压力介于0.01到0.99atm之间。
4.如上述权利要求中任一项所述的方法，其中所述的液体载体为水。
5.如权利要求1所述的方法，其中所述的升华在低于氟聚合物的玻璃化转变温度的温度下实施。
6.如权利要求5所述的方法，其中所述的升华在室温下实施。
7.如权利要求5所述的方法，其中所述的升华在介于室温和氟聚合物的玻璃化转变温度之间的温度下实施。
8.如权利要求1所述的方法，其中所述的在液体载体中的固体氟聚合物颗粒和填充剂的悬浮液在介于-60℃到-20℃之间的温度下冷冻。
9.如权利要求1所述的方法，其中所述的在液体载体中的固体氟聚合物颗粒和填充剂的悬浮液在盘中冷冻。
10.如权利要求1所述的方法，其中所述的填充剂包括颜料和/或粘合剂。
11.如权利要求1所述的方法，其中所述的固体氟聚合物颗粒通过研磨和/或辐照改性。
12.如权利要求1所述的方法，其中所述的氟聚合物为可纤丝化的和/或不可泵送的。
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| GB0600823.9 | 2006-01-16 | ||
| GB0600823A GB2434152A (en) | 2006-01-16 | 2006-01-16 | Fluoropolymer powdered materials |
| PCT/GB2007/000116 WO2007080426A1 (en) | 2006-01-16 | 2007-01-16 | Method for the preparation of fluoropolymer powdered materials |
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| CN101370856B true CN101370856B (zh) | 2011-12-28 |
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| JP2009528255A (ja) | 2005-08-22 | 2009-08-06 | ジェネンコー・インターナショナル・インク | 反復配列タンパク質とフィロケイ酸塩粘土とのナノコンポジットおよびその調製 |
| US8333830B2 (en) | 2005-08-22 | 2012-12-18 | Danisco Us Inc. | Composites of repeat sequence proteins and their preparation |
| GB2434152A (en) * | 2006-01-16 | 2007-07-18 | Whitford Plastics Ltd | Fluoropolymer powdered materials |
| GB2451097A (en) * | 2007-07-17 | 2009-01-21 | Whitford Plastics Ltd | Silicon carbide-modified fluoropolymer powders |
| GB2451096A (en) | 2007-07-17 | 2009-01-21 | Whitford Plastics Ltd | Method of preparing a powdered fluoropolymer blend |
| CN102099416B (zh) * | 2008-05-30 | 2014-03-12 | 华福涂料公司 | 共混含氟聚合物组合物 |
| TW201016800A (en) | 2008-09-26 | 2010-05-01 | Whitford Corp | Blended fluoropolymer coatings for rigid substrates |
| CA2737586C (en) | 2008-09-26 | 2016-11-08 | Whitford Corporation | Blended fluoropolymer compositions and coatings for flexible substrates |
| RU2671258C2 (ru) * | 2017-02-27 | 2018-10-30 | Валерий Владимирович Коваленко | Устройство для вакуумной сублимационной сушки |
| CN114750331A (zh) * | 2021-01-12 | 2022-07-15 | 上海芯密科技有限公司 | 一种采用高分子材料制备微米级或亚微米级填料的方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| PT1987086E (pt) | 2011-04-11 |
| US20100132212A1 (en) | 2010-06-03 |
| BRPI0706632A2 (pt) | 2011-04-05 |
| JP5243968B2 (ja) | 2013-07-24 |
| JP2009523851A (ja) | 2009-06-25 |
| GB2434152A (en) | 2007-07-18 |
| PL1987086T3 (pl) | 2011-08-31 |
| KR20080091344A (ko) | 2008-10-10 |
| ATE501208T1 (de) | 2011-03-15 |
| RU2008133605A (ru) | 2010-02-27 |
| CA2636460A1 (en) | 2007-07-19 |
| GB0600823D0 (en) | 2006-02-22 |
| DE602007013005D1 (de) | 2011-04-21 |
| CN101370856A (zh) | 2009-02-18 |
| DK1987086T3 (da) | 2011-06-27 |
| RU2434895C2 (ru) | 2011-11-27 |
| SI1987086T1 (sl) | 2011-09-30 |
| US8166668B2 (en) | 2012-05-01 |
| EP1987086A1 (en) | 2008-11-05 |
| AU2007204185A1 (en) | 2007-07-19 |
| EP1987086B1 (en) | 2011-03-09 |
| KR101307608B1 (ko) | 2013-09-12 |
| ES2359351T3 (es) | 2011-05-20 |
| WO2007080426A1 (en) | 2007-07-19 |
| BRPI0706632B1 (pt) | 2018-03-06 |
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