CN1106414C - 改性的聚四氟乙烯的制备方法 - Google Patents
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Abstract
一种制备含0.02-0.25wt%且在全氟代烷基链上具有1-4个碳原子的全氟代烷基乙烯基醚单元的四氟乙烯聚合物的方法，该方法包括在低于60℃温度下，使用含高氧化态锰的引发剂，在水溶性介质中，由悬浮工艺来聚合单体。
Description
本发明涉及一种制备用全氟代烷基乙烯醚(PAVE)单元改性的聚四氟乙烯(PTFE)的方法。“改性”的聚四氟乙烯是指四氟乙烯(TFE)聚合物中含有相对少量的醚单元，即通常低于0.1％(摩尔)，而且其共聚物如均聚聚四氟乙烯是无法从熔体中制备的。另一方面，聚合物中的醚单元含量又必须足够高，以便使熔体结晶受到抑制，以及无定形含量在一定范围内得以提高。这样，即使在极低的分子量的情况下，也可取得未改性聚四氟乙烯所具有的良好力学特性如抗拉强度和断裂延伸率。
低分子量改性产物在熔融粘度方面明显改进，按Ajroldi方法(美国专利申请3,855,191，第8列)，其熔融粘度为约1到100GPas；而对于有可比的良好力学特性的未改性的聚四氟乙烯，其熔融粘度则超过了300GPas。
熔融粘度的大幅降低提高了由这些改性的模塑粉末所制成的成型件的性能。因为模塑粉的颗粒更易互相融化在一起，所以成型件含有较少的孔隙并因此得到了改善的电击穿电阻值；而且抗蠕变性几乎成倍增长。特别是成型件的可焊性极大改善。
如上所述，本发明也介绍改性的聚四氟乙烯在预成型自由熔结技术中的用途。为此目的，粗品聚合物必须有好的可研磨性。与此相反，挤料杆式挤塑需要一种硬的，即研磨性差的颗粒以及良好的流动性。
本发明提供了一种制备含0.02-0.25wt％且在全氟代烷基链上具有1-4个碳原子的PAVE单元的TFE聚合物的方法。该方法包括在低于60℃温度下，使用含有高氧化态锰的引发剂，在水溶性介质中，由悬浮工艺来聚合单体。对于本发明的用途来说，由此得到的粗品聚合物被研磨成平均粒径为10到50微米。
优选的PAVE是全氟代正丙基乙烯醚，下文中记作PPVE。
聚合反应温度最好在10℃到50℃范围内，聚合反应的压力为4-25×105Pa，特别是5-15×105Pa的范围内。
合适的引发剂是高锰酸、锰酸以及亚锰酸的盐类。优选高锰酸盐，它们最好与可溶性草酸盐如草酸铵和碱金属草酸盐混合使用。
以下更详细地说明本发明进一步的优选实施方案。
使用高锰酸钾及相似的引发剂来制备包含四氟乙烯(TFE)和全氟代烷基乙烯醚(PAVE)的共聚物的方法，已为人所知。例如，美国专利申请4262101公开了一种以四氟乙烯(TFE)与含1％-6％(摩尔)的全氟代烷基乙烯醚(PAVE)以及含5％-25％(摩尔)的六氟丙烯在链转移剂存在下聚合制备三元聚合物的方法。此聚合反应温度可为10℃到150℃，最好在10℃到50℃。由此得到的三元聚合物可从熔融液中制得。
美国专利申请4078134公开了四氟乙烯(TFE)仅与非常少量〔即含0.0004％-0.0029％(摩尔)〕的全氟代烷基乙烯醚的聚合反应。适宜的聚合反应温度从10℃到35℃，在以高锱酸钾作为引发剂的实例中，温度为15℃到25℃。由此得到的产品与未经改性的聚四氟乙烯(PTFE)以及含有较高比例改性剂〔即含量大于0.0029％(摩尔)〕的产品有明显区别(第4列，18-68)。它们适用于以成形，熔结，特别是挤料杆式挤塑方式来制造成型件。因此，它们无法满足现今用于预成型自由熔结技术中模塑粉的特殊要求。
用全氟代烷基乙烯醚(PAVE)改性且适用于预成型自由熔结技术的四氟乙烯聚合物的制备方法披露在美国专利申请3855191。该聚合反应在50℃到100℃内进行，并优选无机过硫酸盐作为引发剂。虽然特别指出了氧化还原引发剂系统，但没有提到锰酸盐。所需的低于8wt％，优选低于6.5wt％的低无定形含量可通过使用没有调聚作用的氟化分散剂得到。不过，已发现当这些分散剂依本发明使用时，会导致聚合反应中块状物的形成，特别是在低温时。因此，无法保证达到所需固含量约30wt％的受控反应。
而且进一步发现，当使用氟化分散剂时形成特定的块状物，特别是在聚合反应液中较低盐含量的情况下。但是，本发明的方法却允许低的盐含量，这不仅简化了废水的处理，也对产品的特性有积极的影响。
依照本发明所进行的聚合反应生产出一种极易研磨的粗品聚合物。可研磨性的极大改善明显表现在产率的两倍以上增长和/或研磨机的功耗下降。
还发现，粗品聚合物的易研磨性伴随有良好的力学和电学特性。因此得到的模塑粉有很高的可压性和可变形性。对于本发明来说，这就意味着在不同的高压下不用烧结压制的模塑粉(即呈生料形式)的重力测定密度有改变(美国专利申请3245972，第2列，28-37行)。提高可压性或可变形性改善了烧结材料的技术特性，因为各个颗粒间的接触会更易得到保证。
依本发明得到的产品所制造出的成型件有许多有价值的综合特性，特别是高的抗拉强度与良好的断裂延伸率以及高的电击穿电阻值。
良好的研磨性和最终产品改善的特性很可能是由聚合物改性的颗粒结构引起的，这明显表现在比表面积大幅度提高。已发现，这种颗粒的改善在所需方向上受到相对高的四氟乙烯压力(例如在15-25×105Pa范围内)的显著影响。但是，出于技术原因，压力范围最好在5-15×105Pa，因为较高的四氟乙烯(TFE)压力会导致昂贵的全氟代烷基乙烯醚(PAVE)的过高损耗。而且，系统自身存在的爆炸危险也会在高压下增加。
依照本发明，对颗粒结构的有利影响主要通过低的聚合反应温度来达到。如上所述，聚合介质中低的盐分含量也是有利的。就本发明使用的引发剂而言，聚合温度可降低到约10℃，而时空收率(在可比分子量和相同改善程度上)并没有无故降低。这很令人吃惊，因为PAVE大大减缓了聚合反应。
本发明的引发剂有强烈依赖于温度的分解速率。因此，随着降低聚合温度，聚合开始时先加入的引发剂占总量的比例应加大，剩余部分最好在聚合反应整个过程中持续计量加入。计量加入最好以此方式控制，以便全氟代烷基乙烯醚(PAVE)对时间恒定结合度的聚合速率不会下降。
此聚合反应也可由美国专利申请5 153 285公知的方法来进行，其中在聚合之前，加压注入四氟乙烯(TFE)和惰性气体的混合物使总压力为5-50×105Pa，混合物中四氟乙烯(TFE)的浓度在30％-70％(摩尔)，并通过聚合过程中进一步适当的注入来保持在这一范围内。
如果需要一种自由流动的产品，本发明得到的研磨产品可通过已知方式造粒。美国专利申请4 439 385所述的附聚法是合适。
本发明用下面的实施例来说明。百分比以重量计。
实施例
在一个150升的反应器中注入100升去离子水并加入表1中给定量的草酸铵(AmOx)。使反应器内物排除含氧气氛，这可通过反复抽空和用氮气清洗实现。加四氟乙烯(TFE)达到10×105Pa的压力并注入氮气使总压提高到15×105Pa。通过进一步注入四氟乙烯(TFE)，使该压力在整个聚合过程中保持恒定。反应器中计量入表1中给定量的全氟代丙基乙烯醚(PPVE)，反应器内物的温度也要提高到表1中给定值。该温度同样在整个聚合反应中保持恒定。快速计量加入(在5分钟内)表1中“始加量”一栏所给定的溶于300毫升水的高锰酸钾来开始聚合。加入同时，反应几乎马上进行。约20分钟后，表1中给定量的高锰酸钾的水溶液以及追加的全氟代丙基乙烯醚(PPVE)要连续计量加入。
当所需量的四氟乙烯(TFE)加完之后，通过中断加入引发剂、全氟代丙基乙烯醚(PPVE)和四氟乙烯(TFE)中止反应。又过了约20分钟，压力降至约6×105Pa。然后，将反应器内物冷却到室温，并通过反复抽空基本上排除残余单体。
所得产品用去离子水洗3次，在220℃下干燥10小时，并在螺旋喷气(Spiral jet)研磨机中磨碎。研磨过产品的平均粒径d50约为20微米。表1中列有磨碎粉末的进一步特性。这些特性由下述方法测定：
依美国专利申请3855191，第5列所给的方法，在100微米厚薄膜上，用红外光谱法测量778和2353cm-1的吸收值来测定无定形含量。
全氟代丙基乙烯醚(PPVE)的含量也采用红外光谱法，在100微米薄膜上测量995和2353cm-1的吸收值并依下述关系来测定：
全氟代丙基乙烯醚含量％＝0.95×A995/A2353
比表面积依F.M.Nelson和F.T.Eggertson介绍的方法〔Anal.Chem.30，1387(1958)〕，通过测量氮气的吸收来测定。
粗品聚合物在螺旋喷气研磨机中的研磨性是在研磨空气压为6×105Pa和粒径大于33微米(过筛测量)的颗粒有相同份额下，由每小时通过量测定。
表1中所给的分子量(数均分子量)是在指定的反应条件下所用引发剂实际上定量反应这一似乎合理的假定下，由以下关系式估计出来：
Mn＝2·100·mp/Io这里mp代表反应了的四氟乙烯(TFE)的摩尔量，Io代表所使用的引发剂的摩尔量，系数100代表四氟乙烯(TFE)的分子量，系数2代表化合中止系数(Combination termination)。
标准比重可依美国材料试验学会(ASTM)测定标准D-1457-69来测定。
表1在“最终特性”一栏下，也列出了抗拉强度(TS)，断裂延伸率(EB)和电击穿电阻值(EBR)。这些特性可在依下列步骤制得的薄膜上测定：
a)用去离子水冲洗粗品聚合物，
b)在温度高达130℃下，在流化床中预干燥洗净的粗品聚合物，
c)在220℃下，进一步干燥上述产物4小时，
d)在喷气式研磨机中研磨干燥产物，使其平均直径d50达到约20微米，
e)在350×105Pa压力下，将13kg块材压制成高和直径均约为208毫米的圆柱。
f)按照温度程序，在380℃下熔结，以及
g)以200微米阶梯刮削出厚100微米的薄膜。
从柱块中部取出的100微米厚的薄膜样品用于依德国工业标准(DIN-)53455(拉伸法)测定其抗拉强度和断裂延伸率，并依德国工业标准53481测定其电击穿电阻值。
表2列出了对比例。由于本发明所使用的反应引发剂在温度高于60℃时分解速率变得特别高，以至很难实现易于再现的聚合反应，因此，过硫酸铵(APS)用作反应引发剂。除了草酸铵以外，碳酸铵(AmCb)也用作缓冲物质。分子量可由下列关系估算：
Mn＝100·mp/〔Io(1-e-kd·t)〕这里mp代表反应了的四氟乙烯(TFE)的摩尔量，Io代表所使用的反应引发剂的摩尔量，kd是过硫酸铵的分解常数，t是聚合反应时间。该关系式假设过硫酸盐分解成两个引发剂自由基。
用于分解常数Kd的值，于70℃为1.2×10-5秒-1，于63℃为0.5×10-5秒-1”〔I.M.Kolthoff，I.H.Miller，J.Am.Chem.Soc.37(1951)3055〕。
由表1和表2的平均值的比较可知以下特性概貌：
本发明方法的产品，在可比分子量和改进度上，有高的多的比表面积，极大改善的可研磨性，增长30％的电击穿电阻值和增加了10N/mm2的抗拉强度，只是断裂延伸率轻微降低。
表1
| 实施例 | 工艺参数 | 粉末特性 | 最终特性 | ||||||||||||||
| 温度〔℃〕 | 草酸铵〔克〕 | 高锰酸钾始加量〔毫克〕 | 高锰酸钾后续加入量〔毫克〕 | 四氟乙烯〔千克〕 | 全氟代烷基乙烯醚始加量〔克〕 | 计量加入速率〔克〕PPVE/〔克〕TFE | 实验时间〔小时〕 | 全氟代烷基乙烯醚结合量〔％〕 | 无定形含量〔％〕 | 比表面积〔平方米2/克〕 | 可研磨性〔千克/小时〕 | Mn×10-7〔克/摩尔〕 | 标准比重〔克/立方厘米〕 | 抗拉强度〔牛/平方毫米〕 | 断裂延伸率〔％〕 | 电击穿电阻值〔千伏/毫米〕 | |
| 1 | 55 | 1.5 | 50 | 780 | 42.0 | 30.0 | 2.5 | 3.9 | 0.08 | 5.4 | 4.3 | 10 | 1.6 | 2.177 | 45.8 | 635 | 119 |
| 2 | 55 | 1.5 | 35 | 800 | 50.0 | 35.0 | 2.0 | 5.4 | 0.07 | 3.6 | 3.7 | 12 | 1.9 | 2.163 | 46.4 | 665 | 121 |
| 3 | 40 | 1.5 | 30 | 780 | 50.7 | 30.0 | 2.5 | 5.3 | 0.09 | 5.9 | 2.7 | 11 | 2.0 | 2.159 | 44.0 | 605 | 130 |
| 4 | 40 | 1.5 | 40 | 820 | 51.3 | 30.0 | 2.5 | 5.2 | 0.10 | 6.0 | 2.9 | 12 | 1.9 | 2.158 | 43.6 | 590 | 120 |
| 5 | 40 | 3.0 | 40 | 620 | 51.0 | 30.0 | 2.5 | 4.0 | 0.08 | 5.9 | 3.2 | 13 | 2.5 | 2.160 | 42.2 | 615 | 129 |
| 6 | 40 | 1.5 | 300 | 570 | 52.5 | 70.0 | 1.0 | 4.5 | 0.09 | 6.2 | 3.1 | 12 | 1.9 | 2.162 | 47.3 | 625 | 130 |
| 7 | 40 | 1.5 | 300 | 520 | 52.4 | 70.0 | 1.0 | 4.8 | 0.08 | 6.3 | 3.3 | 14 | 2.0 | 2.161 | 48.2 | 640 | 139 |
| 8 | 40 | 1.5 | 70 | 800 | 48.4 | 60.0 | 2.0 | 5.0 | 0.08 | 5.7 | 2.9 | 11 | 1.8 | 2.163 | 42.4 | 670 | 120 |
| 9 | 35 | 1.5 | 20 | 730 | 50.8 | 30.0 | 2.5 | 5.1 | 0.09 | 5.7 | 3.3 | 11 | 2.2 | 2.157 | 51.5 | 595 | 138 |
| 10 | 35 | 5.0 | 30 | 910 | 51.7 | 45.0 | 2.5 | 4.9 | 0.10 | 6.8 | 3.4 | 12 | 1.8 | 2.161 | 46.5 | 625 | 130 |
| 11 | 20 | 1.5 | 300 | 570 | 52.0 | 60.0 | 2.5 | 5.1 | 0.09 | 7.6 | 3.6 | 10 | 1.9 | 2.155 | 48.9 | 555 | 134 |
表2
| 工艺参数 | 粉末特性 | 最终特性 | ||||||||||||||
| 对比例 | 温度(℃) | 缓冲物质量/类型 | 过硫酸钙(克) | 四氟乙烯(千克) | 全氟代烷基乙烯醚始加量(克) | 计量加入速率(克)PPVE/(千克)TFE | 实验时间(小时) | 全氟代烷基乙烯醚结合量(％) | 无定形含量(％) | 比表面积〔平方米2/克〕 | 可研磨性〔千克/小时〕 | Mn×10-7〔克/摩尔〕 | 标准比重〔克/立方厘米〕 | 抗拉强度〔牛/平方毫米〕 | 断裂延伸率〔％〕 | 电击穿电阻值〔千伏/毫米〕 |
| 1 | 70 | 10g/AmCb | 5.0 | 50 | 35.0 | 1.7 | 5.3 | 0.09 | 5.8 | 1.4 | 5.3 | 1.3 | 2.171 | 35.6 | 675 | 94 |
| 2 | 70 | 20g/AmCb | 5.0 | 50 | 70.0 | 0.6 | 5.2 | 0.10 | 6.3 | 1.5 | 5.5 | 1.3 | 2.17 | 36.1 | 655 | 98 |
| 3 | 70 | 20g/AmCb | 4.0 | 50 | 60.0 | 0.7 | 5.2 | 0.10 | 6.1 | 1.4 | 5.1 | 1.7 | 2.169 | 34.8 | 695 | 99 |
| 4 | 70 | 3.2g/AmOx | 3.8 | 50 | 35.0 | 1.7 | 5.0 | 0.09 | 7.1 | 1.5 | 4.3 | 1.8 | 2.17 | 32.8 | 705 | 98 |
| 5 | 70 | 7.5g/AmOx | 4.6 | 50 | 70.0 | 0.6 | 5.0 | 0.10 | 7.7 | 1.5 | 4.1 | 1.5 | 2.173 | 36.6 | 690 | 101 |
| 6 | 63 | 7.0g/AmOx | 7.6 | 50 | 60.0 | 0.7 | 4.7 | 0.11 | 7.8 | 1.3 | 5.0 | 1.9 | 2.171 | 35.4 | 720 | 99 |
| 7 | 63 | 7.0g/AmOx | 7.6 | 50 | 35.0 | 1.7 | 4.7 | 0.09 | 7.6 | 1.4 | 4.8 | 1.9 | 2.169 | 3.73 | 665 | 97 |
| 8 | 63 | 7.5g/AmOx | 7.6 | 50 | 70.0 | 0.6 | 4.7 | 0.12 | 7.5 | 1.3 | 5.1 | 1.9 | 2.164 | 34.5 | 690 | 103 |
Claims (5)
1.一种制备含0.02-0.25wt％且在全氟代烷基链上具有1-4个碳原子的全氟代烷基乙烯基醚单元的四氟乙烯聚合物的方法，该方法包括在低于60℃温度下，使用高锰酸、锰酸或亚锰酸的盐类引发剂，在水溶性介质中，由悬浮工艺来聚合单体。
2.根据权利要求1所述的方法，其中高锰酸盐用作反应引发剂。
3.根据权利要求1或2所述的方法，其中所述的醚是全氟代丙基乙烯醚。
4.根据权利要求1或2所述的方法，其中粗品聚合物被磨成平均粒径10到50微米。
5.根据权利要求4所述的方法，其中磨过的产品被造粒。
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| DEP4335705.9 | 1993-10-20 | ||
| DE4335705A DE4335705A1 (de) | 1993-10-20 | 1993-10-20 | Herstellung eines modifizierten Polytetrafluorethylens und seine Verwendung |
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| US5760151A (en) * | 1995-08-17 | 1998-06-02 | E. I. Du Pont De Nemours And Company | Tetrafluoroethylene copolymer |
| US5756620A (en) * | 1995-11-15 | 1998-05-26 | E. I. Du Pont De Nemours And Company | Tetrafluoroethylene polymer for improved paste extrusion |
| DE19547907A1 (de) * | 1995-12-21 | 1997-06-26 | Dyneon Gmbh | Nichtrieselfähige Formpulver aus modifizierten Polytetrafluorethylenen |
| US5919878A (en) * | 1996-09-13 | 1999-07-06 | E. I. Du Pont De Nemours And Company | Amorphous fluoropolymer containing perfluoro(ethyl vinyl ether) |
| KR100487197B1 (ko) * | 1997-11-03 | 2005-07-11 | 삼성전자주식회사 | 양방향무선데이터송수신기를이용한가정보안시스템 |
| IT1298172B1 (it) | 1998-01-22 | 1999-12-20 | Ausimont Spa | Processo per la preparazione di politetrafluoroetilene (ptfe) modificato |
| US7125941B2 (en) * | 2001-03-26 | 2006-10-24 | 3M Innovative Properties Company | Aqueous emulsion polymerization process for producing fluoropolymers |
| WO2002088206A2 (en) | 2001-05-02 | 2002-11-07 | 3M Innovative Properties Company | Emulsifier free aqueous emulsion polymerization process for making fluoropolymers |
| EP1432744B2 (en) * | 2001-05-02 | 2014-10-01 | 3M Innovative Properties Company | Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers |
| US6737489B2 (en) | 2001-05-21 | 2004-05-18 | 3M Innovative Properties Company | Polymers containing perfluorovinyl ethers and applications for such polymers |
| US7045571B2 (en) | 2001-05-21 | 2006-05-16 | 3M Innovative Properties Company | Emulsion polymerization of fluorinated monomers |
| US7279522B2 (en) | 2001-09-05 | 2007-10-09 | 3M Innovative Properties Company | Fluoropolymer dispersions containing no or little low molecular weight fluorinated surfactant |
| US6870020B2 (en) * | 2002-04-30 | 2005-03-22 | E. I. Du Pont De Nemours And Company | High vinyl ether modified sinterable polytetrafluoroethylene |
| EP1533325B1 (en) * | 2003-11-17 | 2011-10-19 | 3M Innovative Properties Company | Aqueous dispersions of polytetrafluoroethylene having a low amount of fluorinated surfactant |
| ATE433350T1 (de) * | 2004-03-01 | 2009-06-15 | 3M Innovative Properties Co | Verfahren zum beschichten eines gegenstands mit einer fluorhaltigen kunststoffsdispersion |
| US20060160016A1 (en) * | 2004-10-12 | 2006-07-20 | Presstek, Inc. | Inkjet-imageable lithographic printing members and methods of preparing and imaging them |
| GB2427170A (en) * | 2005-06-17 | 2006-12-20 | 3M Innovative Properties Co | Fluoropolymer film having glass microspheres |
| GB0514387D0 (en) * | 2005-07-15 | 2005-08-17 | 3M Innovative Properties Co | Aqueous emulsion polymerization of fluorinated monomers using a perfluoropolyether surfactant |
| GB0514398D0 (en) | 2005-07-15 | 2005-08-17 | 3M Innovative Properties Co | Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant |
| US20070025902A1 (en) * | 2005-07-15 | 2007-02-01 | 3M Innovative Properties Company | Recovery of fluorinated carboxylic acid from adsorbent particles |
| GB0523853D0 (en) | 2005-11-24 | 2006-01-04 | 3M Innovative Properties Co | Fluorinated surfactants for use in making a fluoropolymer |
| US20080015304A1 (en) * | 2006-07-13 | 2008-01-17 | Klaus Hintzer | Aqueous emulsion polymerization process for producing fluoropolymers |
| GB0525978D0 (en) * | 2005-12-21 | 2006-02-01 | 3M Innovative Properties Co | Fluorinated Surfactants For Making Fluoropolymers |
| GB2430437A (en) * | 2005-09-27 | 2007-03-28 | 3M Innovative Properties Co | Method of making a fluoropolymer |
| US7728087B2 (en) | 2005-12-23 | 2010-06-01 | 3M Innovative Properties Company | Fluoropolymer dispersion and method for making the same |
| US20070276103A1 (en) * | 2006-05-25 | 2007-11-29 | 3M Innovative Properties Company | Fluorinated Surfactants |
| US7754795B2 (en) | 2006-05-25 | 2010-07-13 | 3M Innovative Properties Company | Coating composition |
| US8119750B2 (en) | 2006-07-13 | 2012-02-21 | 3M Innovative Properties Company | Explosion taming surfactants for the production of perfluoropolymers |
| US7678859B2 (en) | 2006-09-14 | 2010-03-16 | 3M Innovative Properties Company | Preparation and stabilization of fluoropolymer dispersions |
| US20100084343A1 (en) * | 2007-02-16 | 2010-04-08 | Mader Brian T | System and process for the removal of fluorochemicals from water |
| US20080264864A1 (en) | 2007-04-27 | 2008-10-30 | 3M Innovative Properties Company | PROCESS FOR REMOVING FLUORINATED EMULSIFIER FROM FLUOROPOLMER DISPERSIONS USING AN ANION-EXCHANGE RESIN AND A pH-DEPENDENT SURFACTANT AND FLUOROPOLYMER DISPERSIONS CONTAINING A pH-DEPENDENT SURFACTANT |
| GB0716421D0 (en) | 2007-08-23 | 2007-10-03 | 3M Innovative Properties Co | Method of preparing fluoropolymers by aqueous emulsion polymerization |
| WO2009054629A1 (en) | 2007-10-24 | 2009-04-30 | Lg Electronics, Inc. | Linear compressor |
| CN103210003B (zh) | 2010-11-09 | 2016-09-07 | 纳幕尔杜邦公司 | 减弱含烃表面活性剂在含氟单体含水分散体聚合反应中的调聚性能 |
| EP2638082B1 (en) | 2010-11-09 | 2019-04-17 | The Chemours Company FC, LLC | Nucleation in aqueous polymerization of fluoromonomer |
| EP2638081B1 (en) | 2010-11-09 | 2019-07-03 | The Chemours Company FC, LLC | Aqueous polymerization of fluoromonomer using hydrocarbon surfactant |
| WO2015081055A1 (en) | 2013-11-26 | 2015-06-04 | E. I. Du Pont De Nemours And Company | Employing polyalkylene oxides for nucleation in aqueous polymerization of fluoromonomer |
| JP6742321B2 (ja) * | 2015-09-08 | 2020-08-19 | Ａｇｃ株式会社 | 変性ポリテトラフルオロエチレンファインパウダー、その製造方法、およびチューブまたはホースの製造方法 |
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| US3142665A (en) * | 1960-07-26 | 1964-07-28 | Du Pont | Novel tetrafluoroethylene resins and their preparation |
| NL6716757A (zh) * | 1966-12-15 | 1968-06-17 | ||
| US3855191A (en) * | 1973-04-04 | 1974-12-17 | Du Pont | Polytetrafluoroethylene molding powders of tetrafluoroethylene and perfluoro (alkyl vinyl ether) copolymer |
| DE2523569C3 (de) * | 1975-05-28 | 1980-08-07 | Hoechst Ag, 6000 Frankfurt | Verfahren zur Polymerisation von Tetrafluoräthylen nach dem Suspensionsverfahren |
| DE2639109A1 (de) * | 1976-08-31 | 1978-03-09 | Hoechst Ag | Copolymerisate des tetrafluoraethylens und verfahren zu deren herstellung |
| DE3024450A1 (de) * | 1980-06-28 | 1982-01-28 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von waessrigen, kolloidalen dispersionen von copolymerisaten des typs tetrafluorethylen-ethylen |
| US4576869A (en) * | 1984-06-18 | 1986-03-18 | E. I. Du Pont De Nemours And Company | Tetrafluoroethylene fine powder and preparation thereof |
| US4640955A (en) * | 1984-06-18 | 1987-02-03 | E. I. Du Pont De Nemours And Company | Tetrafluoroethylene fine powder and preparation thereof |
| US4639497A (en) * | 1985-08-28 | 1987-01-27 | E. I. Du Pont De Nemours And Company | Preparation of tetrafluoroethylene fine powder |
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| RU94038263A (ru) | 1996-08-20 |
| DE4335705A1 (de) | 1995-04-27 |
| CN1103870A (zh) | 1995-06-21 |
| KR100350558B1 (ko) | 2002-10-31 |
| KR950011486A (ko) | 1995-05-15 |
| RU2141488C1 (ru) | 1999-11-20 |
| EP0649863B1 (de) | 1996-04-24 |
| JPH07233223A (ja) | 1995-09-05 |
| US5530078A (en) | 1996-06-25 |
| CA2131757A1 (en) | 1995-04-21 |
| DE59400234D1 (de) | 1996-05-30 |
| EP0649863A1 (de) | 1995-04-26 |
| JP3941971B2 (ja) | 2007-07-11 |
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