CN1120343A - 低温全氟弹性体 - Google Patents
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Abstract
含有高分子量全氟聚醚的全氟弹性体组合物具有改善的低温性能。
Description
发明领域
本发明涉及全氟弹性体,特别是提高这类弹性体的低温性能。
发明背景
全氟弹性体(如在美国专利3,682,872、4,281,092、4,487,903和4,983,697中提到的)的性质使之在非常苛刻条件下的应用非常引入瞩目,这些材料适合用于既需要弹性体的性质同时又需耐高温或耐化学侵蚀性的场合。
与其它弹性体一样,全氟弹性体的机械性能通常可通过下面的方法来调整。例如,改变全氟单体在聚合物中的比例、改变炭黑和其它配合物成分的用量以及改变硫化化学方法等。然而某些场合下的用途则需要综合各种性能,而这用通常方法是不可能得到的。比如,我们特别期望能降低弹性体的玻璃化转变温度(Tg)并同时将其使用温度区间扩展到较低温度。
发明的概述
本发明提供了硫化的全氟弹性体,通过将其与选定的全氟聚醚混合,使全氟弹性体的低温性能得到改善而热老化和耐化学侵蚀性不会被破坏。
具体而言,本发明提供了含有全氟烯烃、全氟(烷基乙烯基)醚(其中烷基含1~5个碳原子)的共聚单元和至多3%(摩尔)至少一种含硫化点单体的全氟弹性体组合物,其改进之处在于该组合物还含有约5~20 phr粘度至少为约3000mm2/s的全氟聚醚。
本发明的详细描述
本发明基于下面的发现,即在全氟弹性体配合物中混入全氟聚醚(PFPE)可改善硫化全氟弹性体的低温性能。令人意想不到的是通过选择具有适当粘度的PFPE,可使全氟弹性体的Tg大大降低。当用这种配合物制备密封件时,低温密封能力得到提高。在得到这些改善的同时,高温稳定性和耐化学性并未因此受到损害。
本发明的全氟弹性体主要是由两种或更多种全氟化单体制备的,所述单体例如四氟乙烯(TFE)或其它全氟烯烃和全氟(烷基乙烯基)醚(其中烷基含1~5个碳原子)。典型的这类反应物为全氟(甲基乙烯基)醚(PMVE)和全氟(丙基乙烯基)醚(PPVE)。这些单体通常与可促进交联的共聚单体混用。也可使用少量非全氟化单体。通常使用这类单体的目的是为了得到合适的交联性能,其含量最多可达3%(摩尔)。这类单体的实例包括一溴四氟丁烯、一溴三氟乙烯及含氰基的单体。根据需要可在聚合反应中加入非全氟化的链转移剂以便在聚合物中引入所需的链段以改善硫化性能。这类链转移剂包括二碘代化合物,采用该化合物使聚合物中(通常在分子的末端)含有键合的碘。美国专利3,467,638、4,281,092、4,487,903、4,529,784、4,948,853、4,983,697举例说明了典型的全氟弹性体。
本发明所用的PFPE可有任何链结构,只要分子骨架上的氧原子被饱和氟碳基团隔开即可。一个分子中可包含一种以上氟碳基团。
可用于本发明的PFPE的典型结构包括:(-CFCF3-CF2-O-)n (I)(-CF2-CF2-CF2-O-)n (II)(-CF2-CF2-O-)n-(-CF2-O-)m (III)(-CF2-CFCF3-O-)n-(-CF2-O-)m (IV)这些结构已由Franco Piacenti在Chemistey International,13,p147(1991)中讨论过。如该文所述,PFPE含有全氟端基。本发明所用PFPE的运动粘度应至少为约3000mm2/s,优选3000-4000mm2/s,所述粘度是在20℃时按ASTM-D-445测定的。
可用于本发明的具体PFPE可直接购得,它们是基于一系列化学结构如下的氟封端的六氟环氧丙烷均聚物的通用润滑剂:为确保本发明所需的粘度,聚合物必须含有足够的重复单元。
PFPE可用常规混炼技术混入到氟弹性体组合物中,其用量为每100份全氟聚合物用5-20份。PFPE的含量低于5份时全氟弹性体的性能无明显改观,而大于20phr(每100份橡胶的份数)时并无进一步改善并会从组合物中渗出。
本发明的组合物可广泛应用于那些既需要全氟弹性体的低温性能又需要其通常的优良性能的场合。特殊的用途包括极端低温下的密封及填充,例如由此共混物制备的阀垫片可在零下50℃令人满意地工作。
过去PFPE油曾被用于全氟弹性体的塑化,但以往使用的这种油类挥发性高,有效期短,因此,当以足以用来塑化的量混入时会渗出。为解决渗出问题,早期的试验包括加入与全氟弹性体共硫化的含硫化点的单体。通过使用高粘度的PFPE,本发明综合了以前没有达到的加工和使用性能。
在下面的实施例及对照实施例中,全氟弹性体、全氟聚醚和其他指定成分的配合料是在标准开炼机上制备的,辊筒预先加热到约55℃。在开炼机混炼中,首先将全氟弹性体聚合物单独置于辊缝内,混炼直至形成胶带,聚合物被充分混合,以及开炼机上保持滚胶。然后将预先称重的全氟聚醚加入辊缝内,最后将组合物一直混炼到均匀为止。
实施例及对照实施例中所用的两种PFPE组合物的性质如下:
PFPE X为上面讨论的I型全氟聚醚,20℃时的粘度约为1600mm2/s,商品牌号为KRYTOX氟化油级143D(杜邦公司)或本发明以前的全氟弹性体配合料中所用的PFPE油。
PFPE Y同样属于上述I型全氟聚醚,20℃时的粘度约为3500mm2/s,商品牌号为KRYTOX氟化油级16350(杜邦公司)。
将配合的共混物压缩成型为15cm×15cm×1.9mm的薄片以便进行物理性能测试。硫化和后硫化的方法如各实施例中所述。物理性能测试所用样片按表I所列的试验方法的要求从薄片上冲切。Tg用差示扫描量热法(DSC)测定。
表I.物理性能测试方法 代号
性 能
方法M100 100%伸长模量(psi或MPa) ASTM D-412Tb 断裂抗张强度(psi或MPa) ASTM D-412Eb 断裂伸长(%) ASTM D-412H 硬度(Shore A,粒状) ASTM D-395CS 压缩形变(%,70小时/204℃,粒状) ASTM D-395Tg 玻璃化转变温度(℃) DSC
在所有的实施例和对比实施例中,份数或百分数均是按重量计算的。
实施例1-6和对照实施例A-E
全氟弹性体聚合物P是由TFE和PMVE共聚并加入含硫化点单体5-五氟苯氧基-全氟(5-甲基-3-氧杂-1-戊烯)得到的弹性共聚物,通常可按美国专利3,467,638中所述方法制备。聚合物P与PFPE及表II中所列的其他成分配合、模制后按上面所述方法测试其物理性能。将模制片在190℃加压硫化30分钟,然后将其放入一烘箱内,在氮气气氛下按下述方法进行后硫化,在40小时内将温度慢慢从室温升至260℃,接着在260℃后硫化8小时。表II所列的测试结果表明,PFPE X和PFPE Y对组合物的机械性能影响类似,但当所用PFPE的量大于3phr时,PFPE Y对组合物Tg的影响出人意料地大。在表II中,实施例6的测试结果是两个配合料样品的平均值。其他实施例和对比实施例的结果均由一个配合样品所得。
表II实施例 A B C D E 1 2 3 4 5 6配方:聚合物P 100 100 100 100 100 100 100 100 100 100 100PFPE X - 3 7 10 20 - - - - - -PFPE Y - - - - - 3 5 7 10 15 20炭黑a 10 10 10 10 10 10 10 10 10 10 10DCH-18-冠-6b 4 4 4 4 4 4 4 4 4 4 4MgO 4 4 4 4 4 4 4 4 4 4 4K2AFc 3 3 3 3 3 3 3 3 3 3 3性能:M100 2651 2608 2399 2176 1441 2637 2345 2244 2098 1635 1537Tb 3277 3328 3479 2553 3099 3335 3938 3373 3263 3383 2930Eb 121 121 132 138 159 118 149 134 134 160 151H 95 92 89 89 83 90 88 89 88 86 86CS 28 27 26 26 24 24 26 25 24 25 25Tg -5 -7 -7 -21 -48 -7 -12 -20 -33 -45 -52aSAF型炭黑b PCR,Inc.c双酚-AF二钾盐
实施例7及对照实施例F和G
将全氟弹性体聚合物R与PFPE及表III中所列的其他组成配合、模制后按前述方法测试其物理性能。聚合物R是通常按美国专利4,281,092制备的TFE/PMVE/8-CNVE全氟弹性体。含硫化点单体8-CNVE为全氟(8-氰基-5-甲基-3,6-二氧杂-1-辛烯)。将模制片在200℃加压硫化30分钟,然后在90℃烘箱中在氮气气氛下后硫化6小时,接着在10小时内将温度从90℃均匀升到305℃,最后在305℃保持26小时。从表III所列的测试结果可以看出,弹性体的机械性能与所加炭黑的量有明显的关系。但是,与两组含有PFPE X的共混物相比,尽管在含PFPE Y的共混物中炭黑的加入量介于二者之间,但所得共混物的Tg比二者低得多。
表III实施例
F
G
7配方聚合物R 100 100 100PFPE X 10 10PFPE Y 10炭黑a 15 50 2518-冠-6b 0.3 0.3 0.3四苯基锡 3 3 3性质M100 MPa 2.59 14.4 4.87
psi (375) (2088) (712)Tb MPa 14.1 17.2 11.6
psi (2077) (2562) (1687)Eb 239 121 198H 62 91CS 12 29 19Tg -17 -20 -35 a MT型炭黑b Parish Chemical Co.
实施例8和对比实施例H
将全氟弹性体聚合物S与PFPE及表IV所列的其他成分配合、模制后按上述方法测试其物理性能。聚合物S是TFE、PMVE和BTFB的共聚物,其中BTFB为含硫化点单体4-溴-3,3,4,4-四氟丁烯。这类全氟弹性体及其制备方法如美国专利4,035,565中所述。按前面所述的常规方法混炼并模制后,将样片在177℃加压硫化10分钟,然后按实施例1-6中提到的时间-温度程序在烘箱中于氮气氛下进行后硫化。表IV所列结果表明,既使炭黑的用量较高,PFPE Y的加入也有助于降低聚合物S型全氟弹性体的Tg。
表IV实施例 H 8配方:聚合物S 100 100PFPE X 10PFPE Y 10炭黑a 45 45交联剂b 3 3TMAICc 2 2Proton Sponged 0.5 0.5TMSe 0.5 0.5性能M100 9.5 11.1
(1379) (1611)Tb 13.4 13.35
(1965) (1938)Eb 130 124H 92 88CS 34 31T g -12 -17a.MT型炭黑
b.50% 2,5-二甲基-2,5-二(叔丁基过氧基)己烷载于惰
性载体上,购自Atochem,Inc.,商品牌号Luperco101 XL
c.异氰脲酸三甲代烯丙酯,DiakNo.8硫化剂,杜邦公司。
d.1,8-二(二甲氨基)萘,Aldrich Chemical Co.
e.四氢噻吩砜。
实施例9及对比实施例I和J
按上述方法重新制备实施例4及对比实施例A和D中的配合物,模制后直接进行测试并在空气中于260℃热老化70小时后再进行测试,结果示于表V中。I、J和9也分别以A'、D'和4'进行编号以便于和前面的实施例进行比较。这些结果表明,PFPE对配合物的热稳定性几乎没有影响,且使用高粘度的PFPE将使配合物的失重减少。就失重而言,PFPE Y的优点可由对于由相同配合物制成的O形环的老化测试(分别在260℃老化70小时、168小时和336小时)看出。含PFPE Y的配合物的重量变化与对照实施例A'基本上相同,大约是含PFPE X的配合物(对照实施例D')的一半。336小时后,对照实施例A'、D'和实施例4'的重量变化分别为-3.2%、-5.9%和-2.9%。
表V实施例
I(A')
J(D′)
9(4')性能:模制后
M100 MPa 20.5 14.9 15.4
psi (2986) (2167) (2233)
Tb MPa 24.1 25.4 23.1
psi (3499) (3686) (3340)
Eb 114 153 141
260℃下硫化70小时后
M100 MPa 15.7 12.3 11.8
psi (2277) (1778) (1705)
Tb MPa 23.3 24.9 23.5
psi (3355) (3616) (3401)
Eb 129 160 159
Tg -5 -21 -33
重量变化 (%) -1.9 -2.6 -1.8对比实施例K-M
高粘度PFPE在含氢的含氟弹性体中的作用可利用聚合物T进行说明,聚合物T是VF/HFP/ TEE三元共聚物,通常按美国专利4,123,603的方法制备。将聚合物T与30phr MT型炭黑、3phr氧化镁、6phr氢氧化钙、0.6phr苄基三苯基氯化鏻(于1.2phr含氟弹性体载体上)、1.6phr双酚AF(于1.6phr含少量米糠蜡的含氟弹性体载体上)及表VI所示的PFPE配合、模制后按前述方法测试。表VI的结果表明,两种PFPE均对Tg无大影响,对于这种含氢的含氟弹性体来讲,加入高粘度的PFPE的作用并不象在全氟弹性体中那样明显。
表VI实施例
K
L
M配方聚合物T 100 100 100PFPE X 15PFPE Y 15性能M100 MPa 5.86 4.55 4.63
psi (850) (660) (670)Tb MPa 15.6 11.3 11.5
psi (2260) (1640) (1670)Eb 206 197 194H 72 68 69CS 21 26 24Tg -22 -23 -22
Claims (5)
1.一种含有全氟烯烃、全氟(烷基乙烯基)醚的共聚单元及至多3%(摩尔)至少一种含硫化点单体的全氟弹性体组合物,所述烷基含有1-5个碳原子,其改进之处在于该组合物还含有约5-20phr粘度至少为约3000mm2/s的全氟聚醚。
2.按照权利要求1所述的全氟弹性体组合物,其中全氟聚醚的通式如下:
3.按照权利要求1所述的全氟弹性体组合物,其中全氟聚醚的粘度约为3000-4000mm2/s。
4.按照权利要求1所述的全氟弹性体组合物,其中全氟聚醚的含量约为7-15phr。
5.按照权利要求1所述的全氟弹性体组合物,其中全氟聚醚主要由具有下述重复单元的化合物组成:
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US08/040,813 US5268405A (en) | 1993-03-31 | 1993-03-31 | Low temperature perfluoroelastomers |
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- 1994-03-29 EP EP94912335A patent/EP0691999B1/en not_active Expired - Lifetime
- 1994-03-29 DE DE69403788T patent/DE69403788T2/de not_active Expired - Lifetime
- 1994-03-29 CN CN94191669A patent/CN1120343A/zh active Pending
- 1994-03-29 JP JP52229194A patent/JP3451354B2/ja not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
JPH08508532A (ja) | 1996-09-10 |
JP3451354B2 (ja) | 2003-09-29 |
DE69403788T2 (de) | 1998-01-15 |
WO1994022952A1 (en) | 1994-10-13 |
DE69403788D1 (de) | 1997-07-17 |
EP0691999B1 (en) | 1997-06-11 |
US5268405A (en) | 1993-12-07 |
EP0691999A1 (en) | 1996-01-17 |
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