CN1053200C - 含有源自二烯烃的单体单元的含氟弹性体 - Google Patents
含有源自二烯烃的单体单元的含氟弹性体 Download PDFInfo
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Abstract
一种在具有单体结构的大分子链中和/或链端含有碘和/或溴原子的过氧化可硫化含氟弹性体,包括a)1,1-二氟乙烯,b)四烯乙烯,c)六氟丙烯或全氟甲基乙烯基醚和d)通式为CH2=CH-Z-CH=CH2的双烯烃,其中Z是-(CF2)6-或-CH2OCH2-CF2O-(CF2CF2O)m-(CF2O)n-CF2CH2OCH2-。
Description
本发明涉及具有改善的可加工性和很好的力学性能和高弹性的新含氟弹性体。
本领域已知多种含氟弹性体。它们被广泛地应用于既需要很好的弹性又需要高的热化学稳定性的所有场含。对这些产品的广泛的综述可参见例如“Ullman′s Encyclopedca of Industrial Chemistry”,Vol.A-11,pp.417-429(1988,VCH Verlagsgesellschaft)。
含氟弹性体的硫化可用离子或过氧化物进行。就前者而言,是将适宜的硫化剂(例如多羟基化合物)与促进剂(例如四烷基铵盐)一起加到含氟弹性体中。就过氧化物硫化而言,聚合物必须包含能够在过氧化物的存在下生成自由基的硫化部位。为此,可将含有碘和/或溴的“硫化部位(cure-site)”的单体引入聚合物链中,如US-4,035,565,US-4,745,165和EP-199,138所述;或者在聚合过程中可以使用含有碘和/或溴的链转移剂,这样便可生成碘化和/或溴化的端基(参见例如US-4,243,770和US 5,173,553)。
在硫化混合物的配制过程中常常遇到的问题是可加工性差,尤其是在需要较长时间的压延时可加工性差,特别是要将添加剂和填料混入混合物时,更是如此。所谓“添加剂”是指所有那些加到硫化混合物中起硫化剂、抗氧剂、稳定剂等作用的物质;而“填料”通常是指起颜料、增稠剂、增强剂、增塑剂等作用的物质(炭黑、二价金属氧化物和氢氧化物、硅、滑石粉等)。
人们知道,具有宽分子量分布的聚合物通常表现出较好的可加工性,因此,通过用聚合过程参数来改变含氟弹性体的分子量分布,尤其是用引发剂和链转移剂的送入反应器的数量和方式来改变分子量分布,则有可能克服上述缺陷。然而,这些手段将促使产物显示出明显的挤出膨胀现象,可用Garvey速率测定出来。
人们知道,通过适当地混合分子量分布不同的聚合物可以改善含氟弹性体的可加工性。但是这将除了有挤出膨胀现象外,还不可避免地使最终产品的力学性能和可模塑性变差。
本申请人现在惊异地发现,有可能获得具有改善的可加工性(尤其是在压延硫化混合物时的可加工性)以及很好的挤出和注塑时的力学性能和加工性能并具有很好的脱模性的新的含氟弹性体。通过向聚合物链中引入少量结构如下文定义的二烯烃便可获得所述效果。
因此,本发明的目的是提供一种含氟弹性体,它包含源自通式如下的二烯烃单体单元:式中:R1,R2,R3,R4,R5和R6彼此相同或不同,是H或C1-C5烷基;Z是C1-C18亚烷基或亚环烷基,它们可以是直链或支链的,并可选地
含有氧原子,最好是至少部分氧化的;
或者Z是(全)氟聚氧化亚烷基;
在式(I)中,Z是优选C4-C12全氟亚烷基,更优选C4-C8全氟亚烷基,而R1,R2,R3,R4,R5,R6优选为氢。
当Z是(全)氟聚氧化亚烷基时,它优选具有下式结构;-(Q)p-CF2O-(CF2CF2O)m(CF2O)n-CF2-(Q)p- (II)式中:Q是C1-C10亚烷基或氧化亚烷基;p是0或1;m和n是整数,其取值应使m/n比率在0.2-5之间并且使所述(全)氟聚氧化亚烷基的分子量在500-10,000之间,优选在1000-4000之间。Q优选-CH2OCH2-;-CH2O(CH2CH2O)SCH2-,S=1-3。
Z是亚烷基或亚环烷基的式(I)二烯烃可按照I.L.Knunyants等人,Izv.Akad.Nauk.SSSR,Ser.Khim.,1964(2),384-6所述的方法制备;而含有(全)氟聚氧化亚烷基序列的二烯烃的制备方法可参见US-3,810,874所述。
源自这样的二烯烃的单元在链中的含量,按照每100mol其它基础单体单元计算,通常为0.01-1.0mol,优选0.03-0.5mol,更优选0.05-0.2mol。
含氟弹性体的基础结构尤其可选自:(1)基于VOF的共聚物,其中VDF与至少一种选自下列化合物的共聚
单体共聚:C2-C8全氟烯烃,如四氟乙烯(TFE)、六氟丙烯(
HFP);C2-C8氯和/或溴和/或碘氟烯烃,如一氯三氟乙烯(
CTFE)和一溴三氟乙烯;(全)氟烷基乙烯基醚(PAVE)
CF2=CFORf,其中Rf是C1-C6(全)氟烷基;例如三氟甲基、一溴二
氟甲基、五氟丙基;全氟-烷氧基乙烯基醚CF2=CFOX,其中X
是具有一个或多个醚基团的C1-C12全氟烷氧基,例如全氟-2-
丙氧基丙基;C2-C8非氟代烯烃(01),例如乙烯和丙烯;(2)基于TFE的共聚物,其中TFE与至少一种选自下列化合物的共聚
单体共聚:(全)氟烷基乙烯基醚(PAVE)CF2=CFORf,其中
Rf定义如上;全氟-烷氧基乙烯基醚CF2=CFOX,其中X定义如上
;含有氢和/或氯和/溴和/或碘原子的C2-C8氟化烯烃,C2-
C8非氟代烯烃。
在上文定义的各类化合物中,优选的基础单体如下(摩尔%):
(a)VDF 45-85%,HFP 15-45%,0-30%TFE;(b)VDF 50-80%,PAVE 5-
50%,TFE 0-20%;(c)VDF 20-30%,01 10-30%,HFP and/or PAVE 18-
27%,TFE 10-30%;(d)TFE 50-80%,PAVE 20-50%;(e)TFE 45-65%,
01 20-55%,0-30%VDF;(f)TFE 32-60%,01 10-40%,PAVE 20-40%;
(g)TFE 33-75%,15-45% PAVE,10-22% VDF.
重要的是,必须指出,对于适氧化物可硫化含氟弹性体来说,加入少量本发明的二烯烃可获得更进一步的突出优点。人们的确知道,为了达到较好的硫化水平,必须尽可能增加每条链上活性部位的数量,即碘和/溴的量。为此目的,我们可以努力增加碘化和/或溴化链转移剂的量,同时尽可能避免反应速率降低。除了该方法包含的操作困难之外,每条链上碘和/或溴原子的数目最多为两个,因为本领域已知的链转移剂最多含有两个碘和/或溴原子。实际上,从未达到过该理论极限,因为不可能在不引起反应速率的不可接受的降低的同时,将链转移剂/引发剂之经提高到超过一定的限度。按照该方法,通过每条链上最多只能获得1.8个碘和/或溴原子。因此,最终产物的硫化水平对于许多需要高弹性的应用场合显得不足。例如,该产物的压缩形变通常至少为28-30%(按照标准ASTM D395,方法B,在200℃下70小时测定)。
将本发明的工作实施例与下文报导的比较例比较,显然引入少量本发明的二烯烃可使产物发生一种预硫化(所达到的高分子量便是证明);对于过氧化物硫化的情况,使得与未使用本发明二烯烃制备的同一聚合物相比每条链终端碘和/溴的量显著地增加。因此,能够达到高的硫化水平,从而达到低的压缩形变值。例如,用于O型环来说,压缩形变值通常低于25%(按照标准ASTM D395方法B,在200℃下70小时测定)。
本发明的目标含氟弹性体的制备方法如下:按照本领域熟知的方法,在自由基引发剂(例如碱金属或铵的过硫酸盐、过磷酸盐、过硼酸盐或过碳酸盐)及可选的铁、铜或银盐或其它易氧化金属的存在下,在水性乳液中将单体共聚合。在反应介质中,通常还加有各种表面活性剂,其中特别优选下式氟代表面活性剂:
Rf-X-M+式中Rf是C5-C16(全)氟烷基链或(全)氟聚氧化亚烷基链,X-是-COO-或-SO3 -,M+选自H+,NH4 +和碱金属离子。其中最常用的有:全氟辛酸铵、带有一个或多个羧端基的(全)氟聚氧化亚烷基等。
加到反应混合物中的二烯烃的量取决于期望的最终产物中源自二烯烃的单元的数量,要记住的是,若以本发明目的而采用的量较少,则实际上反应介质中所有的二烯烃都将进入大分子链中。
聚合反应完成后,用常规方法如加入电解质或冷却絮凝的方法将含氟弹性体从乳液中分离出来。
或者,可按照熟知的技术进行本体聚合或者在包含适当自由基引发剂的有机液体中进行悬浮聚合。
聚合反应通常在不超过10MPa的压力下于25-150℃的温度下进行。
本发明的目标含氟弹性体的制备最好是按照US-4,789,717和US-4,864,006所述,在全氟聚氧化亚烷基的乳液、分散液或微乳液的存在下以水性乳液的方式进行聚合。
本发明的目标含氟弹性体优选用过氧化物硫化,因而最好在大分子链中和/或端基中含有碘和/或溴原子。可以这样引入所述碘和/或溴原子:向反应混合物中加进溴化和/或碘化的“硫化部位”共聚单体,如具有2-10个碳原子的溴代和/或碘代烯烃(参见例如US-4,035,565和US-4,694,045所述),或碘和/或溴氟烷基乙烷基醚(参见US-4,745,165,US-4,564,662和EP-199,138所述),其用量通常应使最终产物中“硫化部位”共聚单体的含量为每100mol其它基础单体单元0.05-2mol。
或者,可以与“硫化部位”共聚单体一起引进端基碘和/或溴原子,方法是向反应混合物中加入碘化和/或溴化的链转移剂,例如式Rf(I)x(Br)y化合物,其中Rf是具有1-8个碳原子的(全)氟烷基或(全)氟氯烷基,而x和y是是0-2的整数,且1≤x+y≤2(参见例如US-4,243,770和US-4,943,622)。也可以使用US-5,173,553中所述的碱金属或碱土金属碘化物和溴化物作为链转移剂。
或者,可以与含有碘和/或溴的链转移剂一起使用其它本领域公知的链转移剂,例如乙酸乙酯、丙二酸二乙酯等。
过氧化物硫化按照公知技术通过加入适宜的经加热可产生自由基的过氧化物来进行。在最常用的过氧化物中,我们可以提及:二烷基过氧化物,例如过氧化二叔丁基和2,5-二甲基-2,5-二(叔丁基过氧)己烷;过氧化二枯基;过氧化二苯甲酰;过苯甲酸二叔丁酯;碳酸二[1,3-二甲基-3-(叔丁基过氧化)丁]酯。其它过氧化物体系可参见例如专利申请EP-136,596和EP-410,351。
在硫化混合物中还加有其它物质,例如:(a)硫化活性助剂,其用量为聚合物的0.5-10%(重量),优选1-
7%(重量);其中常用的是:氰尿酸三烯丙酯;异氰尿酸三烯
丙酯(TAIC);三(二烯丙胺)-S-三嗪;亚磷酸二烯丙酯;
N,N-二烯丙基烯酰胺;N,N,N′,N′-四烯丙基丙二酰胺;异氰
尿酸三乙烯酯;2,4,6-三乙烯基甲基三硅氧烷等;特别优选TAIC(b)金属化合的,其用量为聚合物的1-15%(重量),优选2-10%
(重量),它们可选自二价金属的氧化物或氢氧化物,例如Mg,
Zn,Ca或Pb的氧化物或氢氧化物,同时可选地与弱酸盐例如Ba,
Na,K,Pb,Ca的硬脂酸盐、苯甲酸盐、碳酸盐、草酸盐或亚磷
酸盐一起使用;(c)其它常规添加剂,诸如增稠剂、颜料、抗氧化剂、稳定剂等。
在打算离子硫化本发明的目标含氟弹性体时,除上述(b)项和(c)项所述的化合物外,还向硫化混合物中加入本领域熟知的适宜的硫化剂和促进剂。例如,作为硫化剂,可以使用芳族或脂族多羟基化合物或其衍生物,例如EP-355,705和US-4,233,427所述。其中,我们可特别提及二、三和四羟基苯类、萘类或蒽类;双酚类,其中两个芳族通过脂族、环脂族和芳族二价基团相连,或通过氧或硫原子或者还有羰基相连。所述芳环可以被一个或多个氯、氟、溴原子或被羰基、烷基、酰基取代。
作为促进剂,可以使用例如:季铵盐、季鏻盐、季鉮盐或季锑盐(参见例如EP-335,705和US-3,876,654);氨基鏻盐(参见例如US-4,259,463);正膦类(参见例如US-3,752,787);EP-182,299和EP-120,462所述的亚胺化合物等。
也可以使用混合的离子型或过氧化物型硫化体系,如EP-136,596所述。
现在用下列工作实例来更好地说明本发明,它仅仅是对本发明范围的说明而不是限定。
压延可加工性通过测定炭黑加入时间(BIT),即压延过程中聚合物混入填料所需的时间来评定。所述测定在操作上是用辊子直径为150mm的压延机进行的,辊子上粘附大约0.5kg聚合物。一旦在辊子上形成均匀的聚合物层,便立即加进表中所列量的填料:BIT定义为从填料加入到聚合物层不再从辊子自动脱落所经过的时间。当然,BTT越短,填料混入的速率越高,从而压延加工生产率便越高。实施例1
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入4升软化水和41.1ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:- 8.9ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH式中n/m=10,其中均分子量为600;- 8.9ml 30%(体积)的NH4OH水溶液;- 17.8ml软化水;- 5.5ml下式Galden(R)DO2:CF3O(CF2-CF(CF3)O)n(CF2O)mCF3式中n/m=20,其中均分子量为450。
然后,将高压釜加热至85℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 14.7%(摩尔)
六氟丙烯(HFP) 78.3%(摩尔)
四氟乙烯(TFE) 7.3%(摩尔)从而使压力升至22×105Pa。
然后,向高压釜中引入:- 浓度为50g/l的过硫酸铵(APS)水溶液作为引发剂;添加分10
次进行,第一次加30ml,随后,单体转化率每增加10%则每次加
3.4ml;- 溶液形式的1,4-二碘全氟丁烷(C4F8I2)作为链转移剂,所述
溶液通过将4.26ml碘化产物溶解在45.74ml上面制备微乳液所用
的Galden(R)DO2中制得;添加分20次进行,每次2.5ml,从开始聚
合起,单体转化率每增加5%便添加一次;- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过
将2.5ml该二烯烃溶解在45.5ml上面所述的Galden(R)DO2中制得;
添加分20次进行每次2.5ml,从开始聚合起,单体转化率每增加5
%便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持22×105Pa的压力不变:
VDF 50%(摩尔)
HFP 26%(摩尔)
TFE 24%(摩尔)
反应23分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到622g产物,其特性列于表1中。
聚合物的单体组成用19F-NMR和IR分析测定。含碘百分数用X-射线萤光分析测定。平均分子量Mn(数均)、Mw(重匀)和Mz用凝胶渗透色谱(GPC)测定。渗透压分子量(Mosm)用校准曲线计算。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表2。实施例2(比较例)
按照与实施例1所述相同的方法,制备不含所述二烯烃的同一种聚合物。这样制得的产物的特性及经过氧化物硫化的产物的特性分别列于表1和表2。
表1
(*)比较例n.d.:无法测定
实施例 | 1 | 2(*) |
聚合物组合物 (%mol)VDFHFPTFE二烯烃 | 5026240.16 | 502624-- |
碘 (%重量)(每条链) | 0.643.4 | 0.631.5 |
门尼粘度 (ASTM D1646)ML(1+10′) 121℃ML(1+4′) 100℃ | 1125 | n.d.4 |
特性粘数 [η](30℃,MEK) | 37.8 | 23.7 |
Tg起点 (℃)(DSC-ASTM D 3418-82) | -12.3 | -14.3 |
MnMwMzMw/MnMz/MwMonm | 30,000136,000497,0004.53.667,000 | 24,00040,00059,0001,61,535,000 |
表2
(*)比较例n.d.:无法测定Vmax:最大硫化速度实施例3
实施例 | 1 | 2(*) |
硫化混合物组成聚合物 (g)Luperco(R)101 XL (phr)Drimix(R)TAIC ″ZnO ″炭黑MT ″ | 10034530 | 10034530 |
硫化混合物特性*门尼粘度 ML(1+10′)121℃(ASTM D1646)*ODR 177℃ arc 3,12′(ASTM D2084-81)ML (牛顿·米)MH (牛顿·米)ts2 (秒)ts50 ″t′90 ″Vmax (牛顿·米/秒) | 170.4515.144263964.53 | 20.1113.5660781084.61 |
170℃下10分钟加压硫化后的性能*力学性能 (ASTM D412-83)模量 (100%) (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点) | 7.513.215867 | n.d.n.d.n.d.n.d. |
于230℃烘箱中24小时后硫化后的性能*力学性能 (ASTM D412-83)模量 100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点)*压缩形变(200℃,70小时)(ASTM D395 方法B)O型环214 (%)圆片 (%) | 8.016.316.2693815 | n.d.n.d.n.d.n.d.n.d.n.d. |
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入3.5升软化水和36.0ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:- 7.8ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH式中n/m=10,其中均分子量为600;- 7.8ml 30%(体积)的NH4OH水溶液;- 15.6ml软化水;- 5.5ml下式Galden(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3式中n/m=20,其中均分子量为450。
然后,将高压釜加热至80℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 45%(摩尔)
全氟甲基乙烯基醚(MVE) 36%(摩尔)
四氟乙烯(TFE) 19%(摩尔)从而使压力升至22×105Pa。
然后,向高压釜中引入:- 50ml浓度为2g/l的过硫酸铵(APS)水溶液作为引发剂;一次加
完。- 溶液形式的1,4-二碘全氟丁烷(C4F8I2)作为链转移剂,所述
溶液通过将4.26ml碘化产物溶解在45.74ml上面制备微乳液所用
的Galden(R)DO2中制得;添加分20次进行,每次2.5ml,从开始聚
合起,单体转化率每增加5%便添加一次;- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过
将2.9ml该二烯烃溶解在47.1ml上述的Galden(R)DO2中制得;添加
分20次进行每次2.5ml,从开始聚合起,单体转化率每增加5%便
添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持22×105Pa的压力不变:
VDF 58%(摩尔)
MVE 18%(摩尔)
TFE 24%(摩尔)
反应116分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到1500g产物,其特性列于表3中。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表4。实施例4(比较例)
按照与实施例3所进相同的方法,制备不含所述二烯烃的同类型聚合物。这样制得的产物的特性及经过氧化物硫化的产物的特性分别列于表3和表4。
表3
(*)比较例
实施例 | 3 | 4(*) |
聚合物组合物 (%mol)VDFMVETFE二烯烃 | 59.217.623.20.074 | 60.118.221.7-- |
碘 (%重量)(每条链) | 0.292.05 | 0.291.53 |
门尼粘度 (ASTM D1646)ML(1+10′) 121℃ML(1+4′) 100℃ | 5680 | 2037 |
特性粘数 [η](30℃,MEK) | 89 | 72.6 |
Tg起点 (℃)(DSC-ASTM D 3418-82) | -30.7 | -30.8 |
MnMwMzMw/MnMz/MwMonm | 81,000467,0002,688,0005.85.790,000 | 62,000212,0001,038,0003.44.967,000 |
表4
(*)比较例实施例5
实施例3 | 3 | 4(*) |
硫化混合物组成聚合物 (g)Luperco(R)101 XL (phr)Drimix(R)TAIC ″ZnO ″炭黑MT ″ | 10034530 | 10034530 |
硫化混合物特性*门尼粘度 ML(1+10′)121℃(ASTM D1646)*ODR 177℃ arc 3,12′(ASTM D2084-81)ML (牛顿·米)MH (牛顿·米)ts2 (秒)ts50 ″t′90 ″Vmax (牛顿·米/秒) | 431.5815.0348751053.55 | 210.4514.3551811054.30 |
170℃下10分钟加压硫化后的性能*力学性能 (ASTM D412-83)模量 100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点) | 5.116.519969 | 4.416.822469 |
于230℃烘箱中24小时后硫化后的性能*力学性能 (ASTM D412-83)模量 100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点)*压缩形变(200℃,70小时)(ASTM D395 方法B)O型环214 (%) | 5.118.32106924 | 4.717.82256928 |
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入3.5升软化水和36.0ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:- 7.8ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH式中n/m=10,其中均分子量为600;- 7.8ml 30%(体积)的NH4OH水溶液;- 15.6ml软化水;- 5.5ml下式Galden(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3式中n/m=20,其中均分子量为450。
然后,将高压釜加热至80℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 27%(摩尔)
全氟丙烯(HFP) 57%(摩尔)
四氟乙烯(TFE) 16%(摩尔)从而使压力升至25×105Pa。
然后,向高压釜中引入:- 140ml浓度为1g/l的过硫酸铵(APS)水溶液作为引发剂;一次
加完。- 溶液形式的1,4-二碘全氟丁烷(C4F8I2)作为链转移剂,所述
溶液通过将4.4ml碘化产物溶解在50ml上面制备微乳液所用的
Galden(R)DO2中制得;探测到聚合开始便一次加完。- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过
将3.7ml该二烯烃溶解在46.3ml上述Galden(R)DO2中制得;添加分
20次进行,每次2.5ml,从开始聚合起,单体转化率每增加5%便
添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持25×105Pa的压力不变:
VDF 50%(摩尔)
HFP 26%(摩尔)
TFE 24%(摩尔)
反应130分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到1550g产物,其特性列于表5中。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表6中。实施例6(比较例)
按照与实施例5所述相同的方法,用2.6ml碘化的链转移剂制备不含所述二烯烃的同类型聚合物。这样制得的产物的特性及经过氧化物硫化的产物的特性分别于表5和表6。
表5
(*)比较例
实施例 | 5 | 6(*) |
聚合物组合物 (%mol)VDFHFPTFE二烯烃 | 52.223.624.20.093 | 53.123.223.7-- |
碘 (%重量)(每条链) | 0.322.64 | 0.181.1 |
门尼粘度 (ASTM D1646)ML(1+10′) 121℃ML(1+4′) 100℃ | 5499 | 5189 |
Tg起点 (℃)(DSC-ASTM D 3418-82) | -12.0 | -13.2 |
MnMwMzMw/MnMz/MwMonm | 81,000315,000958,0003.93.0105,000 | 69,000163,000333,0002.32.078,000 |
表6
(*)比较例实施例7
实施例 | 5 | 6(*) |
硫化混合物组成聚合物 (g)Luperco(R)101 XL (phr)Drimix(R)TAIC ″ZnO ″炭黑MT ″ | 10034530 | 10034530 |
硫化混合物特性*门尼粘度 ML(1+10′)121℃(ASTM D1646)*ODR 177℃ arc 3,12′(ASTM D 2084-81)ML (牛顿·米)MH (牛顿·米)ts2 (秒)ts50 ″t′90 ″Vmax (牛顿·米/秒) | 411.5817.064061903.64 | 481.6913.56751051602.97 |
170℃下10分钟加压硫化后的性能*力学性能: (ASTM D412-83)模量 100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点) | 7.521.425078 | 5.619.226076 |
于230℃烘箱中24小时后硫化后的性能*力学性能 (ASTM D412-83)模量 100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点)*压缩形变(200℃,70小时)(ASTM D395方法B)O型环214 (%) | 8.523.72607923 | 6.221.62517630 |
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入4.0升软化水和410.1ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:- 8.9ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH式中n/m=10,其中均分子量为600;- 8.9ml 30%(体积)的NH4OH水溶液;- 17.8ml软化水;- 5.5ml下式Galde(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3式中n/m=20,其中均分子量为450。
然后,将高压釜加热至85℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 53.5%(摩尔)
六氟丙烯(HFP) 46.5%(摩尔)从而使压力升至22×105Pa。
然后,向高压釜中引入:- 浓度为50g/l的过硫酸铵(APS)水溶液作为引发剂;添加分10
次进行,第一次加40.4ml,随后,单体转化率每增加10%则每次
加4.4ml;- 溶液形式的乙酸乙酯作为链转移剂,所述溶液通过将66ml乙酸乙
酯溶解在1000ml水中制得,探测到聚合开始便一次加完50ml所述
溶液。- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过
将2.5ml该二烯烃溶解在45.5ml上述的Galden(R)DO2中制得;添加
分20次进行,每次2.5ml,从开始聚合起,单体转化率每增加5%
便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持22×105Pa的压力不变:
VDF 78.5%(摩尔)
HFP 21.5%(摩尔)
反应30分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到622g产物,其特性列于表7中。
然后,将聚合物离子硫化,硫化混合物组成和硫化产物的特性列于表8。实施例8(比较例)
按照与实施例7所述相同的方法,制备不含所述二烯烃的同类型聚合物。这样制得的产物的特性及经离子硫化的产物的特性分别于表7和表8。
表7
(*)比较例
实施例 | 7 | 8(*) |
聚合物组合物 (%mol)VDFHFP二烯烃 | 78.721.30.14 | 78.221.8-- |
门尼粘度 (ASTM D1646)ML(1+10′) 121℃ML(1+4′) 100℃ | 70111 | 5895 |
特性粘数 [η](30℃,MEK) | 104 | 90 |
Tg起点 (℃)(DSC-ASTM D 3418-82) | -24.8 | -26.2 |
MnMwMzMw/MnMz/Mw | 58,000311,000826,0005.32.6 | 70,000292,000792,0004.22.7 |
表8
(*)比较例M1:双酚AF/含氟弹性体(50/50)母料M2:N,N-二乙基-二苯基苄基-氨基氯/含氟弹性体(30/70)
实施例 | 7 | 8(*) |
硫化混合物组成聚合物 (g)M1 (phr)M2 ″MgO ″Ca(OH)2 ″炭黑MT ″ | 10041.53630 | 10041.53630 |
炭黑加入时间 (BIT)(对于炭黑 ,MgO,Ca(OH)2) | 2′43″ | 4′49″ |
硫化混合物特性*门尼粘度 ML(1+10′)121℃(ASTM D1646)*ODR 177℃ arc 3,12′(ASTM D2084-81)ML (牛顿·米)MH (牛顿·米)ts2 (秒)ts50 ″t′90 ″Vmax (牛顿·米/秒) | 1122.2612.651622373361.7 | 961.6911.971532253031.9 |
170℃下10分钟加压硫化后的性能*力学性能 (ASTM D412-83)模量100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点) | 4.511.727070 | 4.211.327470 |
于230℃烘箱中24小时后硫化后的性能*力学性能 (ASTM D412-83)模量 100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点)*压缩形变(200℃,70小时)(ASTM D395方法 B)O型环214 (%) | 7.216.91867217 | 6.417.42037017 |
母料。实施例9
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入3.5升软化水和36.0ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:- 7.8ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH式中n/m=10,其中均分子量为600;- 7.8ml 30%(体积)的NH4OH水溶液;- 15.6ml软化水;- 5.5ml下式Galden(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3式中n/m=20,其中均分子量为450。
然后,将高压釜加热至80℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 30.0%(摩尔)
六氟丙烯(HFP) 54.0%(摩尔)
四氟乙烯(TFE) 16.0%(摩尔)从而使压力升至21×105Pa。
然后,向高压釜中引入:- 140ml浓度为1.0g/l的过硫酸铵(APS)水溶液作为引发剂;- 溶液形式的1,6-二碘全氟己烷(C6F12I2)作为链转移剂,所述
溶液通过将5.5ml碘化产物溶解在14.5ml上面制备微乳液所用的
Galden(R)DO2中制得;- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过
将2.5ml该二烯烃溶解在47.5ml上述Galden(R)DO2中制得;添加分
20次进行每次2.5ml,从开始聚合起,单体转化率每增加5%便添
加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持21×105Pa的压力不变:
VDF 50%(摩尔)
HFP 26%(摩尔)
TFE 24%(摩尔)
反应160分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到1522g产物,其特性列于表9中。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表10中。实施例10
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入3.5升软化水和36.0ml实施例9所述的全氟聚氧化亚烷基微乳液。
然后,将高压釜加热至80℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 30.0%(摩尔)
六氟丙烯(HFP) 54.0%(摩尔)
四氟乙烯(TFE) 16.0%(摩尔)从而使压力升至21×105Pa。
然后,向高压釜中引入:- 140ml浓度为1.0g/l的过硫酸铵(APS)水溶液作为引发剂;- 溶液形式的1,6-二碘全氟己烷(C6F12I2)作为链转移剂,所述
溶液通过将5.5ml碘化产物溶解在14.5ml上面制备微乳液所用的
Galden DO2中制得;- 溶液形式的式
CH2=CH-CH2OCH-CF2O-(CF2CF2O)m(CF2O)n-CF2-CH2OCH2-CH=CH2二烯烃,其中m/n比率为0.5,全氟聚氧化
亚烷基基团的分子量为2,000。所述溶液通过将12.0ml该二烯烃
溶解在38.0ml上述的Galden(R)DO2中制得;添加分20次进行,每
次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持21×105Pa的压力不变:
VDF 50%(摩尔)
HFP 26%(摩尔)
TFE 24%(摩尔)
反应200分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到1589g产物,其特性列于表9中。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表10。
表9
实施例 | 9 | 10 |
聚合物组合物 (%mol)VDFHFPTFE二烯烃 | 53.622.424.00.05 | 54.121.024.90.07 |
碘 (%重量)(每条链) | 0.382.39 | 0.382.45 |
门尼粘度 (ASTM D1646)ML(1+10′) 121℃ML(1+4′) 100℃ | 1843 | 2251 |
特性粘数 [η](30℃,MEK) | 41.8 | 45.3 |
Tg起点 (℃)(DSC-ASTM D 3418-82) | -12.5 | -13.6 |
表10
实施例 | 9 | 10 |
硫化混合物组成聚合物 (g)Luperco(R)101 XL (phr)Drimix(R)TAIC ″ZnO ″炭黑MT ″ | 10034530 | 10034530 |
硫化混合物特性*门尼粘度 ML(1+10′)121℃(ASTM D1646)*ODR 177℃ arc 3,12′(ASTM D2084-81)ML (牛顿·米)MH (牛顿·米)ts2 (秒)ts50 ″t′90 ″Vmax (牛顿·米/秒) | 260.6815.4857901204.22 | 230.5614.860931204.02 |
170℃下10分钟加压硫化后的性能*力学性能 (ASTM D412-83)模量100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点) | 4.316.824469 | 4.216.324370 |
于230℃烘箱中24小时后硫化后的性能*力学性能 (ASTM D412-83)模量100% (MPa)断裂应力 (MPa)断裂伸长 (%)肖氏硬度A (点)*压缩形变(200℃,70小时)(ASTM D395方法B)O型环214 (%) | 6.120.52447228 | 6.220.92327434 |
Claims (2)
1.一种在具有单体结构的大分子链中和/或链端含有碘和/或溴原子的过氧化可硫化含氟弹性体,包括a)50-59.2%摩尔的1,1-二氟乙烯,b)23.2-24.9%摩尔的四氟乙烯,c)21-26%摩尔的六氟丙烯或17.6%摩尔的全氟(甲基)乙烯基醚,上述组分a)、b)和c)之和等于100%摩尔,和d)每100摩尔(a)+(b)+(c)有0.05-0.16摩尔通式为CH2=CH-Z-CH=CH2的双烯烃,其中Z是-(CF2)6-或-CH2OCH2-CF2O-(CF2CF2O)m-(CF2O)-CF2CH2OCH2-基团,其中m/n是0.5和分子量是2,000。
2.根据权利要求1的含氟弹性体,其中含0.29-0.64%(重量)的碘原子。
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ITMI93A002750 | 1993-12-29 | ||
IT93MI002750A IT1265461B1 (it) | 1993-12-29 | 1993-12-29 | Fluoroelastomeri comprendenti unita' monomeriche derivanti da una bis-olefina |
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CN1053200C true CN1053200C (zh) | 2000-06-07 |
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- 1994-12-23 EP EP94120504A patent/EP0661304B1/en not_active Expired - Lifetime
- 1994-12-23 DE DE69406408T patent/DE69406408T2/de not_active Expired - Lifetime
- 1994-12-23 AT AT94120504T patent/ATE159537T1/de not_active IP Right Cessation
- 1994-12-23 AT AT97103588T patent/ATE186309T1/de active
- 1994-12-23 EP EP97103588A patent/EP0784064B1/en not_active Expired - Lifetime
- 1994-12-23 TW TW083112098A patent/TW287172B/zh not_active IP Right Cessation
- 1994-12-23 DE DE69421553T patent/DE69421553T2/de not_active Expired - Lifetime
- 1994-12-27 RU RU94045137A patent/RU2136702C1/ru active
- 1994-12-28 JP JP32905694A patent/JP3574198B2/ja not_active Expired - Lifetime
- 1994-12-29 KR KR1019940038927A patent/KR100359143B1/ko active IP Right Grant
- 1994-12-29 CN CN94119959A patent/CN1053200C/zh not_active Expired - Lifetime
- 1994-12-29 BR BR9405300A patent/BR9405300A/pt not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
---|---|
RU94045137A (ru) | 1996-10-10 |
ITMI932750A1 (it) | 1995-06-30 |
KR100359143B1 (ko) | 2003-02-05 |
JP3574198B2 (ja) | 2004-10-06 |
RU2136702C1 (ru) | 1999-09-10 |
CA2139260A1 (en) | 1995-06-30 |
BR9405300A (pt) | 1995-09-19 |
DE69406408D1 (de) | 1997-11-27 |
ATE159537T1 (de) | 1997-11-15 |
DE69421553D1 (de) | 1999-12-09 |
EP0784064A1 (en) | 1997-07-16 |
EP0661304A1 (en) | 1995-07-05 |
TW287172B (zh) | 1996-10-01 |
DE69406408T2 (de) | 1998-05-07 |
EP0784064B1 (en) | 1999-11-03 |
KR950018107A (ko) | 1995-07-22 |
US5585449A (en) | 1996-12-17 |
CA2139260C (en) | 2005-10-25 |
CN1108263A (zh) | 1995-09-13 |
IT1265461B1 (it) | 1996-11-22 |
EP0661304B1 (en) | 1997-10-22 |
ITMI932750A0 (it) | 1993-12-29 |
DE69421553T2 (de) | 2000-06-21 |
ATE186309T1 (de) | 1999-11-15 |
JPH0812726A (ja) | 1996-01-16 |
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