CN100999595A - 低分子量氢化丁腈橡胶的制备方法 - Google Patents
低分子量氢化丁腈橡胶的制备方法 Download PDFInfo
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- CN100999595A CN100999595A CNA2007100051319A CN200710005131A CN100999595A CN 100999595 A CN100999595 A CN 100999595A CN A2007100051319 A CNA2007100051319 A CN A2007100051319A CN 200710005131 A CN200710005131 A CN 200710005131A CN 100999595 A CN100999595 A CN 100999595A
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- polymer composition
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- polymer
- mooney viscosity
- nitrile rubber
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/08—Depolymerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
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- Polymers & Plastics (AREA)
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Abstract
本发明涉及在没有任何共聚烯烃存在时制备比本技术已知的氢化丁腈橡胶具有更低分子量和更窄分子量分布的氢化丁腈橡胶聚合物的方法。
Description
本申请是申请日为2003年12月5日、申请号为200310124089.4、发明名称为“低分子量氢化丁腈橡胶的制备方法”的发明专利申请的分案申请。
技术领域
本发明涉及一种在没有共聚烯烃存在时,制备比本领域已知的氢化丁腈橡胶聚合物分子量更低且分子量分布更窄的氢化丁腈橡胶聚合物的方法。
另一方面,本发明涉及包含至少一种选择氢化的、门尼粘度(ML 1+4,100℃)为50-30的丁腈橡胶聚合物,至少一种填料和任选的至少一种交联剂的聚合物组合物。
背景技术
由丙烯腈-丁二烯橡胶(丁腈橡胶,NBR,包含至少一种共轭二烯烃,至少一种不饱和腈和任选的其它共聚单体的共聚物)选择氢化制备的氢化丁腈橡胶(HNBR)是一种特种橡胶,它具有非常好的耐热性,优良的抗臭氧和耐化学性,以及优良的耐油性。由于其高水平的机械性能(尤其是高耐磨性),HNBR广泛用于汽车(封条,软管,轴承垫板)石油(定子,油井盖封条,阀板),电气(电缆覆材),机械工程(轮胎,辊子)和造船(管接头密封条,联接器)工业,以及其它工业就并不奇怪了。
市售的HNBR门尼粘度在55-105之间,分子量在200,000-500,000g/mol之间,多分散性大于3.0,残余的双键(RDB)含量在1-18%之间(由红外光谱仪测得)。
HNBR加工中的一个限制就是相对高的门尼粘度。一般来说,分子量更低以及门尼粘度更低,HNBR的加工性能就更好。曾经有人尝试过用塑炼(机械断裂)和化学方法(比如说,使用强酸)来降低聚合物的分子量,但是这些方法有一些缺点,它们往聚合物中引入了功能性基团(如羧酸和酯基),改变了聚合物的微观结构。这些导致了聚合物性质变劣。另外,此类方法,由于其本质特征,得到的是分子量分布宽的聚合物。
用现有的技术是很难制备门尼粘度较低的(<55)并且加工性能改善的,但是和目前市售的此类橡胶具有相同的微观结构的氢化丁腈橡胶。将NBR氢化制备HNBR导致了原料聚合物门尼粘度的增加。门尼增加率(MIR)通常约为2,这取决于聚合物等级,氢化程度和原料的性质。并且,NBR产品自身的局限性决定了HNBR原料的低粘度范围。目前,市售的门尼粘度最低的产品是TherbanVP KA 8837(Bayer公司有售),其门尼粘度为55(ML 1+4,100℃),RDB为18%。
待审查申请PCT/CA02/00967,PCT/CA02/00966和PCT/CA02/00965公开了一种选择氢化的丁腈橡胶的制备方法,此制备方法包含在至少一种共聚烯烃存在下让丁腈橡胶发生反应。本发明公开了一种选择氢化的丁腈橡胶的制备方法,此制备方法包含在没有共聚烯烃存在时让丁腈橡胶发生反应。
发明内容
我们现在知道,比本领域已知产品具有更低分子量和更窄的分子量分布的选择氢化丁腈橡胶可以通过有共聚烯烃存在时丁腈橡胶发生易位反应,接着将易位反应得到的NBR氢化而制得。本发明的方法能够制备出分子量(Mw)范围在20,000-250,000,门尼粘度(ML 1+4,100℃)为1-50,MWD(或者多分散指数)小于2.6的选择氢化的丁腈橡胶。
一方面,本发明涉及一种聚合物组合物,该组合物包含至少一种门尼粘度(ML 1+4,100℃)为50-30,残余双键(RDB)含量在1-18%之间(由红外光谱仪测得)的选择氢化丁腈橡胶聚合物(″NBR″或者,如果氢化的话为″HNBR″),至少一种填充剂和任选的至少一种交联剂。优选NBR完全或者部分氢化(″HNBR″)。特别地,本发明涉及一种聚合物组合物,其包含至少一种门尼粘度(ML 1+4,100℃)范围在50-30,优选低于50,更优选低于45的选择氢化丁腈橡胶。
具体实施方式
说明书通篇使用的术语“腈聚合物”有较宽的含义,意思是要包含一种共聚物,其重复单元衍生自至少一种共轭双烯,至少一种α,β-不饱和腈和任选的另外一种或多种可共聚单体。
共轭双烯可以是任何已知的共轭双烯,尤其是C4-C6的共轭双烯。优选的共轭双烯是丁二烯,异戊二烯,1,3-戊二烯,2,3-二甲基丁二烯和它们的混合物。甚至更优选的C4-C6的共轭双烯是丁二烯,异戊二烯和它们的混合物。最优选的C4-C6的共轭双烯是丁二烯。
不饱和的α,β-不饱和腈可以是任何已知的α,β-不饱和腈,尤其是C3-C5的α,β-不饱和腈。优选的C3-C5的α,β-不饱和腈是丙烯腈,甲基丙烯腈,乙基丙烯腈(ethacrylonitrile)和它们的混合物。最优选的C3-C5的α,β-不饱和腈是丙烯腈。
优选的,共聚物包含40-85重量百分比的由一种或多种共轭双烯得到的重复单元,15-60重量百分比的由一种或多种不饱和腈得到的重复单元。更优选的,共聚物包含60-75重量百分比的由一种或多种共轭双烯得到的重复单元,25-40重量百分比的由一种或多种不饱和腈得到的重复单元。最优选的,共聚物包含60-70重量百分比的由一种或多种共轭双烯得到的重复单元,30-40重量百分比的由一种或多种不饱和腈得到的重复单元。
任选地,共聚物可以进一步包含由一种或多种可共聚合的单体得到的重复单元,如不饱和的羧酸等。非限制性的合适的不饱和羧酸的例子有富马酸,马来酸,丙烯酸,甲基丙烯酸和它们的混合物。由一种或多种可共聚合单体得到的重复单元可代替丁腈橡胶中腈和双烯的部分,并且上述数字必须调整以使重量百分比为100%,这对本领域熟练的技术人员讲是显而易见的。假设有上文提到的不饱和羧酸,丁腈橡胶就优选包含1-10重量百分比的由一种或多种不饱和羧酸得到的重复单元,根据这个量来替换相应的共轭双烯的量。这些共聚单体的存在似乎促进了易位反应并且使得上述反应能够在0-50℃温度范围内进行。
其它优选的任意更多的单体是不饱和的单或二羧酸或它们的衍生物(例如,酯,酰胺以及类似物)包括它们的混合物。
根据本发明,如果优选的HNBR需要的话,反应物先进行易位反应,然后再选择氢化。
易位反应
易位反应是在一种或多种通式I,II,III或IV的化合物存在下进行的,
通式I
其中
M是Os或Ru,
R和R1独立地是氢或烃,所述烃选自C2-C20的链烯基,C2-C20的炔基,C1-C20的烷基,芳基,C1-C20的羧酸酯基,C1-C20的烷氧基,C2-C20的链烯氧基,C2-C20的炔氧基,芳氧基,C2-C20的烷氧基羰基,C1-C20的烷硫基,C1-C20的烷基磺酰基和C1-C20的烷基亚磺酰基,
X和X1独立地是任何阴离子配体,
L和L1独立地是中性配体,如膦,胺,硫醚,咪唑烷亚基(imidazolidinylidenes)或咪唑烷或任何中性carbine,任选地,L和L1可以相互联接起来形成双齿中性配体;
通式II
其中
M1是Os或Ru,
R2和R3独立地是氢或烃,所述烃选自C2-C20的链烯基,C2-C20的炔基,C1-C20的烷基,芳基,C1-C20的羧酸酯基,C1-C20的烷氧基,C2-C20的链烯氧基,C2-C20的炔氧基,芳氧基,C2-C20的烷氧基羰基,C1-C20的烷硫基,C1-C20的烷基磺酰基和C1-C20的烷基亚磺酰基,
X2是一种阴离子配体,
L2是一种中性π-键配体,优选但不局限于芳烃,取代芳烃,杂芳烃,它们可以是单环或多环,
L3是选自于膦,磺化膦,氟化膦,带有最多3个氨基烷基、铵烷基、烷氧基烷基、烷氧羰基烷基、羟基羰基烷基、羟基烷基或酮烷基基团的官能化的膦,亚磷酸酯,次膦酸酯(phosphinites),亚膦酸酯,膦胺,胂,stibenes,醚,胺,酰胺,亚胺,亚砜,硫醚和吡啶;
Y-是一种非配位的阴离子,
n是0-5之间的整数;
通式III
其中
M2是Mo或W,
R4和R5独立地是氢或烃,所述烃选自C2-C20的链烯基,C2-C20的炔基,C1-C20的烷基,芳基的烃,C1-C20的羧酸酯基,C1-C20的烷氧基,C2-C20的链烯氧基,C2-C20的炔氧基,芳氧基,C2-C20的烷氧基羰基,C1-C20的烷硫基,C1-C20的烷基磺酰基和C1-C20的烷基亚磺酰基,
R6和R7独立地选自任何未取代或卤代的烷基,芳基,芳烷基或它们的含硅同类物;
通式IV
其中
M是Os或Ru,
R和R1独立地选自氢,取代或未取代的烷基,以及取代或未取代的烷基,
X和X1独立地是任何阴离子配体,以及
L和L1独立地是任何中性配体,如膦,胺,硫醚,咪唑烷亚基(imidazolidinylidenes)或咪唑烷或任何中性carbine,任选的,L和L1可以相互联接起来形成双齿中性配体。
优选通式I的化合物。更优选L和L1独立地选自三烷基膦、咪唑烷亚基(imidazolidinylidenes)或咪唑烷,X和X1是氯离子,M是钌的通式I的化合物。另一组优选的化合物是被称之为第2代Grubb’s催化剂的化合物,如1,3-二-(2,4,6-三甲基苯基)-2-咪唑烷亚基)-(三环己基膦)(苯基亚甲基)二氯化钌。
化合物的用量取决于所用化合物的性质和催化活性。一般来讲,化合物与NBR的比率在0.005-5之间,优选0.025-1,更优选为0.1-0.5。
易位反应是在没有任何共聚烯烃存在下进行的。
易位反应可以在任何不使催化剂失活或不干扰反应的溶剂中进行。优选的溶剂包括但不局限于二氯甲烷,苯,甲苯,四氢呋喃,甲基乙基酮,环己烷等。最优选的溶剂是单氯代苯(MCB)。在一定情况下共聚烯烃自身可以作为溶剂(比如,1-己烯),在这种情况下就不需要其它的溶剂了。
反应混合物中NBR的浓度并不是决定性的,但是显然,应该使得反应不至于受阻,比如如果混合物太粘稠,搅拌就无法有效的进行。优选的NBR的浓度在1-40重量%之间,最优选的范围是6-15重量%。
易位反应进行的温度范围优选0-140℃;在没有任何共聚单体存在时优选20-100℃。
反应时间取决于一些因素,包括胶浆的浓度、所用催化剂的量和反应进行的温度。在一般情况下易位反应通常在前两个小时之内就结束了。易位反应进程可以通过标准分析技术监测,比如使用GPC或者溶液粘度。说明书中所有引用的聚合物分子量分布是通过凝胶渗透色谱仪(GPC)测定的,该凝胶渗透色谱仪使用Waters 2690分离单元和运行3.05.01版本的Waters Millenium软件的Waters 410差示折射仪。将样品溶解在用0.025%BHT稳定的四氢呋喃(THF)中。测定使用的柱子是从聚合物实验室(Polymer Labs)得到的三个序列混合-B凝胶柱。使用的参考标样是美国Polymer Standards Corp的聚苯乙烯标样。
本发明优选的目的是氢化丁腈橡胶。从相应的NBR获得它们的一个方法就是氢化。
氢化
易位反应所得产物的还原可以用本领域熟知的标准还原技术实现。比如,可以使用本领域技术人员熟知的均相氢化催化剂,如Wilkinson’s催化剂
{(PPh3)3RhCl}以及类似物。
已知的NBR氢化反应方法也用于生产本发明所述的氢化产品。铑或钛通常被用作催化剂,虽然铂,铱,钯,铼,钌,锇,钴或铜以金属的形式存在,但是优选的金属化合物也可以使用,例如参见US3,700,637;DE-PS2,539,132;EP-A-134023;DE-OS35 41 689;DE-OS 35 40 918;EP-A 298 386;DE-OS 35 29252;DE-OS 34 33 392;US 4,464,515;和US 4,503,196。
适合均相氢化反应的催化剂和溶剂在下文中描述,在Bayer AG的GB1558491和EP 471,250中的事先引入这里作为参考。并不是要限制对本发明有用的氢化反应的催化剂和溶剂,提供的这些仅仅是作为例子。
选择氢化反应可以通过含铑的催化剂来实现。优选的催化剂具有如下通式
(R8mB)1RhX3n
其中R8是C1-C8的烷基、C4-C8的环烷基、C6-C15的芳基或C7-C15的芳烷基,B是磷、砷,硫或亚砜基团S=O,X3是氢或阴离子,优选卤素,更优选氯离子或溴离子,1是2,3或4,m是2或3,n是1,2或3,优选1或3。优选的催化剂是三-(三苯基膦)氯化铑(I),三-(三苯基膦)氯化铑(III)和三-(二甲基亚砜)氯化铑(III),通式为((C6H5)3P)4RhH的四-(三苯基膦)氢化铑,以及三苯基膦部分用三环己基膦部分替换得到的相应的化合物。催化剂可以用少量。相对于聚合物的重量,合适的用量范围在0.01-1.0%之间,优选0.03%-0.5%,最优选0.1%-0.3%,以重量计。
使用催化剂时使用一种助催化剂是大家都知道的,该助催化剂是具有通式为R8mB的配体,其中R,m,B与上文定义的一样,m优选3。优选的B是磷,R基团可以相同也可以不同。因此可以使用三芳基、三烷基、三环烷基、二芳基单烷基、二烷基单芳基、二芳基单环烷基、二烷基单环烷基、二环烷基单芳基或二环烷基单芳基助催化剂。美国专利US 4,631,315中给出了一些助催化剂配体的例子,其公开的内容合并过来作为参考。优选的助催化剂配体是三苯基膦。相对于共聚物的重量而言,所使用的助催化剂配体的量,以重量计,优选范围在0.3-5%之间,更优选0.5-4%。同时优选的含铑催化剂化合物与助催化剂的重量比为1∶3-1∶55,更优选1∶5-1∶45。相对于100重量份的橡胶而言,助催化剂的重量合适的范围为0.1-33,更合适的为0.5-20,优选1-5,最优选大于2至小于5。
原位进行氢化反应比较有利,比如在进行易位反应步骤的同一个反应容器中,不需要先分离易位反应产物。简单地将氢化反应催化剂加入到容器中,然后用氢气处理就可以生产出HNBR了。
本发明中的氢化反应优选将待氢化的起始腈聚合物中存在的残余双键(RDB)氢化多于50%,优选氢化RDB多于90%,更优选氢化RDB多于95%,最优选氢化RDB多于99%。
本发明目的之一的低门尼HNBR可以通过本领域已知的标准技术来表征。比如,聚合物的分子量分布是通过凝胶渗透色谱仪(GPC)测定的,该凝胶渗透色谱仪使用Waters 2690分离单元和运行3.05.01版本的Waters Millenium软件的Waters 410差示折射仪。将样品溶解在用0.025%BHT稳定的四氢呋喃(THF)中。测定使用的柱子是从聚合物实验室(Polymer Labs)得到的三个序列混合-B凝胶柱。使用的参考标样是美国Polymer Standards Corp的聚苯乙烯标样。
橡胶的门尼粘度的测定使用ASTM测试仪D1646。
本发明的聚合物组合物进一步包含至少一种填充剂。该填充剂可以是活性的或非活性的填充剂或者它们的混合物。填充剂可以特别为;
-高分散的硅酸盐,例如通过硅酸盐溶液沉淀或者硅的卤化物高温水解制得,具有比表面积5-1000m2/g,基本颗粒尺寸在10-400nm之间;该硅酸盐也可以任选的是与其它金属如Al,Mg,Ca,Ba,Zn,Zr和Ti的氧化物的混合氧化物;
-合成硅酸盐,例如硅酸铝和碱土金属的硅酸盐像硅酸镁或硅酸钙,BET比表面积范围在20-400m2/g,基本颗粒尺寸10-400nm;
-天然硅酸盐,如高岭土和其它天然存在的硅酸盐;
-玻璃纤维和玻璃纤维产品(matting,挤塑制品)或玻璃微球;
-金属氧化物,如氧化锌,氧化钙,氧化镁和氧化铝;
-金属碳酸盐,如碳酸镁,碳酸钙和碳酸锌;
-金属的氢氧化物,如氢氧化铝和氢氧化镁;
-炭黑;这里用的炭黑通过灯黑、炉黑或气黑工艺得到,其优选的BET(DIN66 131)比表面积范围在20-200m2/g之间,如SAF,ISAF,HAF,FEF,FEF或GPF炭黑;
-橡胶凝胶,尤其是那些基于聚丁二烯,丁二烯/苯乙烯共聚物,丁二烯/丙烯腈共聚物和聚氯丁二烯的橡胶凝胶;
或它们的混合物。
优选的矿物填充剂的例子有二氧化硅,硅酸盐,粘土如膨润土、石膏、钒土、二氧化钛、滑石以及它们的混合物等等。这些矿物颗粒的表面有羟基,赋予了它们亲水性和疏油性。这给填充颗粒和橡胶之间达到好的相互作用增加了难度。为了许多方面的目的,优选的矿物是二氧化硅,尤其是由二氧化碳沉淀硅酸钠得到的二氧化硅。根据本发明适合使用的干燥无定形二氧化硅颗粒平均块状颗粒尺寸在1-100微米之间,优选10-50微米,最优选10-25微米。优选尺寸小于5微米或大于50微米的聚集体颗粒少于10体积%。此外合适的无定形干燥二氧化硅通常具有一定的BET表面积,根据DIN(Deutsche IndustrieNorm)66131测量为50-450平方米每克,根据DIN53601测量的DBP吸收量为150-400克每100克二氧化硅,和根据DIN ISO787/11测量的干燥失重为0-10重量%。可以从PPG工业公司得到商标为HiSil210,HiSil233和HiSil243的合适的二氧化硅填充剂。Bayer AG的VulkasilS和VulkasilN也同样适用。
经常,使用炭黑作为填充剂比较有利。通常,在聚合物组合物中存在的炭黑的量为20-200重量份,优选30-150重量份,更优选40-100重量份。此外,在发明聚合物组合物中使用炭黑和矿物填充剂的组合可能会有利。在这种组合中矿物填充剂与炭黑的比通常为0.05-20,优选0.1-10。
聚合物组合物进一步可选择地包含一种或多种交联剂或固化体系。本发明并不局限于某一种特定的固化体系,不过优选过氧化物固化体系。并且,本发明并不局限于某一种特定的过氧化物固化体系,例如,无机的或有机的过氧化物都适合。优选的有机过氧化物有双烷基过氧化物,缩酮过氧化物(ketalperoxide),芳烷基过氧化物,醚过氧化物,酯过氧化物,如二叔丁基过氧化物,二-(叔丁基过氧化异丙基)-苯,过氧化二异丙苯,2,5-二甲基-2,5-二(叔丁基过氧基)-己烷,2,5-二甲基-2,5-二(叔丁基过氧基)-己烯(3),1,1-二-(叔丁基过氧基)-3,3,5-三甲基环己烷,过氧化苯甲酰,叔丁基异丙苯基过氧化物和过苯甲酸叔丁酯。通常聚合物组合物中过氧化物的量为1-10phr(=每一百份橡胶),优选4-8phr。接下来的固化通常是在100-200℃的温度范围内进行的,优选130-180℃。过氧化物以聚合物捆绑(polymer-bound)的形式应用是比较有利的。合适的体系市场有售,如从Rhein Chemie Rheinau GmbH得到的多分散T(VC)D-40 P,D(=聚合物捆绑的二-叔丁基过氧基-异丙基苯)。
根据本发明的橡胶组合物可以包含更多的橡胶助剂,如反应促进剂,硫化促进剂,硫化促进辅助剂,抗氧化剂,起泡剂,抗老化剂,热稳定剂,光稳定剂,臭氧稳定剂,加工助剂,增塑剂,增粘剂,发泡剂,染料,颜料,蜡,填料,有机酸,阻聚剂,金属氧化物,以及活化剂,如三乙醇胺,聚乙二醇,己三醇,等等,这些都是橡胶工业中熟知的。橡胶助剂使用的是常规用量,取决于与使用意图内在关系。相对于橡胶而言,常规的用量例如在0.1-50wt.%之间。优选的组合物包含0.1-20phr的有机脂肪酸作为助剂,优选分子中有一个、两个或更多碳双键的不饱和脂肪酸,其中更优选包括分子中至少有一个共轭碳-碳双键的10%重量或更多的共轭双烯酸。这些脂肪酸优选8-22个碳原子,更优选12-18个。这样的例子有硬脂酸,软脂酸,油酸和它们的钙、锌、镁、钾和氨盐。优选的组合物包含5-50phr的丙烯酸盐作为助剂。合适的丙烯酸盐可以从EP-A1-0319 320中获知,特别是第3页第16-35行,从US-5 208 294中,特别是第2栏25-40行,以及US-4 983 678,特别是第2栏45-62行。特别值得参考的是丙烯酸锌,二丙烯酸锌或二甲基丙烯酸锌或液态丙烯酸酯,如三羟甲基丙烷三甲基丙烯酸酯(TRIM),二甲基丙烯酸丁二醇酯(BDMA)和二甲基丙烯酸乙二醇酯(EDMA)。使用不同的丙烯酸酯和/或它们的金属盐的组合物较为有利。通常尤其有利的是将金属的丙烯酸盐与防焦剂如空间位阻的苯酚(例如甲基取代的氨基烷基苯酚,尤其是2,6-二叔丁基-4-二甲基氨基甲基苯酚)组合使用。
将最后聚合物组合物的各个组分混和在一起,合适的是在25-200℃范围内逐渐升高温度。混和时间一般不超过一小时,2-30分钟一般就足够了。混和适合在密炼机中进行,如Banbury炼胶机,或Haake或Brabender微型密炼机。双辊开炼机也可以使弹性体中添加剂较好分散。挤出机也可以较好的混和,同时能缩短混和时间。可以将混和在两个或多个阶段进行,同时混和可以在不同的设备中进行,比如一个阶段在密炼机中,一个阶段在挤出机中。然而,一定要注意在混和阶段不要有不希望的预交联(=焦化)发生。关于配合和硫化也可以参见:Encyclopedia of Polymer Science and Engineering,Vol.4,p.66 et seq.(配合)及Vol.17,p.66 et seq.(硫化)。
由于其较低的粘度,聚合物组合物非常理想的适合于但不局限于注射成型技术。聚合物组合物也可以用于传递成型,压模,或液体注射成型。含有交联体系的聚合物组合物常被引入到常规的注射成型中,注射到高温(160-230℃)形式,这里发生交联/硫化,取决于聚合物组合物的组分和成型的温度。
本发明的聚合物组合物非常适合于成形物品的加工,例如封条,软管,轴承垫板,挡板,油井盖封条,阀板,电缆覆材,轮胎,辊子,管接头密封,适当位置上的垫圈或注射成型技术制备的鞋类组件。
实施例
实施例1-2
三(三苯基膦)氯化铑(Wilkinson’s氢化催化剂),1,3-二-(2,4,6-三甲基苯基)-2-咪唑烷亚基)(三环己基瞵)(苯基亚甲基)二氯化钌(Grubbs第2代易位反应催化剂)。三苯基膦(TPP)和单氯代苯(MCB)分别从JMI,Materia Inc.,ElfAtochem和PPG购买并直接使用。
易位反应
易位反应在1L玻璃瓶中进行,反应条件如下:
胶浆浓度 6wt.%
烧瓶用工业搅拌器搅拌
反应温度 25℃
催化剂(Grubb’s)加入量 0.05phr
溶剂 单氯代苯
反应物 实施例1:丙烯腈含量为34wt%、门尼粘
度ML(1+4),100℃为29个单位的统
计丁二烯-丙烯腈共聚物。
实施例2:丙烯腈含量为21wt.%、丙烯酸
丁酯含量为32wt.%、门尼粘度ML(1+4),
100℃为29个单位的统计丁二烯-丙烯腈
三元共聚物。
往含有6%胶泥溶液的玻璃瓶中加入15ml含有Grubbs第二代催化剂的单氯代苯溶液。然后往玻璃瓶中充入氮气,盖上盖,室温下搅拌24小时。
氢化反应
氢化反应的条件如下:
胶浆的固含量 6%
H2(g)压力 1200psi
搅拌速度 600rpm
反应器温度 138℃
催化剂(Wilkinson’s)加入量 0.08phr
三苯基膦 1phr
溶剂 单氯代苯
从易位反应得到的胶浆在充分搅拌下用H2(100psi)除气三次。将反应器温度升高到130℃,向其中加入60ml含有Wilkinson’s催化剂和三苯基膦的单氯代苯。在反应期间,反应温度可以升高到138℃并维持不变。氢化反应通过使用红外光谱仪测定不同时间间隔的残余双键(RDB)水平来监测。
或者,钌易位反应催化剂也可以用于氢化聚合物。在这样的原位过程中用氢气处理的易位反应催化剂就转变成了可以作为氢化反应催化剂的化合物。
实施例1:具体细节
将75g原料1(共聚物)溶于1175g MCB(6wt.-%固体)中。然后向胶浆中通入干燥的氮气。更多的实验细节列于表1中。
实施例2:具体细节
将75g原料2(三元共聚物)溶于1175g MCB(6wt.-%固体)中。然后向胶浆中通入干燥的氮气。更多的实验细节列于表1中。
表1原料的NBR聚合物性质一览表
NBR共聚物 | NBR三元共聚物 | 实施例1的产物* | 实施例2的产物* | |
加入的GrubbsML(1+4,100℃)粘度(cP)MnMwPDI | N/A2838770002530003.3 | N/A27136500003080004.1 | 0.0251920750001850002.4 | 0.0051330470001190002.5 |
*氢化之前
表2原料的HNBR聚合物性质一览表
氢化后实施例1的产物 | TherbanA3406作为对比 | |
ML(1+4,100℃)MnMwPDIRDB(由IR测得) | 43740001870002.5<0.9% | 601010002840002.8<0.9% |
实施例3-4:以过氧化物配方(recipe)讲行配合和物理测试
在开炼机中将聚合物组合物混合。在不同的混合步骤向凉的开炼机中加入固化剂。本评估所用的公式基于简化的过氧化物配方。
炭黑N 660 Sterling-V从Cabot tire Blacks商购
MagliteD是从C.P.Hall商购的氧化镁。
Naugard445是从Uniroyal Chemical商购的二苯基胺。
Plasthall TOTM是从C.P.Hall商购的苯三酸三辛酯。
VulkanoxZMB-2/C5是从Bayer AG商购的4-和5-甲基-巯基苯并咪唑锌盐
DIAK#7是从DuPont Dow Elastomers商购的氰脲酸三烯丙酯
Vulcup 40KE是从Harwick Standard商购的2,2’-二(叔丁基过氧二异丙基苯)。
表3过氧化物固化配方
实施例 | 3 | 4 |
TherbanA3406作为对比氢化反应后实施例1的产物炭黑,N 660 Sterling-VMagliteDNaugard445VulkanoxMB-2/C5(ZMMBI)氧化锌(Kadox920)等级PC 216DIAK#7Vulcup 40KE | 10050310.431.57.5 | 10050310.431.57.5 |
聚合物组合物性质
表4显示的是实施例3和实施例4的聚合物组合物的性质汇总。实施例4是作参考用的。MDR固化特征是1.7Hz,1°arc,180℃,30min,100dNm。
表4聚合物组合物性质一览表
实施例 | 3 | 4 |
门尼粘度(ML1+4,100℃)-原料聚合物-聚合物组合物MR(dN.m)ML(dN.m)Delta扭矩:MH-M(dN.m)100%模量(Mpa)肖氏硬度A极限拉伸强度(Mpa)断裂伸长率(%)150℃ 70小时后的压缩变定百分率% | 437449.91.948.17.76824.224821.4 | 609453.53.150.48.46725.923321.3 |
从表4中可以清楚的看出,尽管聚合物组合物3中用到的低门尼HNBR的分子量(Mw)仅仅是TherbanA3406的66%,但是它的物理性质仍然非常好。
Claims (6)
1.一种聚合物组合物,包含至少一种门尼粘度(ML 1+4,100℃)为50-30的选择氢化的丁腈橡胶聚合物,至少一种填料和任选的至少一种交联剂。
2.如权利要求1所述的聚合物组合物,其中原料聚合物的门尼粘度(ML 1+4,100℃)低于50。
3.如权利要求1-2中任一项所述的聚合物组合物,其中聚合物组合物包含一种过氧化物体系。
4.如权利要求1-3中任一项所述聚合物组合物的制备方法,其特征在于,将至少一种门尼粘度(ML 1+4,100℃)为50-30的选择氢化的丁腈橡胶聚合物,至少一种填料和任选的至少一种交联剂混合。
5.一种制备成型制品的方法,包括将聚合物组合物注射成型的步骤,该聚合物组合物包含至少一种门尼粘度(ML 1+4,100℃)为50-30的选择氢化的丁腈橡胶聚合物,至少一种填料和至少一种交联剂。
6.如权利要求5所述的方法,其中成型制品是封条,软管,轴承垫板,挡板,油井盖封条,浮阀塔板,电缆覆材,车轮,辊子,适当位置上的垫圈或管接头密封条。
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EP (3) | EP1426383B1 (zh) |
JP (1) | JP4667738B2 (zh) |
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2002
- 2002-12-05 CA CA002413607A patent/CA2413607A1/en not_active Abandoned
-
2003
- 2003-11-25 EP EP03026918A patent/EP1426383B1/en not_active Expired - Lifetime
- 2003-11-25 EP EP05023925A patent/EP1621577A3/en not_active Withdrawn
- 2003-11-25 DE DE60319325T patent/DE60319325T2/de not_active Expired - Lifetime
- 2003-12-04 US US10/728,029 patent/US7381781B2/en active Active
- 2003-12-04 EP EP03027956A patent/EP1426384A1/en not_active Withdrawn
- 2003-12-04 RU RU2003135265/04A patent/RU2356913C9/ru not_active IP Right Cessation
- 2003-12-05 CN CNB2003101240894A patent/CN100558772C/zh not_active Expired - Lifetime
- 2003-12-05 CN CNA2007100840038A patent/CN101016349A/zh active Pending
- 2003-12-05 JP JP2003406953A patent/JP4667738B2/ja not_active Expired - Fee Related
- 2003-12-05 CN CNA2007100051319A patent/CN100999595A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105622783A (zh) * | 2014-10-29 | 2016-06-01 | 中国石油化工股份有限公司 | 一种共聚物的制备方法 |
CN105622783B (zh) * | 2014-10-29 | 2017-06-30 | 中国石油化工股份有限公司 | 一种共聚物的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1426384A1 (en) | 2004-06-09 |
CA2413607A1 (en) | 2004-06-05 |
EP1621577A3 (en) | 2006-02-08 |
DE60319325T2 (de) | 2009-03-26 |
JP2004190030A (ja) | 2004-07-08 |
RU2356913C9 (ru) | 2010-05-20 |
CN1511855A (zh) | 2004-07-14 |
CN100558772C (zh) | 2009-11-11 |
EP1426383B1 (en) | 2008-02-27 |
DE60319325D1 (de) | 2008-04-10 |
EP1621577A2 (en) | 2006-02-01 |
EP1426383A1 (en) | 2004-06-09 |
JP4667738B2 (ja) | 2011-04-13 |
US20040132891A1 (en) | 2004-07-08 |
CN101016349A (zh) | 2007-08-15 |
RU2356913C2 (ru) | 2009-05-27 |
US7381781B2 (en) | 2008-06-03 |
RU2003135265A (ru) | 2005-05-27 |
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