CN1789326A - High-damping oil-resistant rubber composition - Google Patents

High-damping oil-resistant rubber composition Download PDF

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CN1789326A
CN1789326A CN 200410093146 CN200410093146A CN1789326A CN 1789326 A CN1789326 A CN 1789326A CN 200410093146 CN200410093146 CN 200410093146 CN 200410093146 A CN200410093146 A CN 200410093146A CN 1789326 A CN1789326 A CN 1789326A
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rubber
polynorbornene
weight
nitrile
high damping
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CN 200410093146
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CN100415824C (en )
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张丰
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上海华向橡胶制品有限公司
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Abstract

The invention relates highly damped and oil resistance rubber compound, comprising the following characteristics: using the mixture of polynorbornene rubber and butadiene acrylonitrile rubber as base, using dicumyl peroxide as cross linking agent, and triallyl group isocyanuric esters as auxiliary agent. The content of acrylic nitrile in butadiene acrylonitrile rubber is 23-30úÑ. The weight ratio of polynorbornene rubber and butadiene acrylonitrile rubber is 85-75/15-25, preferring to 80/20.

Description

高阻尼耐油性橡胶组合物 High damping oil-resistant rubber composition

技术领域 FIELD

本发明涉及一种用于制造减震阻尼橡胶制品的橡胶组合物,具体地说,涉及一种以本身具有高阻尼性能为特征的聚降冰片烯橡胶为主体的高阻尼耐油性橡胶组合物。 The present invention relates to a rubber composition for manufacturing a shock absorber damping rubber products, in particular, to a per se having a high damping performance characteristics of polynorbornene high damping rubber as the main oil-resistant rubber composition.

背景技术 Background technique

随着人类生活水平的不断提高,人们对所处环境的要求也越来越高,而科学技术的发展促使机器设备的功率增大,转速加快,由此而造成的振动和噪声危害愈来愈显突出,即除了会影响机器设备的使用寿命,造成设备早期损坏外,还会对人们的工作效率,身心健康产生有害影响,对付这类振动和噪声有效手段是运用高效的阻尼材料来吸收、阻隔、屏蔽震动或噪声的转播。 With the continuous improvement of the human condition, people on the environment have become more sophisticated, and the development of science and technology to promote the power of machinery and equipment increased speed to accelerate, vibration and noise caused thereby increasing harm more obvious, that only affects the life of machinery and equipment, resulting in damage to the older equipment, but also on people's productivity, adversely affect the physical and mental health, to deal with this type of vibration and noise are an effective means of efficient use of damping materials to absorb, barrier shield broadcast vibration or noise. 橡胶是一种具有高内摩擦性能的材料,能够有效地把震动和噪声的机械能转化为热能,而且橡胶材料加工方便,可以通过挤出、模压、注射等各种加工方法,制成各种形状,满足不同的使用条件。 Rubber is a material having a high friction properties, the mechanical vibration can be effectively and noise energy into heat, but a rubber material to facilitate processing, various processing methods can be extrusion, molding, injection, etc., various shapes , to meet the different conditions of use. 因此,橡胶是工程中使用最广泛的阻尼材料之一。 Therefore, the rubber is one of the most widely used engineering damping material.

聚降冰片烯橡胶最初是由法国CDF Chimie公司开发成功的,它是通过Diels-Alder催化剂由乙烯与环戊二烯开环共聚合得到。 Polynorbornene rubber was originally developed by the French company CDF Chimie, which is obtained by Diels-Alder catalyst copolymerization of ethylene to the cyclopentadienyl ring opened. 具有如下的分子结构,ASTM命名代号为PNR。 Has the following molecular structure, ASTM designated as code PNR.

这种橡胶的最大特征是十分柔软,可以制得硬度范围包含海绵橡胶和各种固体橡胶的弹性体材料,鉴于它的高减震阻尼性,可以在汽车、铁路、航海、建筑、体育用品等方面制作防震、减轻噪音的元部件,可望开发适应全频谱的隔震材料(参见于清溪主编《橡胶原材料手册》,化学工业出版社,1996年,P308-310)。 The maximum of this characteristic is very soft rubber, may be prepared comprising a sponge rubber hardness range and variety of solid rubber elastomeric material, in view of its high damping of vibrations, it may be in the automotive, railway, marine, construction, sporting goods, etc. shockproof aspects of production, reducing the noise component parts, is expected to develop isolation material to the whole spectrum (see in the stream editor "rubber raw material Handbook", chemical industry Press, 1996, P308-310). 但是,聚降冰片烯橡胶的最大缺点是,它像天然橡胶一样,不具备足够的耐油性(参见Dr.-lng.W.Goht,《Elastomere Dicht-und Konstruktionswerkstoffe》,P38),当它供减震阻尼应用时,特别是用于一些机械设备时,往往要求它能具有一定的耐油性能,因此,提高聚降冰片烯橡胶的耐油类介质性能具有相当的现实意义。 However, the biggest drawback polynorbornene rubber is that it is like as natural rubber, does not have sufficient oil resistance (see Dr.-lng.W.Goht, "Elastomere Dicht-und Konstruktionswerkstoffe", P38), when it Save for when the shock damping applications, particularly for some mechanical device, it often requires a certain oil resistance, thus improving the performance of oil-based medium polynorbornene rubber having a considerable practical significance.

发明内容 SUMMARY

本发明的目的是提供一种在一般橡胶加工厂都能方便地制备的耐油类介质性能获得明显改善的以聚降冰片烯橡胶为主体的高阻尼耐油性橡胶组合物,由此可使聚降冰片烯橡胶的应用范围得以进一步拓宽。 Object of the present invention is to provide a significant improvement in obtaining a polynorbornene high damping rubber composition is oil-resistant rubber as a main component in oil-based dielectric properties of rubber processing plants generally can be conveniently prepared, thereby allowing drop poly applications norbornene rubbers can be further widened.

本发明是这样实现的,它是一种以聚降冰片烯橡胶为主体的高阻尼耐油性橡胶组合物,其特征是,该组合物以聚降冰片烯橡胶与丁腈橡胶的掺合共混为基础,以过氧化二异丙苯为共交联剂,以三烯丙基异氰尿酸酯为助交联剂。 The present invention is achieved, it is a kind of a polynorbornene high damping rubber as the main oil-resistant rubber composition, characterized in that the blend composition is blended polynorbornene rubber and nitrile rubber is basis, dicumyl peroxide as crosslinking agent, to triallyl isocyanurate as crosslinking aid. 聚合物共混技术是目前常用于橡胶材料改性的技术,可以实现两种或多种材料的取长补短,丁腈橡胶是人们熟知通用型耐油橡胶,所以本发明就着眼于以丁腈橡胶来改善聚降冰片烯橡胶的耐油性能,鉴于聚降冰片烯橡胶的化学结构、溶解参数、共硫化性等方面与丁腈橡胶存在一定的差异,因此为了实现两者的有效共混,本发明者对丁腈橡胶的丙烯腈含量,丁腈橡胶的掺用量和硫化体系作了精心筛选。 Polymer blending techniques are commonly used technique for modifying a rubber material, may be implemented each other two or more materials, are well known nitrile rubber type rubber with general, the present invention will be focused on the nitrile rubber to improve poly oil resistance drop norbornene rubber, in view of the chemical structure of the polynorbornene rubber, there are some differences in dissolution parameters, covulcanizability with nitrile rubber and the like, so in order to achieve effective blending of both, the present inventors acrylonitrile content nitrile rubber, and the doping level of nitrile rubber cure systems were carefully selected.

众所周知,丁腈橡胶的耐油性能是随着丙烯腈含量的增加而提高的,所以增大丙烯腈含量,有利于提高耐油性能;但是随着丙烯腈含量的增加,丁腈橡胶的极性也会增大,于是其与非极性的聚降冰片烯橡胶的相容性变差,不利于实现两者的有效共混,导致物理机械性能下降。 Is well known, oil resistance of nitrile rubber with increasing acrylonitrile content is increased, so that the acrylonitrile content increases, beneficial to improve the oil resistance; but with increasing acrylonitrile content, the polarity of nitrile rubber will increases, so poor compatibility with non-polar polynorbornene rubber, is not conducive to effective blend of both, resulting in physical and mechanical properties decline. 大量试验证明,为了实现聚降冰片烯橡胶与丁腈橡胶的有效共混,改善聚降冰片烯橡胶的耐油性能,丁腈橡胶的丙烯腈含量宜为23~30%。 A large number of tests show that in order to achieve effective blending polynorbornene rubber and nitrile rubber to improve the oil resistance polynorbornene rubber, nitrile rubber acrylonitrile content should be 23 to 30%. 丙烯腈含量过低,在改善耐油性能方面效果不明显。 Acrylonitrile content is too low, in terms of improved oil resistance effect is not obvious. 这时,聚降冰片烯橡胶与丁腈橡胶的掺合共混比,以重量计宜为:85~75/15~25,优选80/20。 In this case, polynorbornene rubber and nitrile rubber blend blend ratio, by weight, should be as follows: 85 ~ 75/15 ~ 25, preferably 80/20. 丁腈橡胶的掺混比例过大,会损及聚降冰片烯橡胶固有的减震阻尼性能,反之,丁腈橡胶的掺混比例不足,会导致耐油性能降低。 Nitrile rubber blend ratio is too large, polyethylene prejudicial drop inherent damping properties of the damping rubbers norbornene, conversely, lack of blend ratio of the nitrile rubber, will lead to lower oil resistance.

两种或多种橡胶共混时,最终产物的性能在很大程度上取决于它们能否实现共硫化,而共硫化的实现,又与选用的硫化系统有着极大的关系。 When two or more rubber blend, the properties of the final product is largely dependent on their ability to achieve co-vulcanization to achieve co-vulcanized, and has a great relationship with the vulcanization system selected. 按照本发明,采用过氧化二异丙苯(DCP)作为这两种橡胶的共硫化剂,这首先是因为以过氧化二异丙苯作为交联剂时,两种橡胶的交联速率相近,有利于实现共硫化,加之这种有机过氧化物通用易得,便于推广应用。 According to the present invention, the use of dicumyl peroxide (DCP) as a co-curing agent, these two rubbers, which at first is because dicumyl peroxide as a crosslinking agent, the crosslinking rates of the two similar rubbers, conducive to co-curing, general purpose combined organic peroxide such readily available, easy application. 制得得材料耐老化、压缩永久变形等性能优良。 Prepared material obtained anti-aging, excellent compression set properties. 如果使用橡胶行业通用的硫黄—促进剂硫化系统,由于这类硫化系统在聚降冰片烯橡胶和丁腈橡胶中的溶解度又很大差异,难以实现两种橡胶共混后的硫化同步,以致最终产物的物理机械性能不理想。 If the rubber industry, a common sulfur - accelerator curing system, the vulcanization system since these polynorbornene rubber and nitrile rubber has a solubility very different, the vulcanized rubber is difficult to achieve blending of the two synchronization, and eventually physical and mechanical properties of the product is not ideal.

试验表明,作为共硫化剂的过氧化二异丙苯的适宜用量为:以聚降冰片烯橡胶和丁腈橡胶加和在一起为100重量份计,为2~3重量份。 Tests showed that a suitable amount of dicumyl peroxide curing co-agents are: the polynorbornene rubber and nitrile rubber added together to 100 parts by weight, 2 to 3 parts by weight. 为了进一步提高交联效率,改善所得产物的物理机械性能,本发明选用三烯丙基异氰尿酸酯(TAIC)作为共交联助剂。 In order to further increase the crosslinking efficiency, improved physical and mechanical properties of the resulting product, the present invention selects triallyl isocyanurate (of TAIC) as the co-crosslinking aid. 其适宜用量为:聚降冰片烯橡胶和丁腈橡胶加和在一起为100重量份计,为1~2重量份。 Suitable amounts of which: polynorbornene rubber and nitrile rubber added together to 100 parts by weight, 1 to 2 parts by weight.

本发明所述的以聚降冰片烯橡胶为主体的高阻尼耐油性橡胶组合物与现有技术相比,具有明显的进步,首先,它改变了聚降冰片烯橡胶耐油性能不足的缺点,使之可以应用于与矿物油类相接触的场合,从而拓宽了聚降冰片烯橡胶的应用领域;其次,本发明选用过氧化二异丙苯作为共混橡胶的共硫化剂、选用三烯丙基异氰尿酸酯作为共交联助剂,这两种材料都是一般橡胶厂中常用的通用助剂,因而来源易得,便于推广应用。 In polynorbornene high damping rubber as the main oil-resistant rubber composition according to the present invention compared to the prior art, having a significant advance, first of all, it changes the shortcoming polynorbornene rubber, oil resistance, so that It may be applied to the case of contact with the mineral oil, which broadens the field of application of polynorbornene rubber; secondly, the present invention is the choice of dicumyl peroxide as a vulcanizing agent were blended rubber selected triallyl isocyanurate as a co-crosslinking aid, both materials are commonly used in general rubber plant common adjuvants, and thus the source of readily available, easy application. 曾用本发明组合物制造某中外合作工程中用的减震阻尼橡胶件,经外方测试性能全面符合要求,获得认证通过。 Damper has damping rubber member manufactured by a foreign cooperative project of the composition of the present invention, the outer full compliance test performance, certified by.

具体实施方式 Detailed ways

下面结合实施例对本发明作进一步说明,但本发明绝不局限于这些实施例。 Below in connection with embodiments of the present invention is further illustrated, but the present invention is not limited to these embodiments. 实施例中所述的性能测试结果,均指采用相应的国家标准规定的方法测得的数值。 Performance test results described in the embodiment, refer to the method defined corresponding national standard values ​​measured.

掺合共混用母胶的制备为便于显示本发明的效果,首先按表1所示配方分别制备聚降冰片烯橡胶和丁腈橡胶母胶,所用的聚降冰片烯橡胶为日本瑞翁公司出品的NS×15AB,并把该母胶称为母胶A,所用丁腈橡胶分别为丁腈-18、丁腈-26和丁腈-40,并依次定名为:母胶B、母胶C和母胶D。 Preparation of total masterbatch mix blend to facilitate the display of the present invention, first according to the formulation shown in Table 1 were prepared polynorbornene rubber and nitrile rubber masterbatch is used polynorbornene rubber produced Zeon Corporation NS × 15AB, the masterbatch and the masterbatch is called A, the nitrile rubber is nitrile used respectively -18, -26 and nitrile nitrile -40, and sequentially named: master batch B, C and female masterbatch gum D.

表1 Table 1

表1各组分在密炼机中混合,排胶温度控制为120~130℃。 Table 1 The components are mixed in an internal mixer, dump temperature controlled to 120 ~ 130 ℃.

实施例1~3和比较例1~9按表1所列组分制备的母胶A、B、C、D母胶,按照表2和表3所示以不同方式掺合共混后,混入不同的硫化体系和用量,以160℃×8min硫化制成测试用标准试片,得到的测试结果归纳如表2和表3。 Examples 1 to 3 and Comparative Examples 1 to 9 A masterbatch prepared according to the components listed in Table 1, B, C, D masterbatch, in Table 2 and Table 3 in a different manner after blending blending, mixing different and amount of vulcanization system, at 160 ℃ × 8min cured into test pieces using a standard test, the test results obtained are summarized in table 2 and table 3.

表2 Table 2

注1:在该例中,母胶A和母胶C内均未加用共交联助剂TAIC。 Note 1: In this example, the masterbatch masterbatch A and C were not co-crosslinking aid added with TAIC.

比较例5是将实施例1中的DCP硫化系统改为硫黄硫化系统,即:掺入N-环己基-2-苯并噻唑次磺酰胺1.5重量份、二硫化四甲基秋兰姆0.7重量份、氧化锌5重量份、硫黄1.5重量份、二苯胍表3 Comparative Example 5 is to DCP vulcanization system in Example 1 was changed to sulfur vulcanization system, namely: the incorporation of N- cyclohexyl-2-benzothiazole sulfenamide 1.5 parts by weight of tetramethylthiuram disulfide, 0.7 wt. parts zinc oxide 5 parts by weight, 1.5 parts by weight of sulfur, diphenylguanidine table 3

0.7重量份。 0.7 parts by weight. 比较例6和7是把实施例1中的DCP用量分别改为1.5和3.5重量份。 Comparative Examples 6 and 7 are the amount of DCP in Example 1 were changed to 1.5 and 3.5 parts by weight. 比较例8和9分别为将实施例1中的母胶A/母胶C=80/20改为母胶A/母胶B=80/20和母胶A/母胶D=80/20,其余都与实施例1相同,试验结果与实施例1的比较如表3所示。 Comparative Examples 8 and 9, respectively, in Example 1. The masterbatch A / masterbatch C = 80/20 to masterbatch A / masterbatch B = 80/20 and the masterbatch A / masterbatch D = 80/20, the rest are the same as in Example 1, the test results as described in Comparative Example 1 shown in table 3. 可见,采用本发明可以在耐各种矿物油介质和物理机械性能等方面取得最佳的综合平衡。 Be seen, the present invention can achieve the best overall balance of the various mineral oil medium resistance and mechanical properties and so on.

Claims (6)

  1. 1.一种以聚降冰片烯橡胶为主体的高阻尼耐油性橡胶组合物,其特征是,该组合物以聚降冰片烯橡胶与丁腈橡胶的掺合共混为基础,以过氧化二异丙苯为共交联剂,以三烯丙基异氰尿酸酯为助交联剂。 A poly polynorbornene rubber as the main oil high damping rubber composition, wherein the composition is a blend blended polynorbornene rubber and nitrile rubber-based, peroxide, diisopropyl propyl benzene as crosslinking agent to triallyl isocyanurate as crosslinking aid.
  2. 2.根据权利要求1所述的高阻尼耐油性橡胶组合物,其特征是,所述的丁腈橡胶的丙烯腈含量为23~30%。 The high damping oil-resistant rubber composition according to claim 1, characterized in that the acrylonitrile content nitrile rubber is 23 to 30%.
  3. 3.根据权利要求1所述的高阻尼耐油性橡胶组合物,其特征是,聚降冰片烯橡胶与丁腈橡胶的掺合共混比,以重量计为:85~75/15~25。 The high damping oil-resistant rubber composition according to claim 1, characterized in that the blending ratio of a poly blend drop norbornene rubber and nitrile rubber, by weight: 85 ~ 75/15 ~ 25.
  4. 4.根据权利要求1所述的高阻尼耐油性橡胶组合物,其特征是,聚降冰片烯橡胶与丁腈橡胶的掺合共混比,以重量计优选80/20。 The high damping oil-resistant rubber composition according to claim 1, characterized in that the blending ratio of a poly blend drop norbornene rubber and nitrile rubber, preferably 80/20 by weight.
  5. 5.根据权利要求1所述的高阻尼耐油性橡胶组合物,其特征是,所述共交联剂过氧化二异丙苯的用量,以聚降冰片烯橡胶和丁腈橡胶加和在一起为100重量份计,为2~3重量份。 The high damping oil-resistant rubber composition according to claim 1, characterized in that, through the co-crosslinking agent is used in an amount of dicumyl peroxide to polynorbornene rubber and nitrile rubber added together 100 parts by weight, 2 to 3 parts by weight.
  6. 6.根据权利要求1所述的高阻尼耐油性橡胶组合物,其特征是,所述的交联助剂三烯丙基异氰尿酸酯的用量,以聚降冰片烯橡胶和丁腈橡胶加和在一起为100重量份计,为1~2重量份。 The high damping oil-resistant rubber composition according to claim 1, wherein an amount of the crosslinking aid is triallyl isocyanurate to polynorbornene rubber and nitrile rubber added together to 100 parts by weight, 1 to 2 parts by weight.
CN 200410093146 2004-12-17 2004-12-17 High-damping oil-resistant rubber composition CN100415824C (en)

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CN102040823A (en) * 2009-10-23 2011-05-04 上海华向橡胶制品有限公司 Damping rubber
CN102140207A (en) * 2011-04-07 2011-08-03 上海交通大学 Rubber base damping material and preparation method thereof
CN103045171A (en) * 2013-01-21 2013-04-17 广东富华重工制造有限公司 Dust inhibitor of friction material and application method thereof
CN103724908A (en) * 2013-12-31 2014-04-16 长城汽车股份有限公司 Low-hardness high-damping rubber composition and preparation method thereof
CN104130539A (en) * 2014-08-11 2014-11-05 上海经纬峰实业有限公司 Flame-retardant high-damping rubber composition using polynorbornene rubber as main body
CN107353451A (en) * 2017-06-05 2017-11-17 薛念念 High-damping shock-reducing rubber material used for automobile suspension bushing and production method thereof

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Publication number Priority date Publication date Assignee Title
CN102040823A (en) * 2009-10-23 2011-05-04 上海华向橡胶制品有限公司 Damping rubber
CN102140207A (en) * 2011-04-07 2011-08-03 上海交通大学 Rubber base damping material and preparation method thereof
CN102140207B (en) 2011-04-07 2012-12-26 上海交通大学 Rubber base damping material and preparation method thereof
CN103045171A (en) * 2013-01-21 2013-04-17 广东富华重工制造有限公司 Dust inhibitor of friction material and application method thereof
CN103724908A (en) * 2013-12-31 2014-04-16 长城汽车股份有限公司 Low-hardness high-damping rubber composition and preparation method thereof
CN103724908B (en) * 2013-12-31 2016-06-29 长城汽车股份有限公司 Low hardness high damping rubber composition and its preparation method
CN104130539A (en) * 2014-08-11 2014-11-05 上海经纬峰实业有限公司 Flame-retardant high-damping rubber composition using polynorbornene rubber as main body
CN104130539B (en) * 2014-08-11 2016-08-17 上海经纬峰实业有限公司 Kind of polynorbornene rubber as the main flame-retardant high damping rubber composition
CN107353451A (en) * 2017-06-05 2017-11-17 薛念念 High-damping shock-reducing rubber material used for automobile suspension bushing and production method thereof

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