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Publication numberCN101501109 A
Publication typeApplication
Application numberCN 200780030004
PCT numberPCT/US2007/015875
Publication date5 Aug 2009
Filing date12 Jul 2007
Priority date14 Jul 2006
Also published asCN101501109B, US7767749, US7816443, US20080015286, US20090286920, WO2008008423A1
Publication number200780030004.2, CN 101501109 A, CN 101501109A, CN 200780030004, CN-A-101501109, CN101501109 A, CN101501109A, CN200780030004, CN200780030004.2, PCT/2007/15875, PCT/US/2007/015875, PCT/US/2007/15875, PCT/US/7/015875, PCT/US/7/15875, PCT/US2007/015875, PCT/US2007/15875, PCT/US2007015875, PCT/US200715875, PCT/US7/015875, PCT/US7/15875, PCT/US7015875, PCT/US715875
Inventors托马斯W威尔逊三世
Applicant耐克国际有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Rubber compositions with activated sulfur cure
CN 101501109 A
Abstract
Cured rubber compositions with reduced divalent metal levels and improved physical properties are prepared using methods that limit or avoid a deleterious side reaction, and that make activator compounds available only during cure and not earlier during mixing. Specifically, the presence of activator soap (or of components that can form the activator soap in situ) and silica filler together is avoided or minimized in process steps where the temperature would tend to be above 100 DEG C or 110 DEG C. The use of ZnO for example can be reduced by as much as 90-95% in a typical rubber compound.
Claims(28)  translated from Chinese
1、一种通过用橡胶可溶盐或皂激活硫硫化的橡胶组合物的硫化方法,所述方法包括:在第一混合步骤中,于高至150℃的温度下,将未硫化的橡胶和填料,或未硫化的橡胶、填料以及硫硫化体系以外的其它橡胶添加剂混合,并排除所述盐本身与至少所述盐的阳离子组分;在不超过110℃的温度下,将硫硫化组分和所述盐或第一混合步骤中未加入的任何组分加入第一混合步骤的产物中;以及随后在接近130℃或更高的温度下通过加热来硫化所得橡胶组合物;其中所述橡胶组合物包括2phr或更少的脂肪酸和2phr或更少的锌化合物,或者所述橡胶组合物包括2phr或更少的锌脂肪酸盐。 1. A method of activating sulfur vulcanized by vulcanizing the rubber soluble salts or soaps of the rubber composition, the method comprising: a first mixing step, at a temperature of up to 150 ℃, and unvulcanized rubber Rubber additives other fillers, vulcanization or rubber, filler and other than sulfur vulcanization system, and the exclusion of the salt itself with at least said cationic component of the salt; at a temperature not exceeding 110 ℃, the sulfur vulcanizing components and the salts or any component of the first mixing step is not added in the mixing step is added to the first product; and subsequently at a temperature close to or higher by heating at 130 ℃ resultant vulcanized rubber composition; wherein said rubber The composition comprises a fatty acid and 2phr 2phr or less or less zinc compound, or the rubber composition comprises less 2phr or zinc salts of fatty acids.
2、 根据权利要求1所述的方法,其中第一混合在桶型剪切混合机中进行。 2. The method of claim 1, wherein the mixing is conducted at a first shear mixer barrel.
3、 根据权利要求1所述的方法,其中第二混合在开炼机上进行。 3. The method according to claim 1 or claim 2, wherein the second mixed on an open roll machine.
4、 根据权利要求1所述的方法,其中盐组分包括氧化锌和Q〜C26的脂肪酸。 4. The method according to claim 1 or claim 2, wherein the salt component comprises zinc oxide and fatty acid Q~C26.
5、 根据权利要求4所述的方法,其中所述第一混合步骤的产物不含氧化锌且不含脂肪酸。 5. The method of claim 4, wherein, said first mixing step wherein the product contains no zinc oxide and free fatty acids.
6. 6.
7、 根据权利要求4所述的方法,包括在第二混合步骤中添加少于或等于2phr的氧化锌以及少于2phr的脂肪酸。 7. The method according to claim 4, comprising adding zinc oxide is less than or equal to and less than 2phr 2phr fatty acids in the second mixing step.
8、 根据权利要求7所述的方法,包括添加0.1 ~ lphr的氧化锌。 8. A method according to claim 7, wherein, comprising adding 0.1 ~ lphr of zinc oxide.
9、 根据权利要求7所述的方法,包括添加0.05 ~ 0.5phr的氧化锌和0.1 ~ 1.5phr的脂肪酸。 9. A method according to claim 7, wherein, comprising adding zinc oxide and 0.05 ~ 0.5phr 0.1 ~ 1.5phr fatty acids.
10、 根据权利要求1所述的方法,其中所述填料包括10 ~ 100phr的二氧化硅填料。 10. A method according to claim 1 or claim 2, wherein said filler comprises silica filler of 10 ~ 100phr.
11、 根据权利要求IO所述的方法,其中所述第一混合步骤的产物不含锌化合物,且其中在第二混合中添加氧化锌和锌脂肪酸盐中的至少一种。 11, according to the claim IO claims, wherein the product of the first step of mixing the zinc compound is not and wherein the addition of at least one of zinc oxide and zinc fatty acid salt in a second mixing. <formula>formula see original document page 2</formula> <Formula> formula see original document page 2 </ formula>
12、 根据权利要求IO所述的方法,其中所述填料包括30〜60phr的二氧化硅填料。 12, according to the requirements of the method as claimed IO, wherein said filler comprises 30~60phr silica filler.
13、 根据权利要求4所述的方法,包括以接近于l摩尔氧化锌比2摩尔脂肪酸的化学计量比添加氧化锌和脂肪酸。 13. A method according to claim 4, wherein, comprising close to the stoichiometric ratio of 2 l molar zinc oxide molar ratio of fatty acid and fatty acid zinc oxide was added.
14、 根据权利要求1所述的方法,其中所述氧化锌是微嚢包封的。 14. A method according to claim 1 or claim 2, wherein said zinc oxide is encapsulated micro Nang.
15、 根据权利要求1所述的方法,其中所述氧化锌包括具有50|mi或更小粒径的颗粒。 15. A method according to claim 1 or claim 2, wherein said zinc oxide comprising a 50 | mi or smaller size of the particles.
16、 一种涉及用脂肪酸的锌盐激活硫硫化的制造硫化橡胶组合物的方法, 所述方法包括:在第一混合中,在约150。 16. A method of producing vulcanized rubber with a fatty acid composition of activated zinc sulfide sulfur is directed, said method comprising: a first mixing at about 150. C或更低的温度下,将未硫化橡胶和填料,或未硫化的橡胶、填料以及硫硫化剂以外的其它橡胶添加剂混合;在第二混合中,在110。 C or less at a temperature of the unvulcanized rubber and a filler, or other additives are mixed rubber vulcanized rubber, sulfur vulcanizing agent and a filler other than; in the second mixing at 110. C或更低的温度下,将硫硫化剂加入到第一混合步骤的产物中;将微嚢包封的氧化锌和/或微嚢包封的锌脂肪酸盐加入到第一混合、或第二混合、或两者中,当第一混合在高于130。 Under C or lower temperature, the sulfur vulcanizing agent is added to the product of the first step of mixing; zinc oxide fine Nang encapsulated and / or zinc salts of fatty acids encapsulated micro Nang added to the first mix, or the first two mix, or both, when the first mixed at above 130. C的温度下进行时,所述微嚢包封的组分只加入到第二混合中,其中所述微嚢包封的氧化锌或锌脂肪酸盐包括氧化锌或锌脂肪酸盐以及包覆锌化合物或各脂肪酸盐的壁材料,所述壁材料对温度稳定以使所述微嚢在第一或第二混合期间不会释放所述锌化合物;以及通过加热至高于或等于120。 C when the temperature was lower, the micro-encapsulated ingredient Nang only added to the second mix, wherein said micro-encapsulated Nang zinc oxide or zinc salts of fatty acids include zinc oxide or a zinc salt of a fatty acid and a coating each fatty acid salt or zinc compound wall material, said wall material so that the temperature stable in the first or second micro Nang during the mixing does not release zinc compound; and by heating to a temperature above or equal to 120. C的温度来硫化所得到的橡胶组合物,此时锌从微嚢中释放并激活硫化,且其中所述橡胶组合物包括2phr或更少的氧化锌或锌脂肪酸盐。 C the temperature of the resulting vulcanized rubber composition, when released from the micro-Nang zinc and activate the vulcanization and wherein the rubber composition comprises less 2phr or zinc oxide, or zinc fatty acid salt.
17、 根据权利要求16所述的方法,其中所述橡胶组合物包括少于或等于lphr的氧化锌或锌脂肪酸盐。 17. A method according to claim 16 or claim, wherein the rubber composition comprises less than or equal to a zinc oxide or a zinc fatty acid salt lphr.
18、 根据权利要求16所述的方法,其中所述橡胶组合物包括少于或等于0.3phr的氧化锌或锌脂肪酸盐。 18. The method according to claim 16 or claim, wherein the rubber composition comprises less than or equal to a zinc oxide or a zinc fatty acid salt 0.3phr.
19、 根据权利要求16所述的方法,其中所述橡胶组合物包括少于或等于lphr的氧化锌和足以激活硫化的脂肪酸。 19. A method according to claim 16 or claim, wherein said rubber composition comprises zinc oxide and less than or equal sufficient to activate the sulfurized fatty lphr.
20、 根据权利要求16所述的方法,其中所述橡胶组合物包括少于或等于0.3phr的氧化锌和足以激活^琉化的脂肪酸。 20. The method according to claim according to claim 16, wherein the rubber composition comprises less than or equal to 0.3phr zinc oxide and sulfur sufficient to activate ^ fatty acid.
21、 根据权利要求16所述的方法,其中所述橡胶组合物包括10~100phr 的二氧化硅填料。 21. The method according to claim 16 or claim, wherein the rubber composition comprises 10 ~ 100phr of silica filler.
22、 根据权利要求16所述的方法,其中所述壁材料包括从蜡、石蜡、聚乙烯、乙烯-醋酸乙烯酯共聚物、聚酰胺、聚丙烯酸酯、聚曱基丙烯酸酯、聚碳酸酯、聚环氧乙烷、聚原酸酯、聚醋酸乙烯酯、聚乙烯吡咯烷酮、酪蛋白酸钙、 聚果胶酸钓和聚乙烯醇构成的组中选择的一种或多种成分。 22. The method according to claim 16, wherein said wall material comprises from wax, paraffin wax, polyethylene, ethylene - vinyl acetate copolymers, polyamides, polyacrylates, poly 曱 acrylate, polycarbonate, polyethylene oxide, polyorthoester, polyvinyl acetate, polyvinyl pyrrolidone, calcium caseinate, one or more components of the group polyethylene, and polyvinyl alcohol pectate fishing consisting selected.
23、 一种可模塑的橡胶组合物,包括:从天然橡胶、合成橡胶和它们的混合物构成的组中选择的橡胶树脂;硫化剂组合物;填料;和用于所述硫化剂的被保护的活化剂组合物。 23. A moldable rubber composition, comprising: selected from the group of natural rubber, synthetic rubber, and mixtures thereof in the rubber resin; curing agent composition; fillers; and a curing agent for the protected The activator composition.
24、 根据权利要求23所述的可模的塑橡胶组合物,其中所述活化剂组合物通过微嚢包封来保护。 24, according to claim 23 wherein the moldable plastic rubber composition, wherein said activator composition Nang protected by micro encapsulation.
25、 根据权利要求24所述的可模塑的橡胶组合物,其中所述活化剂组合物包括金属氧化物和脂肪酸皂中的一种或多种。 25, can be molded according to claim 24 wherein the rubber composition, wherein said activator composition comprises a metal oxide and a fatty acid soap of one or more.
26、 根据权利要求25所述的可模塑的橡胶组合物,其中所述金属氧化物的金属组分选自元素周期表的IIA族和IIB族。 26, according to claim 25 wherein the moldable rubber composition, wherein the metal component of the metal oxide is selected from Group IIA and IIB.
27、 根据权利要求25所述的可模塑的橡胶组合物,其中所述金属氧化物是氧化锌。 27, according to the moldable rubber composition according to claim 25, wherein said metal oxide is zinc oxide.
28、 根据权利要求23所述的可模塑的橡胶组合物,其中所述硫化剂组合物包括元素硫和促进剂。 28, can be molded according to claim 23 wherein the rubber composition, wherein the curing agent composition comprising elemental sulfur and accelerators.
Description  translated from Chinese

激活硫硫化的橡胶组合物 Activation sulfur vulcanized rubber composition

对相关申请的交叉引用 CROSS-REFERENCE TO RELATED APPLICATIONS

本申请要求2006年7月14日提出的美国临时申请60/830,824的权利, 其公开通过引用合并于此。 This application claims the United States July 14, 2006 the right to apply for provisional 60 / 830,824, the disclosure of which is incorporated herein by reference.

背景技术 Background

氧化锌(ZnO),以及诸如CaO和MgO等其它二价金属氧化物通常被当作含促进剂的橡胶混合物(混炼胶),特别是含硫的橡胶混合物的硫化的活化剂。 Other divalent metal oxides of zinc oxide (ZnO), and the like, such as CaO and MgO are generally used as a rubber accelerator containing mixture (mix), in particular sulfur-vulcanized rubber mixture activator. 更精确地, 一分子的阳离子组分(例如ZnO)与两分子的诸如硬脂酸(C17H35COOH)等脂肪酸化合形成盐或皂如硬脂酸锌(Zn(C17H35COO)2) 和水。 More precisely, part of the cationic component (e.g., ZnO) with two molecules of stearic acid such as (C17H35COOH) or the like to form a salt compound of a fatty acid soap such as zinc stearate (Zn (C17H35COO) 2) and water. 该皂(例如硬脂酸锌)被认为是硫化的活化剂。 The soap (e.g., zinc stearate) is considered vulcanizing activator.

在混合和/或硫化期间,ZnO (或其他阳离子组分)和脂肪酸反应生成激活硫硫化的急。 During the mixing and / or sulfide, ZnO (or other cationic component) and fatty acid activation reaction of sulfur-cured urgency. 实际应用中,在橡胶混合物中使用对脂肪酸化学计量过量的阳离子组分来获得足够的激活作用。 In practice, the use of a stoichiometric excess of the fatty cationic component in the rubber mixture to obtain a sufficient activation.

已硫化的橡胶中过量的诸如ZnO等阳离子组分会降低硫化橡胶的物理性能。 Cation club vulcanized rubber, such as ZnO or the like to reduce excessive physical properties of vulcanized rubber. 此外,锌会随时间从硫化的橡胶组合物中浸出,由于氧化锌被认为是生态有毒物质,这会引起人们对污染的顾虑。 In addition, the zinc can leach over time from the vulcanized rubber composition, since the zinc oxide is considered to be eco-toxic substances, which can cause people to pollution concerns.

根据上述情况,有待于提供含有少量锌的用于硫化橡胶的方法和組合物,而且这种方法和组合物仍然能具有可接受的硫化动力学并且能在所得硫化制品中提供合意的物理性能。 Based on the above, to be provided a method and composition containing a small amount of zinc for vulcanized rubber, and this method and compositions still have acceptable cure kinetics and can provide desirable physical properties in the resulting cured products.

发明内容 DISCLOSURE

使用限制或避免有毒副反应的方法来制备具有减少的二价金属量和改善的物理性能的硫化的橡胶组合物,且这些方法使得活化剂化合物仅在硫化期间且不早于混合期间提供给反应使用。 Limit or avoid the use of toxic side effects of the method for preparing vulcanized rubber composition having a reduced amount of the divalent metal and improved physical properties, and these methods so that the activator compound not only during the mixing to provide earlier during the vulcanization reaction use.

5已发现锌皂参与橡胶混合物中常用的二氧化硅填料表面的副反应,该副 5 has been found to participate in the rubber mixture of zinc soaps common side effects of silica filler surface, the deputy

反应消耗可用的锌(为ZnO),再生进一步消耗ZnO的硬脂酸,并降低所得硫化橡胶混合物的物理性能。 The reaction consumes the available zinc (as ZnO), stearic acid regeneration of ZnO is further consumed, and reduces the physical properties of the resulting vulcanized rubber mixture. 尽管这种副反应主要在使用锌活化剂组分时观察到,但是当使用类似的钙或镁激活时这个问题一样会出现。 Although the major side effects when using zinc activator component was observed, but when using a similar problem as calcium or magnesium occur when activated.

根据各种实施方式,通过改变成分添加顺序和精密的工艺控制来消除或抑制副反应。 According to various embodiments, by changing the order of addition of ingredients and precise process control to eliminate or suppress side reactions. 因而,在一个方案中,本发明基于上述情况的发现,即在化学激活意义上,诸如ZnO、锌皂和/或脂肪酸等活化剂组分只需要在硫化期间存在,而作为活化剂在混合期间并不需要。 Thus, in one aspect, the present invention is based on the discovery of the above, that is chemically activated sense, such as the activator component ZnO, zinc soap and / or fatty acids exist only during the vulcanization activator during mixing as not required. 特别是在温度倾向于高于IO(TC 或110。C的工艺步骤中,应避免或尽量少地使活化剂皂(或能原位形成活化剂皂的组分)与二氧化硅填料同时存在;该方法还导致硫化前即使在低温下活化剂皂和填料之间的接触时间也更短。例如,ZnO的用量可减少差不多在常规橡胶混合物中的90 ~ 95%。 Especially at a temperature higher than the IO process steps tend (TC or 110.C of, or as little as possible to avoid making soap activator (or activator can be formed in situ soap component) with the silica filler is present at the same time ; The method also results even at low temperatures before the vulcanization activator contact time between the soap and the filler is shorter, for example, can reduce the amount of ZnO in conventional rubber mixture in almost 90% to 95%.

在其它实施方式中,通过诸如ZnO、硬脂酸锌和/或硬脂酸等活化剂组分的微嚢包封实现所得硫化橡胶的工艺和物理性能调节。 In other embodiments, such as by micro Nang activator component ZnO, zinc stearate and / or stearic acid encapsulated to achieve the physical properties of the resulting rubber vulcanization process and adjustment. 该微嚢对高至120 。 The micro Nang for up to 120. C、高至130C、高至140。 C, up to 130 C, up to 140. C或高至150。 C or as high as 150. C的温度是稳定的,这允许微嚢包封的组分与二氧化硅填料在这些温度下共存,而其参与不需要的副反应的机会降低。 C temperature is stabilized, which allows micro-encapsulated component Nang coexist with the silica filler at these temperatures, while the opportunity to participate in undesired side reactions is reduced. 然后,当在更高的温度下硫化时(高于微嚢稳定的温度),这些微嚢释放出活化剂组分并激活硫化。 Then, when at a higher temperature vulcanized (above micro Nang stable temperature), these micro Nang release the activator component and activate the vulcanization. 有益地,副反应的控制允许使用低于常量的锌。 Control Advantageously, the side effects of allowing the use of less than constant zinc. 在一个示例性实施方式中,使用接近化学计量水平的ZnO和脂肪酸(一摩尔的氧化锌比两摩尔的脂肪酸),该用量显著低于锌的常规用量。 In one exemplary embodiment, using near stoichiometric ZnO and fatty acid levels (zinc oxide molar ratio of two moles of a fatty acid), the amount is significantly lower than conventional amounts of zinc.

以下将说明本发明的更多细节和实施方式。 The following will be described in more detail and embodiments of the present invention.

附图说明 Brief Description

图1示出了描述橡胶组合物的硫化参数。 Figure 1 shows a description of vulcanized rubber composition parameters. 具体实施方式 DETAILED DESCRIPTION

在一个实施方式中,本发明提供了通过用橡胶可溶的盐或皂激活硫硫化的硫化橡胶组合物的方法。 In one embodiment, the present invention provides a method of activation by sulfur-vulcanized rubber-soluble salts or soaps vulcanized rubber composition. 该方法包括第一混合,其中将未硫化的橡胶和填料,或未硫化的橡胶、填料和其它橡胶添加剂混合。 The method includes a first mixing, wherein the unvulcanized rubber and a filler, or vulcanized rubber, rubber additives and other fillers. 第一混合不包括碌u硫化体系的组分,且排除上述盐本身和上述橡胶可溶盐的至少阳离子组分。 First mixing components excluding busy u vulcanization system, and to exclude at least the above-mentioned salts the cationic component of the rubber itself and a soluble salt. 第一 The first

混合在高至约190C,优选在100C ~ 180。 Mixing up to about 190 C, preferably at 100 C ~ 180. C之间,更优选在110C~140C之间的温度下进行。 Between C, more preferably at a temperature of 110 C ~ 140 C will be between. 在第二混合中,在较低温度下将硫硫化组分和第一混合中未加入的任何盐或盐组分一起加入。 In the second mixing, at lower temperatures the sulfur vulcanizing components and any salt or salt component is not added in the first mixing added together. 通常,第二混合的温度不超过ll(TC且优选IO(TC或更低。在第二混合之后,通过在130。C或更高,优选150C或更高的温度下加热来硫化上述橡胶组合物。当上述硫化是使用锌脂肪酸盐激活时,该盐组分包括一种或多种阳离子锌化合物(上述盐的阳离子组分,通常为氧化物ZnO)和有机脂肪酸,诸如8〜26个碳原子的羧酸,而上述盐本身是该脂肪酸的锌盐或皂。 Typically, the second mixing temperature does not exceed ll (TC and preferably IO (TC or below. After the second mixing, by heating at 130.C or higher, preferably 150 C or higher temperature to cure said The rubber composition. When the above cure is activated using zinc salts of fatty acids, the salt component comprises one or more cationic zinc compound (cationic component such salts, typically oxides ZnO) and an organic fatty acid such as 8~ carboxylic acid 26 carbon atoms, and said salt itself or the zinc salt of fatty acids soaps.

上述盐或阳离子盐组分通过上述单独步骤加入。 Said salt or cationic salt component is added by the above individual steps. 由于在此讨论的原因,新的混合方法允许使用更少量的阳离子来提供硫化的激活作用。 For reasons discussed herein, a new mixing method allows the use of a smaller amount of a cationic curing to provide activation. 在又一个示例性实施方式中,当阳离子是锌时,上述橡胶组合物(在第二混合之后且硫化之前)优选包含2phr或更低的脂肪酸和2phr或更低的锌化合物。 In yet another exemplary embodiment, when the cation is zinc, the rubber composition (after mixing and before the second vulcanization) preferably contain 2phr or lower fatty acids and lower 2phr or zinc compound. 或者,上述橡胶组合物包括2phr或更低的锌脂肪酸盐。 Alternatively, the rubber composition comprises less 2phr or zinc salts of fatty acids.

上述第一混合不包括盐本身或至少橡胶可溶盐的阳离子组分,是指第一混合不以能与填料反应而污染填料并消耗硫化激活所需的阳离子的水平包括阳离子组分。 Said first mixing the salt itself, or at least does not include a rubber component soluble salt of a cation, a first mixing means not to be able to react with the filler and the consumption of pollution filler vulcanization activating the desired level cations include cationic component. 在一些配方中,活化剂组分是阳离子脂肪酸盐,又称为皂。 In some formulations, the activator component is a cationic salt of a fatty acid, also known as soaps. 上述盐的实例包括锌、钙和镁的盐。 Examples of such salts include salts of zinc, calcium and magnesium. 在其它配方中,活化剂是由作为橡胶组合物的独立添加剂提供的盐的阳离子组分和阴离子组分在混合或硫化期间原位形成。 In other formulations, the activator is a cationic component and the anionic salt component is provided by a rubber composition as a separate additive or mixed in situ formed during the vulcanization. 通常,该阴离子组分是脂肪酸,同时该阳离子组分是阳离子的氧化物或其它化合物。 Typically, the anionic component is a fatty acid, while the cationic component is a cationic oxides or other compounds. 示例性阳离子组分包括ZnO、 CaO和MgO。 Exemplary cationic component comprises ZnO, CaO and MgO. 因而,为了进一步说明,第一混合不包含脂肪酸的锌盐、钙盐或镁盐,并进一步不包含ZnO、 CaO或MgO。 Thus, in order to further illustrate, a first hybrid does not contain a fatty acid zinc salt, calcium or magnesium, and further does not contain ZnO, CaO or MgO. 第一混合至少排除阳离子组分,且也可以排除阴离子组分(即脂肪酸)。 Excluding at least a first mixing cationic component and an anionic component may be excluded (i.e., fatty acids). 但是,第一混合可包含(即不排除)活化剂皂的阴离子组分,因为根据本发明,脂肪酸不以有害方式与填料反应。 However, the mixing may comprise a first (i.e., does not exclude) activator soap anionic component, because, according to the present invention, the fatty acid is not reactive with the filler in a deleterious manner. 在本发明的组合物和方法中,优选填料是二氧化硅,优选的阳离子组分 In the compositions and methods of the present invention, preferably the filler is silica, the preferred cationic component

是ZnO。 Is ZnO. 将就这些添加剂对本发明进行进一步的非限制性说明。 These additives to the present invention will be further non-limiting illustration.

在示例性实施方式中,第一混合在诸如班伯里密炼机(Banbury)等桶型剪切混合机中进行,而第二混合在开炼机上进行。 In an exemplary embodiment, the first mixed in a mixer such as a Banbury (Banbury) and other bucket shear mixer and, while mixing in the second mill machine. 在各种实施方式中,第一混合时未加入的氧化锌,在与硫化剂包加入之前或之后一起在第二混合期间第一次加入。 In various embodiments, the zinc oxide was not added in the first mixing, and prior to or after the vulcanization agent is added together with the package for the first time was added in the second mixing period. 在第一混合期间,至少省略了橡胶可溶盐的阳离子组分。 During the first mixing at least a rubber omitted soluble salt of the cationic component. 优选地,在第二混合中加入少于2phr的氧化锌。 Preferably, the zinc oxide is added in less than a second mixing 2phr. 例如,在各种实施方式中,氧化锌的量为0.1〜lphr。 For example, in various embodiments, the amount of zinc oxide is 0.1~lphr. 也加入少量的脂肪酸。 Also adding a small amount of fatty acids. 在非限制性实施方式中,加入0.05 ~ 0.5phr的氧化锌和0.1 ~ 1.5phr的脂肪酸。 In a non-limiting embodiment, zinc oxide and 0.05 ~ 0.5phr 0.1 ~ 1.5phr fatty acids.

在优选实施方式中,上述填料包括诸如10 ~ 100phr量的二氧化硅填料。 In a preferred embodiment, it said filler comprises such an amount of 10 ~ 100phr silica filler. 在其它非限制性实施方式中,上述混合物包括30 ~ 60phr的二氧化硅填料或40 ~ 60phr的二氧化珪填料。 In other non-limiting embodiments, said mixture comprises 30 ~ 60phr of silica filler or 40 ~ 60phr Gui dioxide filler.

在优选实施方式中,以接近1摩尔氧化锌比2摩尔脂肪酸的化学计量比将氧化锌和脂肪酸加入橡胶混合物中。 In a preferred embodiment, a stoichiometric ratio of approximately 1 mole of zinc oxide 2 molar ratio of fatty acid and fatty acid was added to zinc oxide in the rubber mixture. 在进一步优选的实施方式中,氧化锌被微嚢包封在壁材料中,该壁材料能承受混合时的温度但在随后的硫化温度下溶解或破裂。 In a further preferred embodiment, the temperature of the zinc oxide is encapsulated in micro Nang wall material, the wall material can withstand when it is dissolved or mixed in the subsequent vulcanization rupture temperature. 在各种实施方式中,氧化锌以具有微米范围直径的颗粒提供。 In various embodiments, the zinc oxide particles having a diameter in the micrometer range provided. 在其它实施方式中,氧化锌至少包括一些至少100nm或更小的颗粒。 In other embodiments, the zinc oxide comprising at least 100nm, or at least some of the smaller particles. 在商业实施方式中,氧化锌具有75nm的平均粒径。 In the commercial embodiment, the zinc oxide having an average particle diameter of 75nm.

在另一个实施方式中,本发明提供使用受保护的硫化剂用活化剂组合物来制造硫化橡胶组合物的方法。 In another embodiment, the present invention provides the use of a vulcanizing agent protected by the activator composition to produce vulcanized rubber composition method. 与以前一样,橡胶组合物的石克化机理涉及使用脂肪酸的锌盐或锌皂激活硫硫化。 As before, the stone digestion mechanism of the rubber composition of fatty acids involves the use of zinc or zinc sulfide sulfur soap activation. 或者,使用钙盐或镁盐激活硫化。 Alternatively, calcium or magnesium sulphide activated. 在第一混合步骤中,将未硫化的橡胶、填料和其它硫硫化包(sulfur cure package )以外的橡胶添加剂在约150。 In the first mixing step, the rubber uncured rubber, fillers, and other sulfur vulcanizing package (sulfur cure package) outside the additive at about 150. C或更低的温度下进行混合,例如在班伯里密炼机中。 C or lower were mixed in a Banbury mixer at for example in. 在第二混合中,例如在开炼机中,优选在110。 In a second mixing, for example in an open mill, preferably at 110. C或更低的温度下将硫硫化剂加入第一混合的产物中。 Under C or lower sulfur vulcanizing agent is added to the product mix in the first. 作为受保护的活化剂组合物的实例,微嚢包封的氧化锌和/或微嚢包封的锌脂肪酸盐被加入到第一混合或第二混合任何一步中,或加入到两者中。 As an example of a protected activator composition, zinc oxide micro Nang encapsulated and / or zinc salts of fatty acids micro Nang encapsulated is added to the first or second mixing any mixing step, or added to both . 在优选实施方式中,当第一混合温度高于130C In a preferred embodiment, when the first temperature is higher than 130 C mixed

8时,受保护的活化剂或微嚢包封的Zn、 Ca或Mg化合物只在第二混合中加入。 8:00, Zn protected activator or micro-encapsulated Nang, Ca or Mg compound is added only in the second mix. 该微嚢包封的锌化合物包括各锌化合物(氧化锌和锌脂肪酸盐或皂)和包覆在锌化合物上的壁材料。 The micro-encapsulated Nang zinc compound including the zinc compound (zinc oxide and zinc salts of fatty acids or soaps) and coated on a zinc compound wall material. 该壁材料在足够高的温度下稳定,使得它在第一或第二混合期间不释放锌化合物。 The wall material at a high enough temperature stable, making it the first or second zinc compound is not released during mixing. 这样,防止了锌与二氧化硅填料的接触,直至橡胶组合物在更高的温度下硫化。 Thus, the zinc and the silica filler to prevent contact until the rubber composition vulcanized at a higher temperature. 上述方法进一步包括在高于120。 Said method further comprising at above 120. C或高于130C,优选在15(TC及以上的温度下通过加热来硫化所得的橡胶组合物。在硫化时,锌化合物(或4丐或镁,若使用了的话)从微嚢中释放。如果氧化锌是微嚢包封的,在释放时与脂肪酸化合产生激活橡胶组合物的硫硫化的锌皂。优选地,橡胶组合物包含2phr或更少的氧化锌或锌脂肪酸盐。在优选实施方式中,上述混合物包含少于lphr,优选少于0.5phr或少于0.3phr的氧化锌或锌皂。 C or higher than 130 C, preferably at 15 (at a temperature above the TC and by heating the resulting vulcanized rubber composition in vulcanization, zinc compound (4 or hack or magnesium, when using the words) from the micro Nang release. If the zinc oxide is encapsulated micro Nang, generated activated when released sulfur vulcanizing the rubber composition of the zinc compound and a fatty acid soap. Preferably, the rubber composition comprising 2phr or less of zinc oxide or zinc salts of fatty acids. In a preferred embodiment, the above-mentioned mixture comprises less than lphr, preferably less than or less than 0.3phr 0.5phr zinc oxide or zinc soaps.

在各种实施方式中,上述橡胶混合物包含少于2phr的氧化锌与充足的脂肪酸一起形成足以提供适宜的硫化动力学的量的皂。 In various embodiments, the rubber mixture comprises less than 2phr zinc oxide with a fatty acid together form a sufficient amount sufficient to provide a suitable soap vulcanization kinetics. 在优选实施方式中,橡胶组合物包括10 ~ 100、 30 ~ 60phr,或40 ~ 50phr的二氧化硅填料。 In a preferred embodiment, the rubber composition comprises 10 ~ 100, 30 ~ 60phr, or 40 ~ 50phr of silica filler. 在多种实施方式中,上述壁材料选自蜡、石蜡、聚乙烯、乙烯-醋酸乙烯酯共聚物和聚乙烯醇。 In various embodiments, the wall material is selected from the above-described wax, paraffin wax, polyethylene, ethylene - vinyl acetate copolymer, and polyvinyl alcohol.

橡胶配方通常用每100份橡胶的份数(phr)来表示。 Rubber formulations usually parts per 100 parts of rubber (phr) to represent. 为了说明,常规的橡胶配方可包含IOO份的橡胶、45phr的填料、5phr的ZnO、 lphr的硬脂酸、2phr的硫和各种诸如促进剂、阻滞剂、工艺用油、抗氧化剂等其它成分。 To illustrate, the conventional rubber formulations may contain IOO parts of rubber, 45phr filler, 5phr of ZnO, lphr stearate, 2phr variety such as sulfur and accelerators, retarders, process oils, antioxidants and other ingredients. 在该配方中,诸如ZnO等组分的重量百分比以整体总重量的分数或百分比计算。 In this formulation, the weight percentage ZnO and other components such as a fraction or percentage of the overall total weight.

本发明的橡胶组合物包含天然或合成橡胶或橡胶的混合物,以及诸如硫化剂和促进剂等常规橡胶添加剂。 The mixture of the rubber composition of the present invention comprise a natural or synthetic rubber or rubbers, as well as vulcanizing agent and conventional rubber additives promoting agent. 在各种实施方式中,本发明的组合物是包含橡胶树脂、硫化剂组合物、填料和受保护的用于硫化剂的活化剂组合物的可模塑橡胶组合物。 In various embodiments, the compositions of the present invention is a rubber resin, curing agent compositions, fillers and protected activator composition for the curing agent can be molded rubber composition. 在具体的实施方式中,受保护的活化剂组合物包括微嚢包封的金属氧化物或微嚢包封的金属皂或脂肪酸盐。 In a specific embodiment, the protected activator composition comprising a metal oxide micro Nang encapsulated or micro encapsulated Nang metal soaps or fatty acid salts. 上述金属选自元素周期表IIA族和IIB族的金属,但优选为锌、钙或镁,特别优选为氧化物ZnO、 The metal is selected from Group IIA and IIB of the Periodic Table of the metal, but is preferably zinc, magnesium or calcium, particularly preferably an oxide ZnO,

9CaO和MgO。 9CaO and MgO. 用于活化剂组合物的金属优选为锌。 Activator composition for the metal is preferably zinc.

通常,可使用能通过硫硫化交联的任何橡胶来制备本发明的组合物。 Typically, the compositions of the present invention are prepared using any rubber crosslinked by sulfur vulcanization. 硫硫化说明了制造橡胶的常规4化工艺。 Sulfur vulcanized rubber described manufacturing process of a conventional 4. 也可使用橡胶的混合物。 Rubber mixture can also be used. 用于本发明的橡胶实例包括,但不限于,天然橡胶和诸如基于聚异戊二烯的改性天然橡胶。 Examples of the rubber used in the present invention include, but are not limited to, natural rubber and modified natural rubbers such as polyisoprene based.

合成橡胶也可用于本发明。 Synthetic rubber can also be used in the present invention. 其实例包括但不限于,合成聚异戊二烯、聚丁二烯、丁腈橡胶、苯乙烯-丙烯腈-丁二烯橡胶、氯丁橡胶、苯乙烯-丁二烯共聚物橡胶、异戊二烯-异丁烯共聚物橡胶及其囟代衍生物、诸如乙烯-丙烯-环戊二烯三元共聚物、乙烯-丙烯-5-亚乙基-降冰片烯三元共聚物和乙烯-丙烯-l,4-己二烯三元共聚物等乙烯-丙烯-二烯共聚物橡胶、丁二烯-丙烯共聚物橡胶、丁二烯-乙烯共聚物橡胶、丁二烯-异戊二烯共聚物、聚戊烯(polypentenamer )及它们的混合物。 Examples include, but are not limited to, synthetic polyisoprene, polybutadiene, nitrile rubber, styrene - acrylonitrile - butadiene rubber, chloroprene rubber, styrene - butadiene copolymer rubber, isoprene diene - isobutylene copolymer rubber and halogenated derivatives thereof, such as ethylene - propylene - cyclopentadiene terpolymers, ethylene - propylene-5-ethylidene - norbornene terpolymer and an ethylene - propylene - ethylene-l, 4- hexadiene terpolymers, etc. - propylene - diene copolymer rubber, a butadiene - propylene copolymer rubber, a butadiene - ethylene copolymer rubber, a butadiene - isoprene copolymer , polyprenyl (polypentenamer), and mixtures thereof. 通常,这些化合物的特征是聚合物的骨架有重复的烯类不饱和性,这种不饱和性通常是由于聚合物结构中含有丁二烯或异戊二烯单体而造成。 Typically, these compounds are characterized by the polymer backbone duplicate ethylenically unsaturation, this unsaturation is usually due to polymer structure comprising butadiene or isoprene monomer caused.

常规的硫类硫化剂也可用于本发明的组合物中。 Conventional sulfur-based vulcanizing agent may also be used in the compositions of the present invention. 这类硫化剂在本领域是公知的,包括可溶元素硫、不溶元素碌^和它们的混合物,以及各种有枳J克化物、二硫化物和多硫化物化合物。 Such curing agents are well known in the art, including soluble elemental sulfur, insoluble elements Lu ^, and mixtures thereof, and various compounds have grams, disulfide and polysulfide compound trifoliate J. 非限制性实例包括诸如二硫化吗啉、2-(4'-吗啉基二硫)-苯并漆唑,和诸如四曱基秋兰母二硫化物、四乙基秋兰母二硫化物和二亚戊基秋兰母四硫化物等秋兰母化合物等硫化剂。 Non-limiting examples include such as morpholine disulfide, 2- (4'-morpholino disulfide) - benzo oxazole paint, such as four, and Yue-yl Orchids mother disulfide, tetraethyl Orchids mother disulfide and two pentamethylene sulfide Orchids Orchids mother four parent compound vulcanizing agent. 上述硫化剂可单独使用或互相组合使用。 It said vulcanizing agents may be used alone or in combination with one another. 在优选实施方式中,硫用作硫化剂。 In a preferred embodiment, the sulfur vulcanizing agent is used.

本发明的橡胶组合物也通常包含常规促进剂。 The rubber composition of the present invention also typically comprise conventional accelerators. 这类促进剂和共促进剂在 Such promoters and co-promoters in

本领域是已知的,且非限制性包括基于二硫代氨基曱酸盐、噻唑、胺、胍、 Are known in the art, including those based and non-limiting Yue dithiocarbamate salts, thiazole, amine, guanidine,

黄原酸盐、硫脲、秋兰母、二硫代磷酸盐和亚磺酰胺等的化合物。 Xanthate compounds, thiourea, Orchids mother, dithiophosphates and sulfenamides like. 促进剂的 Accelerator

非限制性实例包括:二异丁基二硫代氨基曱酸锌、2-疏基苯并噻唑的锌盐、 Non-limiting examples include: diisobutyl dithiocarbamate Yue zinc, 2-mercaptobenzimidazole zinc salt of thiazole,

己撑四胺、1,3-二苯基胍、异丙基黄原酸锌、三曱基硫脲、四节基秋兰母二 Hexamethylene tetramine, 1,3-diphenyl guanidine, zinc isopropyl xanthate, three 曱 thiourea, mother of two four groups Orchids

硫化物、O,O-二-正丁基二硫代磷酸锌和N-叔丁基-2-苯并噻唑基亚磺酰胺。 Sulfide, O, O- two - zinc dithiophosphate and butyl N- tert-butyl-2-benzothiazolyl sulfenamide.

在各种实施方式中,上述促进剂活化剂包括称作"皂(soap)"的脂肪酸的金属配合物。 In various embodiments, the above-mentioned promoters include activators referred to as "soap (soap)" of the fatty acid metal complexes. 锌皂包括诸如具有8〜36个碳原子或8〜26个碳原子的脂肪酸的皂或盐。 Zinc soaps of fatty acids include, for example having 8~36 8~26 carbon atoms or carbon atoms soap or salt. 在非限制性实施方式中,脂肪酸具有10〜24个碳原子。 In a non-limiting embodiment, the fatty acid having 10~24 carbon atoms. 非限制性实例包括月桂酸、油酸和硬脂酸。 Non-limiting examples include lauric, oleic, and stearic acid. 通过将两摩尔的脂肪酸与一摩尔的锌化合,上述脂肪酸与锌形成皂。 By two moles of fatty acid with one mole of zinc compounds, the formation of the fatty acid and zinc soap.

为了发挥其激活作用,锌皂可直接加入橡胶组合物中,也可根据上述方法胶嚢包封。 In order to play its role in the activation, zinc soap can be directly added to the rubber composition, according to the method described above can also be encapsulating plastic Nang. 作为另一种选择或另外,诸如ZnO和脂肪酸等单独的化合物可共混进入可硫化的橡胶组合物中。 Alternatively or additionally, such as a separate compound ZnO and fatty acids may be blended into the vulcanizable rubber composition. 在诸如硫化等高温处理期间,上述单独的化合物原位反应形成皂。 During the curing process, such as high temperature, etc., the above individual compounds in situ to form soaps. 在另一种情况下,该皂被认为是活性物质。 In another case, the soap is considered to be the active substance. 此处所用的术语皂组分、活化剂组分、盐组分等,除非文中特别说明,是指任何的ZnO或其它锌盐、锌皂本身及脂肪酸组分。 The term soap component used herein, the activator component, salt component, etc., unless the context otherwise indicated, refers to any of ZnO or other zinc salts, zinc soap and fatty acid composition in itself. 因而添加皂组分是指在化合期间添加任何的上述组分到橡胶组合物中。 Add soap component therefore refers to a compound added during any of the above components to the rubber composition.

在各种实施方式中,本发明提供在高温硫化前避免作为锌皂存在的锌与二氧化硅填料接触的方法和组合物。 In various embodiments, the present invention provides a high temperature before vulcanization to avoid the presence of zinc soap as methods and compositions for zinc in contact with the silica filler. 只要没有或很少的锌组分与填料同时存在,或可选地如果利用胶嚢包封防止存在的任何锌组分与其表面发生反应,就可避免锌和二氧化硅填料的有毒副反应。 As long as little or no zinc component and the filler is present at the same time, or alternatively, if the use of plastic encapsulated Nang prevent any zinc component present in the surface to react therewith, zinc and silica filler can avoid toxic side effects. 如果ZnO、硬脂酸锌或硬脂酸(后两者作为皂和脂肪酸的非限制性实例)这三种成分之一是胶嚢包封的,则Zn被保护并在硫化期间提供给反应使用。 If ZnO, zinc stearate or stearic acid (the latter two are non-limiting examples of soaps and fatty acids) is one of these three components encapsulated gum Nang, the Zn is protected and supplied to the reactor during the vulcanization using . 在优选实施方式中,ZnO或硬脂酸锌是胶嚢包封的。 In a preferred embodiment, ZnO or zinc stearate is encapsulated gum Nang. 硬脂酸可以是胶嚢包封的,但因为其它辅助化学品可能将微量硬脂酸作为分散剂引入,所以优选将ZnO或硬脂酸锌胶嚢包封。 Stearic acid may be encapsulated gum Nang, but because other auxiliary chemicals may be introduced into the micro stearate as a dispersing agent, it is preferable to ZnO or zinc stearate gel Nang encapsulated.

有益地,因为上述方法提供对锌的保护(即,锌保持可用于激活硫化促 Advantageously, since the above method provides protection for zinc (ie, zinc remains available for activation vulcanization accelerator

进剂,而不是在二氧化硅填料表面结合和分解),加入橡胶混合物中以提供 Into the agent, and not the surface of the silica filler and binding decomposition), was added to provide a rubber mixture

适宜的或可接受的硫化所需锌的量相对较低。 Suitable relatively low amount of the desired or acceptable zinc sulfide. 为便于说明,通常当将5phr For ease of explanation, usually when the 5phr

的ZnO和约lphr的脂肪酸一起使用时,ZnO的量可减少至低于2phr,甚至 When used in conjunction with ZnO and about lphr fatty acids, the amount of ZnO can be reduced to less than 2phr, even

低于lphr,且不会对硫化橡胶的性能有负面影响。 Lower than lphr, will not have the properties of vulcanized rubber have a negative impact. 实际上,其表现出提高的 In fact, the exhibit increased

物理性能。 Physical properties. 尽管本发明不受理论限制,认为该物理性能的提高是由于锌对填 Although the present invention is not limited by theory, that the increase is due to the physical properties of zinc to fill

料表面的污染降低,且橡胶组合物中相对大(与其它添加剂和填料相比)的 Contaminated material surface decreases, and the rubber composition is relatively large (compared with other additives and filler)

ZnO颗粒数量降低,这些ZnO大颗粒作为应力集中点,会导致块状材料的裂纹和破坏。 Reduce the number of particles of ZnO, ZnO large particles such as stress concentration points, can cause cracks and damage bulk material.

在优选实施方式中,受保护的锌以1摩尔的Zn对2摩尔的脂肪酸的量 In a preferred embodiment, the zinc protected with one mole of Zn on the amount of 2 moles of fatty acids

存在于橡胶组合物中。 Present in the rubber composition. 该比例称作"化学计量比",因为它对应于脂肪酸和 This ratio is called "stoichiometric ratio", because it corresponds to the fatty acid and

二价锌的皂的分子式。 Divalent zinc soap formula. 对lphr的脂肪酸,化学计量的锌通常低于0.5phr。 For lphr fatty acids, zinc is usually less than stoichiometric 0.5phr. 因而在多种实施方式中,本发明提供锌的量的降低大于90% (即从5phr的常规量降至0.5phr或更低)。 Thus in various embodiments, the present invention provides a reduced amount of Zn is greater than 90% (i.e., dropped from the 0.5phr 5phr conventional amounts or less). 在典型的实施方式中,激活作用由约0.3phr的ZnO和lphr的脂肪酸提供,约等于化学计量比。 In the exemplary embodiment, activation by approximately 0.3phr of ZnO and fatty acid lphr, approximately equal to the stoichiometric ratio. 一旦Zn相对于酸类物质的量低于化学计量,因为活性物质(锌盐)含量较低,硫化的激活就会被抑制。 Once the amount of Zn with respect to acids is less than stoichiometric, because less active material (zinc salt) content, activation is inhibited vulcanized.

为提高性能、节省资金、筒化工艺、改善物理性能或因为其它原因,在橡胶组合物中使用填料。 To improve performance, save money, of the process cartridge, improvement in the physical properties or because of other reasons, the use of fillers in the rubber composition. 多种填料材料是公众所知的。 More filler materials are known to the public. 在多种实施方式中,上述组合物包括二氧化硅填料。 In various embodiments, the above compositions comprise silica filler. 二氧化硅的常规含量为约10phr〜100phr或更高。 Conventional silica content of about 10phr~100phr or higher. 在多种实施方式中,组合物包含10~80、 30 - 70、 40~60、 50 ~ 60或35 ~ 60phr的填料。 In various embodiments, the composition comprises from 10 to 80, 30--70, 40 ~ 60, 50 ~ 60 35 ~ 60phr or filler.

适用于橡胶配料的氧化锌可采用多种粒径。 Zinc oxide for rubber particle size can be a variety of ingredients. 例如,纳米粒子Zn0(75。/0的母料)可从Cosmos Chemical商购,报告具有75nm的粒径。 For example, the nanoparticles Zn0 (75. / 0 masterbatch) commercially available from Cosmos Chemical, report having a particle size of 75nm. 来自Atman的标准ZnO ( 80%的母料)净艮告具有50pm的粒径。 Standard ZnO from Atman (80% of the masterbatch) Net Burgundy reported having a particle size of 50pm. 与母料相对,还可使用具有任何可分散粒径的氧化锌粉末。 And the master batch opposite may also be used with any of the zinc oxide powder dispersed particle diameter.

本发明的方法提倡在第一混合和第二混合中加入各种组分。 The method of the present invention is added to promote the mixing of the various components in the first and second mixing. 上述混合是指操作步骤,且可以限定必需将混合的化合物从一个容器转移到另一个容 Refers to the mixing procedure, the mixing of the compound is necessary and can be defined to be transferred from one container to another container

器,也可以不。 Device, you can not. 例如,第一混合可在诸如班伯里密炼机等混合机中进行,而从班伯里密炼机中取出后,第二混合在开炼机中进行。 For example, the first mixed in a mixer such as a Banbury mixer, etc. carried out, and after removal from the Banbury mixer, a second mixing carried out in an open mill. 或者,第一混合和第二混合可在相同的混合容器或装置中进行。 Alternatively, the first mixing and the second mixing may be carried out in the same mixing vessel or device. 一个实施例是将部分总配方组成在诸如开炼机等装置中混合,并在第一混合和随后的混合中继续加入各组分。 One example is the portion of the total formula composition in a device such as open mixing mill, etc., and in the first mixing and subsequent mixing continue adding the ingredients.

所谓"第一"和"第二"混合也并非必要地意味着如此表述的步骤是一个接着另一个立即连续进行的。 The so-called "first" and "second" also does not necessarily mean the mixing step such statements are immediately one after another continuously. 相反,该表述允许存在中间步骤,例如当添加其它组分时。 Instead, there is an intermediate step that allows the expression, for example, when you add the other ingredients. 在各个实施方式中,在约130~ 150。 In various embodiments, at about 130 to 150. C的较高温度下进行第一混合(在一个实施方式中不包括锌组分,而在另一个实施方式中,只有当锌组分是微嚢包封的时才包括锌组分)。 A first mixing at high temperatures of C (in one embodiment, does not include a zinc component, and in another embodiment, only when the zinc component is only slightly Nang encapsulated include zinc component). 这些温度是如班伯里密炼机的桶型剪切混合机的常规温度。 These temperatures are as a conventional Banbury mixer barrel temperature type shear mixer. 在班伯里密炼机或类似混合机中,橡胶和其它组分(通常不包括硫化组分)剪切混合。 In a Banbury mixer or similar mixer, rubber and other components (not usually including curing component) shear mixing. 剪切产生热,且热会有利于混合。 Cut generates heat, and the heat will facilitate mixing. 诸如二氧化硅等填料通常在该步骤中加入。 A filler such as silica is generally added in this step.

第二混合,在该步骤中少量的锌可与^5克化包一起加入,优选在较低的温 A second mixing, in this step may be to join a small amount of zinc and ^ 5 g of package, preferably at a lower temperature

度,优选低于约ll(TC下进行,部分避免早期硫化。在多种实施方式中,该温度是100。C或更低。在非限制性实施例中,第二混合在开炼机中进行。材 Degrees, preferably less than about ll (TC conducted under partly to avoid scorching. In various embodiments, the temperature is 100.C or less. In a non-limiting embodiment, the second mixing in an open mill conduct. Material

料在辊中的温度通过冷却辊来调节,通常低于班伯里密炼机中出现的高温。 The temperature of the feed roll is adjusted by means of a cooling roll, a Banbury mixer temperature is usually lower than appearing. 混合装置的其它组合对本领域技术人员是熟知的,并适用于进行第一混合和第二混合,以及任何其它配制和硫化橡胶混合物所需的混合步骤。 Other combinations of the mixing device to the skilled person is well known, and applied to the first mixing and the second mixing, and mixing step further formulated and vulcanized rubber compounds needed for any conduct.

微嚢包封的方法有多种,且部分取决于被包封材料和所需释放包封组分的模式。 There are a variety of micro-encapsulation method Nang, and partially depends on the encapsulating material and the desired release encapsulated component model. 因为理想结果是在硫化循环期间释放包封的组分,上述微囊必须具有某些性能。 Because the ideal result is the release of the encapsulated component during the curing cycle, said microcapsules must have certain properties. 首先,必须能经受诸如在开炼机上,或者,若需要的话,在班伯里密炼机中的较高温度下混合。 First, it must be able to withstand, such as in the open mill, or, if desired, higher temperatures were mixed in a Banbury mixer. 该微嚢必须具有足够的强度以承受粉碎中遭受的剪切力,而不会有大量破裂。 The micro Nang must have sufficient strength to withstand shear forces suffered crushing, instead of a large number of rupture. 优选地,上述微嚢在某一温度下破裂使 Preferably, the above-mentioned micro Nang rupture at a certain temperature so

得锌活化剂在硫化期间提供给反应使用。 Zinc activator was provided during the vulcanization reaction to use. 在多种实施方式中,在130土20。 In various embodiments, the soil 20 130. C、130 IO'C或125土5。 C, 130 IO'C or 125 5. C的温度下,微嚢破裂并释放包封的锌。 C of temperature, micro Nang rupture and release the encapsulated zinc. 微嚢材料不应对体系的硫化性能有负面影响,也不应导致硫化橡胶最终性能的任何不可接受的降低。 Micro Nang material curing properties of the system should not have a negative impact, should not lead to any unacceptable reduction in the final properties of vulcanized rubber. 在多种实施方式中,通过微嚢包封活化剂,硫化动力学稍微变慢。 In various embodiments, by micro-encapsulated activator Nang, cure kinetics slightly slower. 这并不必然不利于生产。 This does not necessarily conducive to production.

选择与橡胶混合组分有良好相容性的微囊壁材料。 Selection and rubber blending components have good compatibility microcapsule wall material. 非限制性实例包括蜡、石蜡、聚乙烯(PE)、乙烯-醋酸乙烯酯共聚物、聚乙烯醇(PVA)以及它们的混合物。 Non-limiting examples include waxes, paraffins, polyethylene (PE), ethylene - vinyl acetate copolymer, polyvinyl alcohol (PVA) and mixtures thereof. 其它非限制性实例包括酪蛋白酸4丐、聚果胶酸4丐、聚丙烯酸及其衍生物、聚碳酸酯、聚环氧乙烷、聚曱基丙烯酸酯、聚原酸酯、聚醋酸乙烯酯、聚乙烯吡咯烷酮和热塑性聚合物。 Other non-limiting examples include caseinate 4 beggar, beggar poly pectate 4, polyacrylic acid and derivatives thereof, polycarbonate, polyethylene oxide, poly Yue acrylate, polyorthoester, polyvinyl acetate ester, polyvinylpyrrolidone and a thermoplastic polymer. 在多种实施方式中,适宜的涂布材料也包括可聚合组合物。 In various embodiments, the coating material also comprises a suitable polymerizable composition. 非限制性实 Non-limiting

例包括液态聚丙烯酸酯组合物,该组合物可包含:由光引发剂和热引发剂组成的催化剂体系;包含二氢嘧啶、四唑和可溶离子盐的可聚合混合物;聚氨酯;可选择地包含叔胺基团的无定形聚酯;聚氨基组合物和2,4,6-三氨基-1,3,5-三溱与乙醛的衍生物的混合物;聚乙烯和聚乙烯醇的混合物;氨基塑料树脂;和硅树脂聚合物。 Examples include polyacrylates liquid composition, the composition may comprise: from the photoinitiator and the thermal initiator catalyst system consisting agent; dihydropyrimidine comprising the polymerizable mixture of tetrazole and a soluble ionic salt; polyurethane; alternatively a mixture of polyethylene and polyvinyl alcohol; contains a tertiary amine group amorphous polyester; poly-amino-1,3,5-mixture composition and 2,4,6-triamino three helmets and acetaldehyde derivatives ; aminoplast resins; and silicone polymers.

在一些优选实施方式中,适宜的壁材料应在一定温度范围内熔融,该温度范围对于橡胶硫化非常重要,即约100〜260。 In some preferred embodiments, a suitable wall material should melt at a certain temperature range, the temperature range is important for rubber vulcanization, or about 100~260. C之间。 Between C. 它们优选在低于150 r时熔融,且优选具有120~ 140。 They are preferably melt at temperatures below 150 r, and preferably 120 to 140. C范围内的熔点,特别是约130C。 C melting point within the range, especially about 130 C. 优选地, 在熔融前,优选直至120~ 140。 Preferably, prior to melting, preferably up to 120 to 140. C的温度,特别是直至约130。 C temperature, especially up to about 130. C,涂布材料在橡胶或橡胶混合物中相对不溶。 C, the coating material is relatively insoluble in rubber or rubber mixture. 在多种实施方式中,该材料在更高的温度下溶于橡胶,例如高于120或130C。 In various embodiments, the rubber material is dissolved at a higher temperature, e.g., above 120 or 130 C.

在非限制性实施方式中,通过将ZnO加到聚合壁材料在第I-IV族金属的卣化物或硝酸盐的醇溶液的溶液中进行微嚢包封。 In a non-limiting embodiment, the ZnO was added to the polymerization by the wall material of micro encapsulated in solution Nang first I-IV metals in the wine container or nitrate compound in an alcohol solution. 为了说明的目的,将10g聚酰胺溶解在190g饱和氯化钙的曱醇溶液中。 For purposes of illustration, the polyamide is dissolved in 10g 190g 曱 saturated alcoholic solution of calcium chloride. 加入10g ZnO形成悬浮液。 10g ZnO was added to form a suspension. 将该悬浮液加入至1升1:1的MeOH:水的混合物中,并搅拌约15分钟以得到ZnO微嚢。 The suspension was added to one liter 1: MeOH 1: The mixture of water and stirred for about 15 minutes to obtain a ZnO micro Nang.

在另一个实施方式中,粉末ZnO以约7:3的比例与聚乙烯蜡在高于其熔点的温度下结合,然后在熔融状态传送到旋转工作台上并在冷却塔内雾化提 In another embodiment, the ZnO powder to about 7: 3 ratio of the polyethylene wax at a temperature above its melting point in combination, in a molten state and then transferred to the rotary table and atomization in the cooling tower

供微嚢。 For micro Nang.

实施例 Example

实施例1 Example 1

如上所述,Zn在副反应中消耗。 As described above, Zn consumed in side reactions. 硬脂酸锌能与诸如沉淀的二氧化硅等填料表面的羟基反应。 Zinc stearate can react with hydroxyl groups such as precipitated silica filler surface. 在该反应的第一阶段,产生一个硬脂酸分子。 In the first stage of the reaction, to produce an acid molecule. 假如有更多的ZnO,会释放另一个硬脂酸分子,然后Zn与两个表面氧原子键合。 If there are more of ZnO, stearic acid will release another molecule, then Zn and oxygen atoms bonded to both surfaces. 以下更完整地i兌明该反应才几理。 The following more fully i against the rationale on which the reaction only a few.

ZnO的消耗及硬脂酸的生成步骤1:氧化锌与2分子的硬脂酸反应生成硬脂酸锌和水。 Generating step of ZnO and stearic acid consumed 1: Reaction of zinc oxide and stearic acid to generate two molecules of zinc stearate and water. ZnO + 2 CI7H35COOHh Zn(C17H35COO)2 +H20 ZnO + 2 CI7H35COOHh Zn (C17H35COO) 2 + H20

步骤2:硬脂酸锌和二氧化硅颗粒表面的羟基反应产生一个硬脂酸分子。 Step 2: The hydroxyl group of zinc stearate and silica particle surface reaction produces an acid molecule. II II

oo oo

-SiOH -SiO-Zn(C17H^COO》 -SiOH -SiO-Zn (C17H ^ COO "

0 + Zn(G17H35CO0)2 ~* O -SiOH SiOH 0 + Zn (G17H35CO0) 2 ~ * O -SiOH SiOH

1 I 1 I

步骤3:进一步与二氧化硅羟基反应会产生另一个硬脂酸;从而污染二氧化石圭表面。 Step 3: Further silica react with hydroxyl groups will produce another stearate; thus dioxide pollution Kyu stone surface.

0 0

-SiO -SiO

1 \ 1 \

I / I /

当ZnO相对于硬脂酸大量过剩时,上述反应进行到步骤3。 When ZnO large excess relative to the acid, the above reaction proceeds to step 3. 当少量过剩或对硬脂酸化学计量不足,当ZnO消耗完时该反应在步骤2停止。 When a small amount of excess or shortage of the stoichiometric stearate, ZnO depleted when the reaction is stopped in step 2.

当ZnO (硬脂酸锌)消耗完时上述反应的停止已通过FTIR示出,其中 When ZnO (zinc stearate) consumed stop has been shown by FTIR, wherein said reaction

15当ZnO和随后的硬脂酸锌浓度接近零时,反应2中第二部分所示物质仅通过FTIR解析。 15 When the ZnO and the subsequent concentration of zinc stearate is close to zero, the reaction mass in Figure 2 in the second part only by FTIR resolution. 这表明消耗Zn并生成硬脂酸(步骤2和3)的反应非常快。 This suggests that consumption of Zn and generate stearate (steps 2 and 3), the response was very fast. 实施例2 Example 2

因为在常规混合中,ZnO和硬脂酸在橡胶组分的初始混合(班伯里密炼机)中加入,它们存在于从初始混合至最终硫化的整个循环中。 Because conventional mixing, ZnO and stearic acid in the initial mixing of the rubber component (Banbury mixer) was added, they exist in a mixed from initial to final curing of the entire cycle. 此外,除硫化外,初始混合是橡胶混合物遭受最高温度之处,通常>130匸。 Furthermore, in addition to curing, the initial mixing rubber mixture is subjected to at a maximum temperature of typically> 130 Xi.

通过在工艺后期加入活化剂,例如在第二混合中添加硫和促进剂期间, 减少了硫化所需的ZnO总量。 Was added late in the process by an activating agent, such as sulfur and accelerators added during the second mixing, reducing the total amount of ZnO required for vulcanization. 即使不减少ZnO,直至等到工艺后期,由于填料表面污染减少,也改善了硫化橡胶混合物的物理性能。 If not reduced ZnO, up until the latter part of the process, since the filler to reduce surface contamination, but also to improve the physical properties of vulcanized rubber compound. 而且,如图l所示硫化加快。 Moreover, as shown in Figure l accelerate curing.

如图l所示,只通过将ZnO加到开炼机上(在第二混合中于ll(TC或更低温度)而不是在班伯里密炼机中,硫化时间(T90)就减少了40秒。ZnO 浓度的进一步降低(即从5phF2.9wt。/。降低)直至ZnO浓度接近与硬脂酸的化学计量比,也导致了硫化进行更快。随着ZnO的量进一步减少到低于化学计量点,由于促进剂激活不充分,硫化变慢。 Shown in Figure l, just by the ZnO was added on the mill (in the second mixing at ll (TC or lower), rather than in a Banbury mixer, vulcanization time (T90) is reduced by 40 further reducing the concentration of the second .ZnO (i.e. from 5phF2.9wt. /. decreased) until the ZnO concentration close to the stoichiometric ratio of stearic acid, also resulted in a faster cure. With the amount of ZnO is further reduced to less than Chemistry metering point, the activation is not sufficient because the accelerator, curing slow.

实施例3 Example 3

以下数据表明ZnO浓度变化怎样对物理性能产生戏剧性作用。 The following data show how the concentration of ZnO changes have a dramatic effect on the physical properties. 变化百分比最大的是抗磨损性(测定为立方厘米的材料损失),数值越低越好。 The biggest change is the percentage of abrasion resistance (measured as cubic centimeters of material loss), the lower the better value.

16在表1的组合物中,使用了以下橡胶添加剂: 16 compositions in Table 1, using the following rubber additives:

<table>table see original document page 17</column></row> <table>对于实施例3-1 ,除了硫化剂包以外的所有成分在班伯里密炼机中混合。 <Table> table see original document page 17 </ column> </ row> <table> For Example 3-1, all of the ingredients except the curing agent package mixed in a Banbury mixer. 对于实施例3-2~3-8,除了硫化剂包和ZnO-80以外的所有成分在130。 For Example 3-2 to 3-8, all of the ingredients except the vulcanizing agent package and ZnO-80 than in the 130. C的温度下于班伯里密炼机中混合。 C temperature mixed in a Banbury mixer. 再将硫化组分的组分和ZnO在约70。 Then the vulcanizable constituent components and ZnO at about 70. C的温度加入到开炼机中。 Temperature C is added to an open mill. 然后该组合物中15(TC硫化T90+l分钟的总时间。 Then the composition 15 (TC total cure time T90 + l minute.

对于表1中的结果,硬度为肖氏A,300。 For the results in Table 1, a hardness of Shore A, 300. /。 /. 模量和拉伸强度单位为kg/cm2, 拉伸比为百分比,撕裂单位为kg/cm,磨损(Akron阿克隆)为立方厘米损失/3000转,密度单位为g/cm3。 Modulus and tensile strength in units of kg / cm2, draw ratio as a percentage, tear unit kg / cm, and wear (Akron Akron) loss of cc / 3000 rpm, the density in units of g / cm3. 表1 Table 1

3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-13-23-33-4 3-53-63-73-8

phr ZnO 6,25 6.25 2.5 0.625 0.313 0.156 0.0625 0 phr ZnO 6,25 6.25 2.5 0.625 0.313 0.156 0.0625 0

wt% ZnO 2.94 2.94 1.2 0.3 0.15 0.08 0.03 0 wt% ZnO 2.94 2.94 1.2 0.3 0.15 0.08 0.03 0

硬度 68.5 70.5 72.5 71.5 74 66 68.5 66 Hardness 68.5 70.5 72.5 71.5 7466 68.5 66

300%模量 48 55 57 54 52 29 37 21 300% modulus 4,855,575,452,293,721

拉伸强度 137 138 137 145 178 125 119 90 Tensile strength 137 138 137 14517812511990

%拉伸比 616 560 549 608 716 818 775 834 616 560 549% elongation than 608,716,818,775,834

撕裂 52 58 60 64 71 80 78 58 Tear 5,258,606,471,807,858

磨损 0.249 0.231 0.167 0.103 0.08 0.141 0.215 0.349 Wear 0.249 0.231 0.167 0.103 0.141 0.215 0.349 0.08

密度 1.155 1,141 1.13 1.145 1.129 1.142 1,119 1.1 Density 1.13 1.145 1.129 1.142 1.155 1,141 1,119 1.1

18 18

Classifications
International ClassificationC08K5/09, C08L21/00, C08J3/24
Cooperative ClassificationC08J2321/00, C08K5/098, C08K5/09, C08K3/22, C08J3/241, C08K9/10
European ClassificationC08J3/24B, C08K9/10, C08K5/098, C08K5/09, C08K3/22
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