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CN1099409A - 无氢放出的硅氧烷基润滑剂组合物 - Google Patents

无氢放出的硅氧烷基润滑剂组合物 Download PDF

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Publication number
CN1099409A
CN1099409A CN94107976A CN94107976A CN1099409A CN 1099409 A CN1099409 A CN 1099409A CN 94107976 A CN94107976 A CN 94107976A CN 94107976 A CN94107976 A CN 94107976A CN 1099409 A CN1099409 A CN 1099409A
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CN
China
Prior art keywords
polydimethylsiloxane
nonactive
lubricant compositions
weight
active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN94107976A
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English (en)
Inventor
A·M·克罗
D·M·弗雷德曼
J·A·罗德林兹
J·J·法乃理
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience Inc USA
Original Assignee
Rhone Poulenc Specialty Chemicals Co
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Publication of CN1099409A publication Critical patent/CN1099409A/zh
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Abstract

本发明公开了一种硅氧烷基润滑剂组合物，该组 合物含有非活性和活性聚二甲基硅氧烷的混合物、交 联剂和足够量的制备乳液用的表面活性剂以及水。 该组合物不含甲基氢硅烷、二甲基氢硅烷和/或聚甲 基氢硅氧烷，因此，在贮存或使用期间没有氢气释 出。

Description

本发明涉及硅氧烷基润滑剂组合物，具体涉及一种可在作为车胎制造工序的步骤中用来涂敷硫化车胎气囊的组合物。
在制造车辆的橡胶气胎时，车胎的成形是通过在未硫化的车胎胎身内，将一个橡胶袋囊或硫化气囊充气，迫使车胎贴紧模具的表面而完成的。通常，在车胎完全硫化之前、气囊处于膨胀状态的期间，气囊的外表面和未硫化车胎的内表面之间有明显的相对运动。同样，气囊与硫化后的车胎之间也有明显的相对运动，在车胎已成形和硫化后，该气囊被放气而从车胎内表面剥落，为了减小气囊和车胎内表面之间的摩擦，在成形过程中，当未硫化的车胎和气囊彼此处于相对运动时，需要提供最佳的气囊滑移。
美国专利Re.32，318中叙述了一种预定用来涂敷在气囊表面上的硫化车胎气囊的润滑剂。该润滑剂包括（A）25℃时具有粘度约为12-28兆厘沲的约20-40份（以重量计）聚二甲基硅氧烷，（B）至少一种约35-70份（以重量计）的选自下列的硅烷：（ⅰ）25℃时具有粘度约为20-40厘沲的甲基氢硅烷，（ⅱ）25℃时具有粘度约为80-120厘沲的二甲基氢硅烷和（ⅲ）甲基三甲氧基硅烷，（C）任选的约3-2份（以重量计）有机酸的金属盐，（D）约10-25份（以重量计）一种或多种表面活性剂和（E）约500-1500份（以重量计）水，备作制备乳液或分散体之用。该专利指明，在上述的润滑剂中，（A）成分优选的是羟基封端的聚二甲基硅氧烷，优选甲基氢硅烷和二甲基氢硅烷的混合物作为成分（B）。
虽然美国专利Re.32，318中含有甲基氢硅烷的润滑剂对其预定的目的是有效的，但是已观察到在贮存和/或用于硫化车胎作业的过程中，由于甲基氢硅烷的分解，释放出有潜在危险的氢气。
已发现，不用甲基氢硅烷、二甲基氢硅烷和/或聚甲基氢硅氧烷，而使用非活性和活性的聚二甲基硅氧烷以及少量交联剂的混合物，可以得到一种特别适合于用作车胎气囊脱涂层的润滑剂组合物，这种组合物在贮存和/或使用期间没有氢放出，并可在硫化过程中，在接触表面之间具有有效而耐久的润滑/脱模性能。
因此，本发明提供了一种不含甲基氢硅烷、二甲基氢硅烷和/或聚甲基氢硅氧烷的没有氢放出的润滑剂组合物，该组合物包括：
（a）至少一种25℃时具有粘度约为50-30兆厘沲的非活性聚二甲基硅氧烷;
（b）至少一种25℃时具有粘度约为15-5兆厘沲的活性聚二甲基硅氧烷;
（c）至少一种交联剂;
（d）至少一种表面活性剂;和
（e）水，
以存在量约为非活性聚二甲基硅氧烷（a）和活性聚二甲基硅氧烷（b）量之和的20-95%（以重量计）的非活性聚二甲基硅氧烷（a）、以存在量约为非活性聚二甲基硅氧烷（a）和活性聚二甲基硅氧烷（b）量之和的5-80%（以重量计）的活性聚二甲基硅氧烷（b）、存在量约为活性聚二甲基硅氧烷（b）的0.01-5%（以重量计）的交联剂（c）和存在量足以备作乳液的表面活性剂（d）和水（e）。
在上述配方中，为了提供具有有效的润滑/脱模性能和耐久性能的润滑剂组合物，非活性聚二甲基硅氧烷（a）和活性聚二甲基硅氧烷（b）两者都必须存在，耐久性能可以理解为单独使用润滑剂组合物时，通过几次车胎的生产循环，例如在5次这样的循环范围内均具有提供有效润滑/脱模的性能，而不需要重新涂敷润滑剂组合物。
非活性聚二甲基硅氧烷（a）具有粘度约为50-30兆厘沲，且最好由能增强润滑剂组合物耐久性的高粘度非活性聚二甲基硅氧烷（ⅰ）和能提高其润滑性的低和/或中等粘度的非活性聚二甲基硅氧烷（ⅱ）的混合物组成。当非活性聚二甲基硅氧烷（a）由这类混合物组成时，高粘度的硅氧烷（ⅰ）通常在25℃时具有的粘度至少为100，000厘沲，优选约10-25兆厘沲，而低至中等粘度的硅氧烷（ⅱ）通常在25℃时具有粘度小于100，000厘沲，例如低粘度的硅氧烷在25℃时的粘度约为50-200厘沲，中等粘度的硅氧烷在25℃时的粘度约为10，000-50，000厘沲。当然，低和中等粘度的硅氧烷混合物可以用作非活性聚二甲基硅氧烷组分（ⅱ）。高粘度的聚二甲基硅氧烷组分（ⅰ）与低至中等粘度的聚二甲基硅氧烷组分（ⅱ）的重量比可在约1∶10-约10∶1之间变化，优选约1∶5-约5∶1。非活性聚二甲基硅氧烷（a）在润滑剂组合物中的量约占非活性聚二甲基硅氧烷（a）和活性聚二甲基硅氧烷（b）总重的20-95%（以重量计），优选40-75%（以重量计）。
具体的用于本发明的非活性高粘度聚二甲基硅氧烷（ⅰ）包括Rhone-Poulenc Inc.的Rhodorsil Emulsion M-405，一种硅氧烷乳液，25℃时其硅氧烷组分具有的公称粘度大于100，000厘沲;General Electric Co.的Silicone  2068，一种硅氧烷乳液，25℃时其硅氧烷组分具有的公称粘度大于100，000厘沲;Union Carbide Corp.的L45-300，000，25℃时其所具有的公称粘度为300，000厘沲和Hüls America Inc.的PS050，25℃时其所具有的公称粘度为2.5兆厘沲。
具体的用于本发明的非活性低至中等粘度聚二甲基硅氧烷（ⅱ）包括Rhone-Poulenc Inc.的Rhodorsil Fluid H47V100，25℃时其所具有的公称粘度为100厘沲;Hüls America Inc.的PS041和PS047，25℃时其所具有的公称粘度分别为100和30，000厘沲;Dow-Corning Corp.Dow 200，25℃时其所具有的公称粘度为200厘沲和Union Carbide Corp.的L45-100，25℃时其所具有的公称粘度为100厘沲。
活性聚二甲基硅氧烷组分（b）可以从任一种25℃时具有粘度约为15-5兆厘沲，优选50-10，000厘沲的羟基和/或烷氧基封端的聚二甲基硅氧烷中选择。具体的用于本发明结果较好的活性聚二甲基硅氧烷组分（b）包括Union Carbide Corp.羟基封端的聚二甲基硅氧烷L-9000（25℃时，1，000厘沲）、Hüls America Inc.的PS-340、PS-343.8和PS-349.5（25℃时，按顺序为15-35、3500和800，000-1.2兆厘沲）、Dow-Corning Corp.的DCQ13563、DCQ2-7132和DC-109（25℃时，按顺序为100、1800和5，000厘沲）以及上述这些和类似的活性聚二甲基硅氧烷的组合。通常，活性聚二甲基硅氧烷（b）的量可以约为非活性聚二甲基硅氧烷（a）和活性聚二甲基硅氧烷（b）重量之和的5-80%，优选约25-60%。
交联剂组分（c）可以从已知的和通常用于交联活性聚二甲基硅氧烷组分（b）的化合物中选择，例如美国专利No.4，889，770中叙述的那些化合物，其内容合并在此作为参考。已知的和常用的交联剂包括有机三烷氧基硅烷类、有机三酰氧基硅烷类、有机三肟硅烷类和硅酸四烷基酯类。烷基三烷氧基硅烷类优选用于本发明，其中，甲基三甲氧基硅烷是特别优选的。
在将润滑剂组合物涂敷到硫化车胎气囊（或其它的表面）上时，交联剂组分（c）与活性聚二甲基硅氧烷组分（b）的封端羟基和/或烷氧基基团反应，使后者交联而产生粘附薄膜。该交联反应只需少量的交联剂，例如约为活性聚二甲基硅氧烷（b）重量的0.01-5%，优选约0.02-2%，并可在添加或不添加催化剂的情况下产生反应（虽然在某些情况下该反应可以被涂敷润滑剂组合物到硫化车胎气囊上的组分催化）。
迄今在制造硫化车胎气囊粘合剂组合物中所采用的任一种表面活性剂也可以用于本发明。适用于本发明粘合剂组合物的表面活性剂的实例是阴离子、阳离子和非离子的表面活性剂，例如烷基或芳基聚乙二醇醚或烷基苯基例如聚氧乙烯烷基苯基、聚氧乙烯六硬脂酸脱水山梨醇酯、聚氧乙烯异癸醚、每分子含3-15个环氧乙烷单元的聚乙二醇的三甲基壬醚、具有皂化值为102-108和羟基数为25-35的聚氧乙烯油酸脱水山梨醇酯、聚氧乙烯十六烷基硬脂烷基醚、等。
只要能获得乳液，表面活性剂和水的使用量当然可以有相当的变化。稳定的乳液可以含组分（a）、（b）和（c）之和约2-50%（以重量计），优选约5-40%（以重量计），约0.5-5%（以重量计），优选约1-4%（以重量计）表面活性剂（d）和约50-95%（以重量计），优选约60-90%（以重量计）水。采用已知的和常规的方法和设备可容易地制备水基乳液。
本发明的润滑剂组合物也可以含一种或多种任选的组分例如聚合成膜剂，如丙烯酸类的、用于交联反应的催化剂、另外的润滑剂和滑移剂（slip agent）、吸气剂（air bleed agent）、消泡剂、增稠剂、填料、稳定剂、防腐剂，如生物杀伤剂、等，这些组分的用量范围较宽，例如为组合物重量的0.2%（以重量计）多至50%（以重量计）。
该润滑剂组合物可以采取喷涂、刷、抹、涂敷或其它任一种能均匀涂敷涂料在硫化车胎气囊上的方法施涂。然后，该组合物可以在室温下至少放置10小时，或最好采取在车胎的装置中车胎胎身固化和硫化的过程中所达到的温度下，在气囊上熟化。通常，随着在约为或少于20分钟之内发生硫化，上述温度可达到约175°-350°F。一旦发生硫化，通过反复的膨胀-收缩程序，该润滑剂组合物连续地粘附在气囊的表面上，这样即可单独施用润滑剂，而为多次车胎的生产循环提供有效的润滑/脱模性能。
下列实施例将对根据本发明的硫化车胎气囊的润滑剂组合物进行说明。
实施例1
本实施例说明本发明的已添加一些任选成分的润滑剂组合物。
组分  重量百分率
低粘度非活性聚二甲基硅氧烷17.48
聚氧乙烯十六烷基硬脂烷基醚的混合物21.19
羟基封端的聚二甲基硅氧烷34.76
甲基三甲氧基硅烷  0.05
蒸馏水    59.50
消泡剂40.10
生物杀伤剂50.10
黄原胶    0.46
聚氧乙烯化的异癸醇60.92
羟基乙酸    0.14
高粘度非活性聚二甲基硅氧烷721.00
丙烯酸胶乳成膜树脂84.30
总计    100.00
125℃时具有公称粘度为100厘沲的Rhodorsil Fluid H47V100（Rhone-Poulenc）。
22.20%（以重量计）的Ethal CSA-3和1.30%（以重量计）的Ethal CSA-17（Ethox Chemicals），两者均为表面活性剂。
325℃时具有公称粘度为85厘沲的二羟基封端的聚二甲基硅氧烷Fluid QI-3563（Dow-Corning）
4Foamex AD100（Rhǒne-Poulenc），一种聚二甲基硅氧烷消泡剂。
5Proxel GXL（Zeneca），一种防腐剂。
6Emulphogene DA-530（Rhǒne-Poulenc），一种表面活性剂。
7Emulsion M-405（Rhǒne-Poulenc），一种表面活性剂。
8WRL-01197（Rhǒne-Poulenc），一种丙烯酸类胶乳。
上述润滑剂组合物通过添加低粘度非活性聚二甲基硅氧烷和聚氧乙烯十六烷基硬脂烷基醚，在一起加热至130°F，并在中速下搅拌20分钟而制备。然后，添加羟基封端的聚二甲基硅氧烷和甲基三甲氧基硅烷，继而再搅拌15分钟。此后，将占总量11.7%（以重量计）的水加热至125°F，并添加到该混合物中，接着再混合20分钟。然后，将该混合物冷却至100°F，在2500psi下搅匀两次，将占总水量22.8%（以重量计）的水添加到混合物中，接着在中速下混合30分钟。将其余的水装入另一个容器中，添加生物杀伤剂和消泡剂，并将其搅拌10分钟。将黄原胶和聚氧乙烯化的异癸醇装入另一个容器中，搅拌10分钟，然后，将其添加到装有水、生物杀伤剂和消泡剂的容器中。接着再搅拌20分钟，添加羟基乙酸，然后，添加高粘度非活性聚二甲基硅氧烷，最后，搅匀混合物。在中速下将该组合的配料搅拌15分钟后，添加丙烯酸胶乳，最后，再将该配料搅拌30分钟。
实施例2
基本上采用实施例1中叙述的方法制备下列润滑剂组合物。
组分  重量百分率
实施例1的低粘度非活性聚二甲基硅氧烷  6.60
实施例1的聚氧乙烯十六烷基硬脂烷基醚混合物  1.05
实施例1的羟基封端的聚二甲基硅氧烷  4.20
实施例1的甲基三甲氧基硅烷  0.04
蒸馏水  63.01
实施例1的消泡剂  0.10
实施例1的生物杀伤剂  0.10
聚氧乙烯十六烷基硬脂烷基醚混合物91.52
羟基乙酸  0.08
高粘度非活性聚二甲基硅氧烷1019.00
实施例1的丙烯酸胶乳成膜树脂  4.30
总计  100.00
9Ethal CSA-3和Ethal CSA-17，分别为0.96%（以重量计）和0.56%（以重量计）。
10GE Silicone2068（General Electric Company），一种聚二甲基硅氧烷。

Claims (15)

1、一种不含甲基氢硅烷、二甲基氢硅烷和/或聚甲基氢硅氧烷的无氢放出的硅氧烷基润滑剂组合物，该组合物包括：
(a)至少一种25℃时具有粘度约为50-30兆厘沲的非活性聚二甲基硅氧烷；
(b)至少一种25℃时具有粘度约为15-5兆厘沲的活性聚二甲基硅氧烷；
(c)至少一种交联剂；
(d)至少一种表面活性剂；和
(e)水，
以存在量约为非活性聚二甲基硅氧烷(a)和活性聚二甲基硅氧烷(b)量之和的20-95%(以重量计)的非活性聚二甲基硅氧烷(a)、以存在量约为非活性聚二甲基硅氧烷(a)和活性聚二甲基硅氧烷(b)量之和的5-80%(以重量计)的活性聚二甲基硅氧烷(b)、存在量约为活性聚二甲基硅氧烷(b)的0.01-5%(以重量计)的交联剂(c)和存在量足以备作乳液的表面活性剂(d)和水(e)。
2、根据权利要求1的润滑剂组合物，其中非活性聚二甲基硅氧烷（a）含有至少一种在25℃时具有粘度至少为100，000厘沲的非活性聚二甲基硅氧烷（ⅰ）和至少一种在25℃时具有的粘度小于100，000厘沲的非活性聚二甲基硅氧烷（ⅱ）。
3、根据权利要求2的润滑剂组合物，其中非活性聚二甲基硅氧烷（ⅰ）在25℃时具有粘度约为10-25兆厘沲和非活性聚二甲基硅氧烷（ⅱ）是选自在25℃时具有的粘度约为50-200厘沲的非活性聚二甲基硅氧烷、在25℃时具有粘度约为10，000-50，000厘沲的非活性聚二甲基硅氧烷及其它们的组合。
4、根据权利要求2的润滑剂组合物，其中非活性聚二甲基硅氧烷（ⅰ）与非活性聚二甲基硅氧烷（ⅱ）的重量比约为1∶10-约10∶1。
5、根据权利要求2的润滑剂组合物，其中非活性聚二甲基硅氧烷（ⅰ）与非活性聚二甲基硅氧烷（ⅱ）的重量比约为1∶5-约5∶1。
6、根据权利要求3的润滑剂组合物，其中非活性聚二甲基硅氧烷（ⅰ）与非活性聚二甲基硅氧烷（ⅱ）的重量比约为1∶10-约10∶1。
7、根据权利要求3的润滑剂组合物，其中非活性聚二甲基硅氧烷（ⅰ）与非活性聚二甲基硅氧烷（ⅱ）的重量比约为1∶5-约5∶1。
8、根据权利要求1的润滑剂组合物，其中交联剂（C）25℃时具有的粘度约为50-10，000厘沲。
9、根据权利要求1的润滑剂组合物，其中交联剂（C）选自有机三烷氧基硅烷、有机三酰氧基硅烷、硅酸四烷基酯及它们的组合。
10、根据权利要求1的润滑剂组合物，其中交联剂（C）是甲基三甲氧基硅烷。
11、根据权利要求1的润滑剂组合物，其中非活性聚二甲基硅氧烷（a）在润滑剂组合物中的量约占非活性聚二甲基硅氧烷（a）和活性聚二甲基硅氧烷（b）总重的40-75%（以重量计），活性聚二甲基硅氧烷（b）的量约为非活性聚二甲基硅氧烷（a）和活性聚二甲基硅氧烷（b）总重的25-60%（以重量计）和交联剂（c）的量约为活性聚二甲基硅氧烷（b）重量的0.02-2%（以重量计）。
12、根据权利要求1的润滑剂组合物，含聚合物类成膜剂。
13、根据权利要求12的润滑剂组合物，其中该聚合物类成膜剂是丙烯酸类成膜剂。
14、根据权利要求1的润滑剂组合物，含有至少一种附加成分，它选自交联反应用的催化剂、另外的润滑剂、吸气剂（airbleed agent）、消泡剂、增稠剂、填料、稳定剂、防腐剂及其组合。
15、根据权利要求14的润滑剂组合物，含聚合物类成膜剂。
CN94107976A 1993-07-23 1994-07-20 无氢放出的硅氧烷基润滑剂组合物 Pending CN1099409A (zh)

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