CN1377935A - 受阻酚类抗氧剂组合物 - Google Patents

受阻酚类抗氧剂组合物 Download PDF

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CN1377935A
CN1377935A CN02108204A CN02108204A CN1377935A CN 1377935 A CN1377935 A CN 1377935A CN 02108204 A CN02108204 A CN 02108204A CN 02108204 A CN02108204 A CN 02108204A CN 1377935 A CN1377935 A CN 1377935A
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otbp
phenol
tert
dtbp
hinered phenols
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V·J·加托
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Ethyl Corp
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Abstract

通过在催化剂的存在下、在溶剂中,使超纯邻叔丁基苯酚(OTBP)、超纯2,6－二叔丁基苯酚(DTBP)的特定混合物和甲醛发生反应,得到一种受阻叔丁基酚类抗氧剂组合物,该组合物的特征在于具有少量挥发性的不需要的单环叔丁基酚类抗氧剂和大量的非挥发性多环(或亚甲桥)叔丁基酚类抗氧剂。这些抗氧剂进一步的特征在于具有少量2,6－二叔丁基苯酚、少量邻叔丁基苯酚和痕量的2,4,6－三叔丁基苯酚。

Description

受阻酚类抗氧剂组合物
技术领域
本发明涉及含有极少量单环受阻酚的新型受阻酚类抗氧剂组合物、制备所述组合物的方法以及含有所述受阻酚类抗氧剂组合物的润滑剂和燃料。与所含单环受阻酚的量超出本发明范围的受阻酚类组合物相比，本发明的受阻酚类组合物向含有所述受阻酚的燃料和润滑剂组合物提供改进的氧化稳定性。
背景技术
受阻叔丁基酚类抗氧剂被广泛用于润滑剂工业以保护曲轴箱润滑油和工业用油免受氧化。如果要配制低成本的曲轴箱润滑油或工业用油，适当选择不同抗氧剂类型是很关键的。例如已知某种受阻酚类抗氧剂与烷基化二苯胺的混合物在稳定润滑剂方面是极有效的。还已知酚类抗氧剂与二烷基二硫代磷酸锌(ZDDP)有协同作用。其它的例子有将某种受阻酚类抗氧剂与烷基化二苯胺和苯基-α-萘胺的混合物结合使用以稳定工业润滑剂。还有别的例子有将两种不同受阻酚类抗氧剂的混合物与烷基化二苯胺一起使用以稳定曲轴箱润滑油，使其免于氧化，例如EP 0 456 925 B1。
一种更广泛使用的酚类抗氧剂是具有下述通用结构的亚甲桥多环酚类抗氧剂：其中n等于0-3或更大。本领域技术人员非常清楚，对于单独的分子，“n”是整数，而对于氧化剂组合物，“n”可以是分数，代表将组合物作为一个整体时的平均值。这些抗氧剂是通过在烷基化催化剂的存在下，在反应溶剂中，使2，6-二叔丁基苯酚和邻叔丁基苯酚的混合物与甲醛源(例如含水甲醛或低聚甲醛)发生反应制备的。许多这些物质已被商业生产，以商品名为HiTEC4702抗氧剂、HiTEC4727抗氧剂、HiTEC4728抗氧剂、HiTEC4738抗氧剂和HiTEC4782抗氧剂进行销售，所有上述抗氧剂均为弗吉尼亚Ethyl Corporation ofRichmond出品。制备这些抗氧剂时的污染物包括下示单环酚：
Figure A0210820400052
 
Figure A0210820400053
 
Figure A0210820400054
2，6-二叔丁基苯酚           2，4，6-三叔丁基苯酚        邻叔丁基苯酚
    (DTBP)                      (TTBP)                 (OTBP)
OTBP和DTBP是制备多环受阻酚类抗氧剂的原料，它们在生产之后残留在产品中。TTBP是在用于制备多环受阻酚类抗氧剂的OTBP和DTBP中通常作为污染物被发现的物质。这些单环受阻酚可溶于水，比多环受阻酚类抗氧剂更易挥发。多环受阻酚类抗氧剂由于具有更高的分子量，因而具有更低的水溶性和更低的挥发性。
发明内容
已经发现当超纯的邻叔丁基苯酚(OTBP)和超纯的2，6-二叔丁基苯酚(DTBP)的特定混合物在催化剂的存在下、在溶剂中发生反应时，产生含有大量所需多环受阻酚类抗氧剂和少量不需要的单环受阻酚类抗氧剂的混合物。对于本发明的目的来说，“超纯”指含有0-10ppm三叔丁基苯酚污染物的OTBP和DTBP单体。
本发明描述了一种受阻叔丁基酚类抗氧剂组合物，其特征在于具有少量挥发性的不需要的单环叔丁基酚类抗氧剂和大量的非挥发性多环(或亚甲桥)叔丁基酚类抗氧剂。此外，这些抗氧剂具有改进的在油中的溶解度，并且通过在适当的芳族、链烷或环烷操作油中进行混合，可以以液体形式容易地进行处理。这些抗氧剂进一步的特征在于具有少量2，6-二叔丁基苯酚、少量邻叔丁基苯酚和痕量2，4，6-三叔丁基苯酚。少量被定义为在纯净物即未稀释的抗氧剂中的含量低于3.0％重量，而痕量则被定义为在纯净物即未稀释的抗氧剂中的含量低于50ppm。
通过使超纯DTBP、超纯OTBP的特定混合物和甲醛源在催化剂的存在下、在溶剂中发生反应，得到含有少量2，6-二叔丁基苯酚(DTBP)和邻叔丁基苯酚(OTBP)以及痕量2，4，6-三叔丁基苯酚(TTBP)的受阻酚类抗氧剂组合物。
超纯DTBP和超纯OTBP原料含有0-10ppm三叔丁基苯酚(TTBP)。
原料中OTBP和所有酚的比例(OTBP/(OTBP+DTBP))基于重量/重量为0.25-0.35。
可以在OTBP(每个酚环2个活性氢)和2，6-二叔丁基苯酚(每个酚环1个活性氢)中活性氢数目的基础上，使用化学计算当量的甲醛或摩尔过量的甲醛。典型的过量范围为2％重量过量-25％重量过量。在本申请中术语“甲醛”包括甲醛和甲醛的任何来源，例如含水甲醛和低聚甲醛。
反应溶剂与所有酚的比例(反应溶剂/(OTBP+DTBP))为0.45或更大。可以使用任何极性质子溶剂，反应溶剂可以是挥发性有机溶剂和水的混合物。适当的溶剂包括甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇和叔丁醇。优选的溶剂包括乙醇、1-丙醇和2-丙醇。
可以使用任何无机碱作为催化剂。适当的催化剂包括LiOH、NaOH、KOH、CsOH、Mg(OH)2和Ca(OH)2。优选的催化剂包括NaOH和KOH。
反应通常在混合物的回流温度或回流温度附近进行约30分钟-6小时，如果需要可以反应更长时间。但是在反应温度实际上低于或高于回流温度时也都会产生所需的产物。正如本领域技术人员所易于理解的，可以调节在这些温度下的反应时间。
在这些反应条件下生产出含有少量单环酚和痕量TTBP的低聚产物。低聚物由酚类二聚体、三聚体、四聚体和高分子量酚组成。通过被称为低分子量凝胶渗透色谱法(GPC)或尺寸排阻色谱法(SEC)的分析方法分析的这些低聚物的特征在技术文献(Journal ofChromatography A，841(1999)45-54)中是普遍已知的。该报道还进一步定义了术语酚类二聚体、三聚体、四聚体和高分子量即高-Mr，并提供了分析多环受阻酚类抗氧剂二聚体、三聚体、四聚体和高分子量受阻酚试样的步骤。在该出版物中高分子量受阻酚被定义为大于四聚体即n＞2的任何组分。
在这些反应条件下生产出多环受阻酚类反应产物，该产物含有少于10.0％面积的低分子量单环组分，该组分的上述报道的方法所定义的GPC保留时间大于22.5分钟。该产物还包含通过气相色谱法和质谱(GC-MS)测定为小于50ppm的TTBP。这些产物进一步的特征在于具有大于5％面积和小于15％面积的高分子量酚(高-Mr)，所述高分子量酚的上述报道的方法所定义的保留时间小于20.5分钟。
在这些条件下所生产的多环受阻酚类抗氧剂提供了在润滑剂中是有效抗氧剂的组合物，它具有低挥发性、低生物累积性，可以作为油稀释物，如在芳族、环烷或链烷稀释油中为25-60％重量，容易地被处理。
这些抗氧剂在润滑剂和燃料中具有效用。典型的润滑剂包括客车机油、重型柴油机油、机车油、天然气机油(natural gas engine oils)、汽轮机油、防锈防氧化油、滑道油、液压油、自动润滑液、手动润滑液、润滑脂、工业齿轮油、汽车齿轮油。典型的燃料包括喷气式发动机燃料、汽油、燃料油和柴油。
这些产品的重要的优点在于它们具有低挥发性和少量单环受阻酚。低挥发性组分是更为有效的抗氧剂，这是因为它们不会在润滑剂的有效期内由于蒸发而损失。因此它们保留在润滑剂中以保护润滑剂免受热量和氧气即氧化的不良影响。
虽然上面只详细描述了本发明的一些示范性的实施方案，但是本领域技术人员都明白只要实质上不背离本发明的新技术和优点，则在示范性的实施方案中可以进行多种修改。因此，所有这些修改都包括在由随后的权利要求所定义的本发明的范围内。

Claims (5)

1.一种受阻酚类抗氧剂组合物，该组合物包含：
Figure A0210820400021
其中n为0-3或更大；在未稀释的基础上，该组合物含有各自少于3.0％重量的邻叔丁基苯酚和2，6-二叔丁基苯酚；并且在未稀释的基础上，该组合物含有少于50ppm的2，4，6-三叔丁基苯酚。
2.一种制备受阻酚类抗氧剂组合物的方法，该方法包括在催化剂的存在下、在反应溶剂中，使邻叔丁基苯酚(OTBP)、2，6-二叔丁基苯酚(DTBP)和甲醛源发生反应，其中：
i)OTBP和DTBP原料各自含有0-10ppm三叔丁基苯酚(TTBP)；
ii)原料混合物中OTBP和所有酚的比例(OTBP/(OTBP+DTBP))在0.25-0.35范围内；
iii)反应溶剂与所有酚的比例(反应溶剂/(OTBP+DTBP))为0.45或更大。
3.权利要求2的制备受阻酚类抗氧剂组合物的方法，其中所述组合物在未稀释的基础上，含有各自少于3.0％重量的OTBP和DTBP；并且其中所述组合物在未稀释的基础上，含有少于50ppm的2，4，6-三叔丁基苯酚。
4.权利要求2的制备受阻酚类抗氧剂组合物的方法，其中所述甲醛源选自甲醛、含水甲醛和低聚甲醛。
5.一种通过下述方法制备的受阻酚类抗氧剂，所述方法包括在催化剂的存在下、在反应溶剂中，使邻叔丁基苯酚(OTBP)、2，6-二叔丁基苯酚(DTBP)和甲醛源发生反应，其中：
i)OTBP和DTBP原料各自含有0-10ppm三叔丁基苯酚(TTBP)；
ii)原料混合物中OTBP和所有酚的比例(OTBP/(OTBP+DTBP))在0.25-0.35范围内；
iii)反应溶剂与所有酚的比例(反应溶剂/(OTBP+DTBP))为0.45或更大。
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CN101831347A (zh) * 2010-05-28 2010-09-15 大连克林尔化学品科技有限公司 金属板冷塑成型用清洗防锈润滑剂及生产方法
CN104345085A (zh) * 2013-08-01 2015-02-11 中国石油化工股份有限公司 电解液及其用途
CN115975694A (zh) * 2021-10-15 2023-04-18 中国石油化工股份有限公司 一种液压油组合物及其制备方法

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US20060223724A1 (en) * 2005-03-29 2006-10-05 Gatto Vincent J Lubricating oil composition with reduced phosphorus levels
US8383563B2 (en) * 2007-08-10 2013-02-26 Exxonmobil Research And Engineering Company Method for enhancing the oxidation and nitration resistance of natural gas engine oil compositions and such compositions

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CN101831347A (zh) * 2010-05-28 2010-09-15 大连克林尔化学品科技有限公司 金属板冷塑成型用清洗防锈润滑剂及生产方法
CN101831347B (zh) * 2010-05-28 2014-08-06 大连克林尔化学品科技有限公司 金属板冷塑成型用清洗防锈润滑剂及生产方法
CN104345085A (zh) * 2013-08-01 2015-02-11 中国石油化工股份有限公司 电解液及其用途
CN115975694A (zh) * 2021-10-15 2023-04-18 中国石油化工股份有限公司 一种液压油组合物及其制备方法

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