CN1070529C - 含有腐蚀抑制剂的烷基醚胺传输机用润滑剂 - Google Patents

含有腐蚀抑制剂的烷基醚胺传输机用润滑剂 Download PDF

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CN1070529C
CN1070529C CN97190620A CN97190620A CN1070529C CN 1070529 C CN1070529 C CN 1070529C CN 97190620 A CN97190620 A CN 97190620A CN 97190620 A CN97190620 A CN 97190620A CN 1070529 C CN1070529 C CN 1070529C
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acid
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weight
lubricant
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CN1194665A (zh
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K·L·普森海
M·E·比希
B·E·施密特
C·S·希克斯
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Ecolab Inc
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Abstract

本发明涉及润滑剂浓缩物组合物，应用溶液以及使用方法。该润滑剂含有结构式为R1-O-R2-NH2、R1-O-R2-NH-R3-NH2的胺类化合物及其混合物，其中R1是直链C6-C18烷基，R2是直链或支链C1-C8烷基，R3是直链的C1-C8烷基；以及腐蚀抑制剂。该润滑剂组合物优选含有多元羧酸作为腐蚀抑制剂。该组合物还可以含有水溶助长剂、稳定剂、以及使组合物在稀释和使用时产生消毒作用的表面活性剂。本发明还包括稀释该浓缩物得到的润滑剂应用溶液。

Description

含有腐蚀抑制剂的烷基醚胺传输机用润滑剂
本发明涉及以胺为基础的润滑剂组合物及其使用方法。更具体地讲，本发明涉及含有腐蚀抑制剂的抗菌传输机用润滑剂，所述润滑剂是基于含有直链烷基醚胺和/或二胺化合物的组合物。
饮料和其它食料通常是在机械化的传输机系统上进行加工和包装的。需要对这些传输系统进行润滑以减少包装品和传输机承重表面之间的摩擦。
抗菌剂用于传送食品物料的传输系统。在传输机上溅出的饮料和其它食料常常会导致细菌、酵母和霉菌生长，并可能产生烂泥状物和污物，这些物质又会损害传输机性能，同时也可能会损害产品纯度和外观。抗菌剂特别适用于降低传送食料的传输系统中这种烂泥状物的形成。
以前，通常用于传输系统承重表面的润滑剂含有脂肪酸皂作为活性润滑成份，采用抗菌剂控制微生物生长。然而，由于脂肪酸皂润滑剂会与水硬性离子发生反应，从而会牺牲润滑剂的总体性能。
近年来，人们已开发了不合脂肪酸的润滑剂组合物，以避免或消除采用含硬离子的水稀释润滑剂所碰到的沉淀问题。例如，U.S.专利4,839,067(Jansen)公开了一种保持链型传输带的方法，该方法用包含润滑量的中性化C12-18脂肪伯胺的润滑组合物处理传送带。但是，如Jansen指出的那样，由于水中通常含有阴离子如SO4 -2、PO4 -3和CO3 -2等杂质，当存在所述的这些阴离子时，脂肪酸伯胺会发生沉淀现象，所形成的沉淀会堵塞喷嘴并使传输系统表面污染，特别是在存在水硬度时，脂肪酸皂更是如此。
U.S.专利5,182,035(Schmidt等)公开了一种脂族醚二胺乙酸酯，它可与用于增加物理稳定性的醇性水溶助长剂一起用于润滑剂组合物中。
U.S.专利5,062,978(Weber等)也公开了一种基于脂族烷基醚胺的含水润滑剂组合物，该组合物可用于传送带操作中，特别是用于传输瓶子。
EP专利0,533,522 A1(Schapira)公开了包含支链饱和/或不饱和C6-C21烷基醚胺和二胺的润滑剂组合物。该润滑剂组合物可用于传输机操作，且该组合物还可包含一种表面活性剂以及醇溶剂。
随着在某些食品的生产过程中会发生黑色沉淀物形成现象，附加的沉淀问题也发生了。这种黑色沉淀物大部分是在生产过程中产生的，特别是在充气饮料如啤酒的加工及罐装过程中产生的。以前，这种沉淀物的形成甚至会导致改变所给定的应用过程。据信，所述的沉淀物是来自金属损耗、金属腐蚀上的金属，以及某些食品污物(存在于加工环境中)与所用润滑剂的相互作用。
因此，人们仍然希望找到一种用于所有包装材料和传输机表面中的抗菌润滑剂，这种润滑剂应能改善金属润滑性及腐蚀抑制性。
一方面，本发明提供了一种润滑剂浓缩组合物，该组合物含有有效润滑量的下式胺化合物及其混合物，
        R1-O-R2-NH2
      R1-O-R2-NH-R3-NH2
其中R1可以是直链饱和或不饱和C6-C18,R2可以是直链或支链的C1-C8烷基，R3可以是直链或支链的C1-C8烷基。该浓缩物含有腐蚀抑制剂，并且还可以含有表面活性剂，表面活性剂的用量足以使浓缩物在稀释和使用时具有洗涤作用，浓缩物中还含有有效量的酸以稳定胺。浓缩物中还可以选择性地含有增加产物稳定性的水溶助长剂。
本发明还提供了一种通过稀释上述浓缩物而形成的润滑剂应用溶液，胺类化合物的浓度约为10ppm-10000ppm。
本发明还提供了一种润滑传输系统的方法，该方法包括使用本发明的润滑剂浓缩组合物的应用溶液。
本发明的润滑剂中包含直链烷基醚胺和腐蚀抑制剂。直链烷基醚胺润滑剂可促进在离子与饮料污物存在时水系统的润滑性和溶解性，并使溶液保持在较宽的pH值范围内。本发明的润滑剂可保持稳定，基本上不会与系统中的游离阴离子及食料中的污物反应。进而，为保持浓缩物的物理稳定性，本发明的直链烷基醚胺无需使用醇型溶剂。本发明的组合物还同时能够降低金属腐蚀，改善金属润滑性。本发明还提供了对于聚对苯二酸乙二醇酯(PET)、玻璃及金属表面优良的滑动性。此外，本发明的润滑剂对非食料接触表面也具有抗菌效能，在5分钟内，细菌可降低99.9％。
本发明涉及润滑剂浓缩组合物以及应用溶液。该浓缩物可以是固体或液体。本发明的组合物包括直链烷基醚胺化合物，该化合物可以提供润滑作用，具有抗菌特性，还能降低各种沉淀物的形成，所述沉淀物是在应用环境中经常会出现的。本发明的组合物包括腐蚀抑制剂、洗涤剂、酸，以及选择性成份水溶助长剂，及其它成份。本发明也包括使用所述组合物的方法。
                        A．烷基醚胺化合物
本发明的润滑剂含有胺类化合物。该胺类化合物的功能是增强组合物的润滑性、抗菌性，减少或消除各种因水稀释引起的沉淀物的形成和/或减少或消除应用表面上的污染物。
本发明的胺类化合物可以含有任意种胺类物质。该胺类化合物优选为下式的胺化合物及其混合物，
        R1-O-R2-NH2           (1)
        R1-O-R2-NH-R3-NH2    (2)
其中R1可以是直链饱和或不饱和C6-C18烷基，R2可以是直链或支链的C1-C8烷基，R3可以是直链或支链的C1-C8烷基。
更优选R1是直链的C12-C16烷基，R2是C2-C6直链或支链烷基，R3是直链或支链的C2-C6烷基。
优选的本发明组合物含有式(1)和(2)的直链烷基醚胺化合物，其中R1是C12-C16，R2和R3是C3。
当使用的胺类化合物是式(1)和/或(2)的胺时，R1是直链C12-C16烷基或是C10-C12和C14-C16直链烷基的混合物。
总的来说，用于本发明组合物的直链烷基醚胺混合物在稀释时可以提供低的使用浓度并增强其润滑性。浓缩物中胺类化合物的量通常为约0.1％(重量)至90％(重量)，优选为约0.25％(重量)至75％(重量)，更优选为约0.5％(重量)至50％(重量)。
可以从Tomah Products Incorporated购买到商品名为PA-19、PA-1618、PA-1816、DA-1618、DA-18、DA19和DA-1816等的胺类物质。
浓缩物的应用稀释液优选能在应用时产生消毒或清洁效果。因此，本发明组合物中的活性胺类化合物的浓度为约10ppm-10000ppm，优选约20ppm-7500ppm，首选约40ppm-5000ppm。
                        B．腐蚀抑制剂
本发明的浓缩组合物和应用稀释组合物还可含有腐蚀抑制剂。有用的腐蚀抑制剂包括多元羧酸例如短链二元羧酸、三元羧酸，以及磷酸酯以及它们的混合物。有用的磷酸酯包括烷基磷酸酯、单烷基芳基磷酸酯、二烷基芳基磷酸酯、三烷基芳基磷酸酯、以及它们的混合物，例如可以从Witco化学公司购买到的Emphos PS 236。
更具体地讲，酯化磷酸或磷酸酯对应于通式(3)：
R1-O-[-CH2CH2-O]n-PO3X2    (3)其中R1是直链或支链的饱和C8-C12伯烷基，X是氢和/或碱金属，n是约3-10的整数。
酯化的烷基芳基磷酸或磷酸对应于通式(4)：
R2R3-C6H3-O-[-CH2CH2-O]n-PO3X2    (4)其中R2是直链或支链的饱和C8-C10伯烷基，R3是氢或直链或支链的饱和C8或C10伯烷基，X是氢和/或碱金属，n是约4-10的整数。
其它有用的腐蚀抑制剂包括三唑，例如苯并三唑、甲苯基三唑和巯基苯并三唑，以及膦酸酯如1-羟基亚乙基-1,1-二膦酸和表面活性剂如油酸二乙醇酰胺和椰子基两性羟丙基磺酸钠(sodium cocoamphohydroxy propylsulfonate)等。
根据本发明，优选的腐蚀抑制剂是多元羧酸如二元羧酸。优选的酸包括己二酸、戊二酸、琥珀酸及其混合物。首先己二酸、戊二酸、琥珀酸的混合物，该物质是由BASF以SOKALANDCS商品名出售的原料。
在浓缩物中，组合物中腐蚀抑制剂的浓度从0.05％-25％，优选从0.1％-20％。在一个优选方案中，浓缩物含有约1％(重量)-6％(重量)的腐蚀抑制剂并含有 SokalanDCS二酸混合物。
                          C．中和剂
通常，还可使用中和剂以在浓缩物和应用溶液中提供约5和10之间的有效pH。
酸的例子包括有机和无机酸。可用于本发明组合物的无机酸包括盐酸、磷酸、氢氟酸、硫酸、硝酸、氢溴酸、氨基磺酸及其它。
可用于本发明的有机酸包括乙酸、羟基乙酸、葡糖酸、乳酸、苯甲酸、C8-C20饱和及不饱和脂肪酸如油酸，以及它们的混合物。
酸的浓度应足以并能有效地溶解和稳定本发明的各种组分以及浓缩组合物和应用稀释组合物。
                        D．表面活性剂
本发明的润滑剂组合物可以选择性地、但优选还另外含有表面活性剂。表面活性剂的功能是增强消毒和润滑作用。可在本发明中用作表面活性剂的化合物包括，非离子表面活性剂、两性表面活性剂、阴离子表面活性剂、阳离子表面活性剂以及其它化合物。
阴离子表面活性剂通常是含有疏水的烃基部分和带负电荷的亲水部分的化合物。一般购买到的产品中带有羧酸盐、磺酸盐、硫酸盐或磷酸盐基团作为带负电荷的亲水部分。特别适用于本发明润滑剂组合物的阴离子表面活性剂是磷酸酯。总的来说，任何可购买到的阴离子表面活性剂均可用于本发明的润滑剂组合物。
非离子表面活性剂通常是基本不带电荷的疏水化合物，由于在分子中存在氧而表现出亲水倾向。非离子表面活性剂包括多种聚合物，其中包括但不限于，乙氧基化的烷基酚、乙氧基化的脂肪醇、乙氧基化的胺、乙氧基化的醚胺、羧酸酯、羧酸酰胺、以及聚氧化烯嵌段共聚物。
特别适用于本发明润滑剂组合物的非离子表面活性剂是通式为R10O((CH2)mO)n的烷氧基化的(优选乙氧基化的)醇，其中R10是含有约8到约24个碳原子的脂族基团，m是1至约5的整数，n是1至约40的数，它表示分子上环氧乙烷的平均数量。
阳离子表面活性剂也可用于本发明并具有抗菌功能。代表性的例子包括季铵盐酸盐表面活性剂如正烷基(C12-18)二甲基苄基氯化铵、正烷基(C14-18)二甲基苄基氯化铵、正十四烷基二甲基苄基氯化铵一水合物、正烷基(C12-14)二甲基1-萘甲基氯化铵。
两性表面活性剂，即同时含有酸性和碱性亲水基团的表面活性剂也可以用于本发明。两性表面活性剂可以含有阴离子或阳离子表面活性剂中常见的阴离子或阳离子基团，此外还可含有羟基或其它可以改善表面活性剂特性的亲水基团。所述两性表面活性剂包括三甲铵内酯类(甜菜碱)表面活性剂、磺基甜菜碱表面活性剂、两性咪唑啉衍生物及其它。
在浓缩物中，表面活性剂的的浓度通常为约0.01％(重量)至50％(重量)，优选从0.1％(重量)至20％(重量)。更优选表面活性剂的浓度从约1至10％(重量)并且表面活性剂是非离子的醇乙氧基化物如Shell Chemical的Neodol 25-7。
                        E．水溶助长剂
本发明的润滑剂组合物还可以选择性地含有有效量的水溶助长剂，以控制粘度并保持浓缩物的低温稳定性。
多种可混溶的水溶助长剂可用于润滑剂组合物，包括单官能基和多官能基的醇以及醇醚化合物。其中，最有用的化合物包括烷基醇如乙醇、异丙醇等。多元醇包括甘油、己二醇、聚乙二醇、丙二醇、山梨醇等。
优选的水溶助长剂为双官能的醇类，如烷基醇。业已发现，已二醇是一种显著提高浓缩物和其应用溶液稳定效能的化合物。通常，浓缩物中水溶助长剂的浓度为约0.1-40％(重量)，优选约1-25％(重量)。在本发明优选的实施方案中，浓缩物中水溶助长剂的浓度为约3-10％(重量)，并且它可包含己二醇。
                          实施例
下述实施例用于说明本发明的各种性质、特征及实施方案。但它们并不构成对本发明保护范围的限定。
          实施例1：摩擦试验和磨耗试验
如表1所述摩擦试验和磨耗试验用润滑剂浓缩物这样制备：将软水与水溶助长剂和酸混合，加热至120°F，搅拌下加入其余的原料。这些浓缩物的应用溶液是用1000份自来水(5-6颗粒硬度)与2.5份浓缩物混合而形成的0.25％溶液。
                            表1用于摩擦试验和磨耗试验制备的配方
    原料     1A     1B     1C     1D
    ％(重量)
C12/C14烷氧基丙基-1,3-二氨基丙烷N-油基-1,3-二氨基丙烷N-椰子基-1,3-二氨基丙烷戊二酸/己二酸/琥珀酸1乙酸磷酸酯2水溶助长剂非离子表面活性剂软化水     9.04.07.07.073.0     8.018.210.010.053.8     8.01.810.010.070.2 4.04.01.810.010.070.2
1购自BASF公司商品名Sokalan DCS的二酸混合物。2购自Witco Chemical的Emphos PS 236磷酸酯。
配有低碳钢v-块(1137)的法列克司摩擦与磨耗机(Faville-LeVallyCorp.,Model:Pin and V-Block)用于测定润滑剂应用溶液的破坏点(failpoint)。以100ml/min的速度，使溶液在v-块(block)和销(pin)上循环。期间，在Falex上施加50psi的压力5分钟，然后在5分钟的间隔内增加压力至200、250、300psi等，直至大体上不稳定的扭矩读数或突然的压力损失表明销和/或v-块磨坏，因而损坏。在1分钟间隔时间内，将压力重新设置至所要求值，结果，产生最小的压力损失。记录每分钟时通过啮合调节测量的扭矩、压力和磨损。
                           表2摩擦和磨耗破坏点测定
配方 胺类型     酸     pH 破坏点(psi) 消耗时间(分:秒)
    1A11B11C1D 直链醚二胺直链醚二胺直链醚二胺烷基二胺 二酸混合物磷酸酯乙酸乙酸  6.87.37.67.6  330200190200     20:006:455:005:30
1配方代表本发明的教导。
直链胺与二酸混合物的中和导致低碳钢和不锈钢间摩擦和磨耗减少。在50psi下平衡5分钟后，采用乙酸中和的商购和实验用润滑剂均很快损坏。
          实施例2：腐蚀抑制
按照表3制备润滑剂浓缩物：使软化水与特定酸及水溶助长剂混合，加热至120°F，混合下再加入其它原料。
                           表3用于低碳钢腐蚀试验制备的配方
    原料     2A     2B     2C     2D     2E
    ％(重量)
十四烷氧基丙基-1,3-二氨基丙烷C12/C15烷氧基丙基-1,3-二氨基丙烷戊二酸/己二酸/琥珀酸1乙酸乙醇酸磷酸酯2水溶助长剂非离子表面活性剂腐蚀添加剂3软化水     6.04.03.010.077.0     6.02.23.010.078.8     6.01.19.13.010.070.8 6.04.05.010.05.070.0 6.04.05.010.075.0
1购自BASF公司商品名Solkalan DCS的二酸混合物。2购自Witco的Emphos PS 236磷酸酯。3如下提到的腐蚀添加剂。
为了测试低碳钢对包含各种中和剂的润滑剂浓缩物的腐蚀抑制性，用1000份包含5-6颗粒硬度的自来水制备0.25％的应用溶液，用稀KOH调节pH值至9。将预清洁的1×3英尺的冷轧制钢(1018#)面板浸入应用溶液中，如此使应用溶液盖住取样管。在24小时后，目视评价面板的腐蚀和应用溶液澄清情况，并按照如下描述进行评定。所有试验进行两次。样品以下列单位为基础进行评判。
等级 溶液外观     面板腐蚀
    1 溶液无变化     未观察到腐蚀的迹象
    2 溶液轻微变色 轻微腐蚀，1-5％面板表面面积显示发生腐蚀
    3 溶液变色 中等腐蚀，6-10％面板表面面积显示发生腐蚀
    4 溶液为黑琥珀色 重度腐蚀，11-90％面板表面面积显示发生腐蚀
                           表4低碳钢对配方2A、2B和2C的腐蚀试验结果(0.25％溶液，调节至pH9,24小时后评级)
配方     组成     2次读数的腐蚀计数
溶液澄清 面板外观
 2A2B2C 戊二酸/己二酸/琥珀酸乙酸磷酸酯/乙酸     2,23,3--     2,13,22,3
为了测试低碳钢对包含各种腐蚀剂抑制剂的润滑剂浓缩物的腐蚀抑制性，由配方2D和2E制备0.5％的应用溶液。为了进行该评价试验，用5份浓缩物和1000份包含5-6颗粒硬度的自来水制备制备应用溶液，用稀KOH调节pH值至8。将预清洁的1×3英尺的冷轧制钢(1018#)面板浸入应用溶液中，如此使应用溶液盖住取样管。在48小时后，目视评价面板的腐蚀和应用溶液澄清情况，并对其定级。所有试验进行两次。
                            表5
               低碳钢对配方2D和2E的腐蚀试验结果
              (0.50％溶液，调节至pH8,48小时后评级)
配方     腐蚀添加剂     2次读数的腐蚀计数
溶液澄清 面板外观
 2D2D2D2D2D2D2E     己二酸D-异抗坏血酸乳酸苹果酸油酸二乙醇酰胺1椰子基两性羟丙基磺酸钠2无     1,12,23,32,23,33,33,3     2,21,21,11,21,11,12,2
1由Rhone Poulenc出售的商品名WRS-166的Alkamide。2由Rhone Poulenc出售的商品名CS的Miranol。
各种腐蚀抑制剂特别是二元酸以直链烷基醚胺制剂提供了对低碳钢的腐蚀防护。进而，很明显，酸性产品可具有双重作用，即作腐蚀抑制剂，又作胺中和剂，这有益于生产成本及效益。
如上说明、实施例及数据对本发明的组合物的生产和应用提供了的完整的说明。由于在不背离本发明的精神实质的基础上可完成本发明的多种实施方案，因此，本发明提出了如下的权利要求。

Claims (20)

1．润滑剂浓缩物组合物，含有：
a．0.1-90％重量的一种或多种胺化合物，所述胺化合物分别具有选自下式结构
        R1-O-R2-NH2
    R1-O-R2-NH-R3-NH2
及其混合物，
其中R1是直链饱和或不饱和C6-C18烷基，R2是直链或支链C1-C8亚烷基，R3是直链或支链的C1-C8亚烷基；
b．0.05-25％重量的腐蚀抑制剂，所述腐蚀抑制剂包括二羧酸、三羧酸或其混合物；和
c．0.01-50％重量的能有效地给组合物在稀释和使用时提供洗涤作用量的表面活性剂，表面活性剂选自阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性表面活性剂，及其混合物，其中，浓缩物的pH大于7。
2．稀释权利要求1的浓缩物所得的润滑剂，其中润滑剂含有10-10000ppm的至少一种胺类化合物和主要部分的稀释剂。
3．权利要求1或2的组合物，其中所述胺类化合物是单胺化合物并且R1是直链C12-C16烷基，R2是C2-C6亚烷基。
4．权利要求1或2的组合物，其中所述胺类化合物是单胺化合物，R1选自C10-C12烷基；C14-C16烷基，及其混合物，R2是C2-C6亚烷基。
5．权利要求1或2的组合物，其中所述胺类化合物是二胺化合物，R1是C12-C16烷基，R2是C2-C6亚烷基，R3是C2-C6亚烷基。
6．权利要求1或2的组合物，其中所述胺类化合物是二胺化合物，R1选自C10-C12烷基；C14-C16烷基，及其混合物，R2是C2-C6亚烷基，R3是C2-C6亚烷基。
7．前述任一权利要求的组合物，还另外含有水溶助长剂。
8．权利要求7的组合物，其中所述水溶助长剂选自二元醇、醇、二醇醚、以及它们的混合物。
9．权利要求7或8的组合物，其中所述水溶助长剂包括己二醇，其浓度为0.1％重量至40％重量。
10．权利要求1的组合物，其中所述腐蚀抑制剂包括二元羧酸，其浓度为0.05％重量至25％重量。
11．权利要求10的组合物，其中所述二元羧酸选自己二酸、戊二酸、琥珀酸以及它们的混合物。
12．权利要求1的组合物，其中所述表面活性剂包括非离子表面活性剂。
13．权利要求12的组合物，其中所述非离子表面活性剂具有约1至40摩尔的乙氧基化。
14．权利要求1或2的组合物，其中所述组合物是固体。
15．权利要求1或2的组合物，其中所述组合物是液体。
16．权利要求1的组合物，还另外含有中和剂。
17．权利要求16的组合物，其中所述中和剂包括酸，所述酸选自乙酸、羟基乙酸、葡糖酸、乳酸、苯甲酸、以及它们的混合物。
18．权利要求1或2的组合物，其中所述组合物具有消毒水平的抗菌效果。
19．使用前述任一权利要求的组合物润滑传输机系统的方法，所述方法包括如下步骤：
a．配制含有0.1％重量至90％重量所述胺类化合物的润滑剂浓缩组合物；
b．用稀释剂稀释浓缩组合物以形成应用溶液；以及
c．将所述润滑剂组合物的应用溶液涂抹于待应用表面。
20．权利要求19的方法，其中所述润滑剂应用溶液可与聚对苯二甲乙二醇酯混溶。
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US5723418A (en) 1998-03-03
TW409144B (en) 2000-10-21
AU703374B2 (en) 1999-03-25
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CN1194665A (zh) 1998-09-30
JP3128138B2 (ja) 2001-01-29
BR9702268A (pt) 1999-07-20
PL324797A1 (en) 1998-06-22
CA2224966A1 (en) 1997-12-04
CA2224966C (en) 2001-09-18
ZA972431B (en) 1997-12-29
ATE201044T1 (de) 2001-05-15
DE69704757D1 (de) 2001-06-13
EP0847436B1 (en) 2001-05-09
AR007144A1 (es) 1999-10-13
WO1997045509A1 (en) 1997-12-04
EP0847436A1 (en) 1998-06-17
JPH10511140A (ja) 1998-10-27
MX9800882A (es) 1998-04-30
NZ329858A (en) 1999-04-29
DE69704757T2 (de) 2001-09-20
AU2213797A (en) 1998-01-05

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