CN117624954A - 胺官能化有机硅烷/脂肪酸组合体系作为施用于铝及其合金的污染/腐蚀抑制剂 - Google Patents
胺官能化有机硅烷/脂肪酸组合体系作为施用于铝及其合金的污染/腐蚀抑制剂 Download PDFInfo
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- CN117624954A CN117624954A CN202311608955.0A CN202311608955A CN117624954A CN 117624954 A CN117624954 A CN 117624954A CN 202311608955 A CN202311608955 A CN 202311608955A CN 117624954 A CN117624954 A CN 117624954A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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Abstract
根据本发明,用于处理含铝表面的组合物包含至少一种胺官能化的有机硅烷和/或其低聚物和/或聚合物与至少一种脂肪酸的反应产物,其中至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物的氨基与至少一种脂肪酸的摩尔为1.2:1‑1:2,并且其中至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物通过至少一个羧酸/胺盐键和/或至少一个酰胺键与至少一种脂肪酸连接。
Description
本申请是申请号为201680061510.7、申请日为2016年10月19日、发明名称为“胺官能化有机硅烷/脂肪酸组合体系作为施用于铝及其合金的污染/腐蚀抑制剂”的专利申请的分案申请。
发明领域
本发明涉及一种用于处理含铝表面的组合物,该组合物对铝污染/腐蚀提供改进的抑制,本发明还涉及一种用于制备所述组合物的方法、一种用所述组合物处理含铝表面的方法以及所述组合物作为金属加工液和/或防锈剂的用途。
发明背景
术语“污染”描述了一种腐蚀,其主要用于包括铝在内的有色金属。关于金属加工液(MWF)体系,铝污染来自4以下的低pH或8.5以上的高pH。铝及其合金上的污染/腐蚀对其表面特性具有不利影响,并且通常结果是最终产品的价值受损。因此,显著的技术努力和研究活动已经致力于消除或至少最小化金属表面上的这种不利损害。
根据这种风险,例如现代MWF技术利用各种磷酸盐、磺酸盐或硅酸盐,其在配制剂中主要用作腐蚀抑制剂。然而,含磷或硫的化合物具有在含水体系中累积过量营养物造成微生物增殖的固有缺点。尽管硅酸盐不会引起微生物生长,但尤其是小烃基硅酸盐由于其倾向于在含水体系中形成不溶性三维网络而具有胶凝/沉淀问题。
因此,开发无微生物生长和胶凝问题的新抑制剂化学一直是建立MWF平台技术的极大关注点。例如,Noble等(US 7,674,754 B2)建议将具有包含硅和/或磷的侧链的聚合硼物质用于水基金属加工液。
如下文将解释的,本发明涉及一种用于处理含铝表面的组合物,该组合物在无微生物增殖和胶凝问题存在下提供改进的铝污染/腐蚀抑制。优选地,所述组合物在润滑性方面,更优选就浓缩物稳定性、硬水稳定性和/或消泡性而言应表现出改进的性质。
发明简述
根据本发明,用于处理含铝表面的组合物包含至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物与至少一种脂肪酸的反应产物,其中至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物的氨基与至少一种脂肪酸的重量比为1.2:1-1:2,并且其中至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物通过至少一个羧酸/胺盐键和/或至少一个酰胺键与至少一种脂肪酸连接。
用本发明组合物处理的含铝表面显示出在金属表面和液相之间的界面中的阻挡层,从而防止腐蚀性化学物质接近金属表面。此时,源于胺官能化有机硅烷的所述反应产物的极性首基吸附在金属表面上,而源于脂肪酸的非极性尾基朝向排斥水接近的液相设置。
优选实施方案的详述
以下段落描述了本发明组合物的优选实施方案。
待处理的含铝表面优选由铝或含有其他元素如Cu、Si、Mg和/或Zn的铝合金,更优选由铸造铝合金Al319和Al356-T6中的一种或锻造铝合金Al6061-T6和Al7075中的一种组成。就本发明而言,“含铝表面”也可以由涂覆有转化层或钝化层的铝或铝合金组成。
在下文中,术语“胺官能化有机硅烷”表示胺官能化的有机硅烷和/或其低聚物和/或聚合物,其可以源于胺官能化有机硅烷的(部分)水解和随后水解产物(即相应的有机硅烷醇)的(部分)缩合。
至少一种胺官能化有机硅烷可以是单一的有机硅烷或者两种或更多种不同的有机硅烷的混合物。
至少一种胺官能化有机硅烷具有至少一个带有至少一个氨基的烃基结构部分。作为氨基,伯-NH2是优选的。有机硅烷优选具有一个带有一个氨基的烃基结构部分。然而,它也可以具有两个或更多个带有一个或两个或更多个氨基的烃基结构部分。
作为烃基结构部分,优选烷基,更优选具有三个或更多个碳原子的烷基。根据一个实施方案,可使用在水解方面更稳定的至少一种具有两个或更多个烷基和/或支化烷基的胺官能化有机硅烷。然而,该类有机硅烷与经处理的含铝表面的粘附性较低。
除了至少一个烃基结构部分外,至少一种胺官能化的有机硅烷优选具有一个或多个烃氧基结构部分,其中烃基和烃氧基结构部分的总和优选为4,即在有机硅烷的中心硅原子上没有其他结构部分。作为烃氧基结构部分,优选烷氧基。
然而,至少一种胺官能化有机硅烷还可以具有一个或多个-OH基团而非一个或多个烃氧基。
尤其优选至少一种胺官能化有机硅烷是氨基烷基三烷氧基硅烷,最优选3-氨基丙基三乙氧基硅烷。
优选地,组合物包含至少一种胺官能化有机硅烷的低聚物和/或聚合物。该类低聚物和/或聚合物的使用导致组合物的稳定性增强。
至少一种脂肪酸可以是单一脂肪酸或者两种或更多种不同脂肪酸的混合物。
至少一种脂肪酸优选具有至少8个,更优选至少12个,更优选至少16个,尤其优选至少20个碳原子。长链脂肪酸导致组合物的润滑性增加,因此是优选的。
此外,长烃尾部的疏水性通过防止过量水解和随后的缩合而抑制组合物内不期望的凝胶形成。非极性烃链排斥水,从而减少水与胺官能化有机硅烷接触的机会。
为了将组合物用作金属加工液,至少一种脂肪酸优选具有8-22个碳原子。
根据一个实施方案,至少一种脂肪酸具有支化的烃尾部,优选具有的至少一个侧链具有至少2个碳原子,更优选具有的至少一个侧链具有至少4个碳原子。如果含铝表面用具有大的极性首基(例如3-三乙氧基甲硅烷基丙基氨基-)的胺官能化有机硅烷和/或其低聚物和/或聚合物处理,则该类支化烃尾部是有利的。
由于在C=C双键和铝之间存在吸引力,所以至少一种脂肪酸对含铝表面的粘附性可以通过将至少一个C=C双键引入至少一种脂肪酸中而增强。
因此,至少一种脂肪酸优选具有显现出至少一个C=C双键,更优选至少一个呈顺式构型的C=C双键的烃尾部,因为预期后者尤其会增强对含铝表面的吸附。最优选至少一种脂肪酸是芥酸。
通过使用具有不同烃尾部(碳原子数、疏水性/亲水性、非支化/支化、饱和/不饱和)的至少两种脂肪酸的混合物作为至少一种脂肪酸,可以对预期应用调整本发明组合物的性能以及所得阻挡层的性能。
在经处理的含铝表面上的阻挡层的厚度和密度以及吸附取决于所施用的至少一种脂肪酸的烃尾部的长度和结构以及所用至少一种胺官能化有机硅烷的结构。支化尾部导致薄膜不太致密且不太厚,但表现出强吸附性,而长的线性尾部以一定吸附强度为代价导致膜具有较高的密度和厚度。源于有机硅烷的大的首基导致薄膜具有较低的密度和厚度但具有强吸附性,而小的首基导致薄膜更致密且更厚,伴随着一些吸附强度的损失。
在一个优选实施方案中,至少5摩尔%,优选约至少10摩尔%,更优选约至少15摩尔%(借助FT-IR光谱法通过1640cm-1处的酰胺键和1560cm-1处的羧酸/胺盐键的峰强度比来检测)的至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物与至少一种脂肪酸之间的键是酰胺键。由于它们的共价性质,酰胺键比相应的盐形式更耐水解。
在组合物中,至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物的氨基与至少一种脂肪酸的摩尔比优选为1.1:1-1:1.5,更优选1.0:1-1:1.2。
根据本发明用于处理含铝表面的组合物可以通过用合适的溶剂(优选去离子水),优选以1:10-1:20(相当于5-10重量%的浓缩物)的因数稀释合适的浓缩物,并且如果需要,则随后用合适的pH调节剂调节pH值而制备。
在该浓缩物中,至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物优选以0.1-4重量%,更优选0.2-2.0重量%,尤其优选0.6-1重量%的浓度包含,并且至少一种脂肪酸优选以0.1-4重量%,更优选0.3-3重量%,尤其优选1.0-1.4重量%的浓度包含。
相应地,在通过稀释所述浓缩物可获得的用于处理含铝表面的组合物中,至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物优选以0.005-0.4重量%,更优选0.01-0.2重量%,尤其优选0.03-0.1重量%的浓度包含,并且至少一种脂肪酸优选以0.005-0.4重量%,更优选0.015-0.3重量%,尤其优选0.05-0.14重量%的浓度包含。
优选地,上述浓缩物额外包含30-60重量%的环烷油,5-25重量%的去离子水,2-6重量%的2-氨基-2-甲基丙醇,2-6重量%的三乙醇胺,0.2-2重量%的硼酸,3-7重量%的十二烷二酸与三乙醇胺的约1:1摩尔比混合物,1-3重量%的3-氨基-4-辛醇,1-3重量%的羧酸的聚氧化乙烯,0.2-2重量%的二羧基脂肪酸,2-6重量%的聚合蓖麻油酸,2-6重量%的聚合酯,2-6重量%的芥酸,2-6重量%的作为非离子表面活性剂的乙氧基化脂肪醇,0.2-2重量%的3-碘-2-丙炔基丁基氨基甲酸酯,0.02-0.2重量%的消泡剂混合物和0.5-2.5重量%的油醇(条件是所有组分总计达100重量%)。
因此,在这种情况下,用于处理含铝表面的组合物额外地包含0.1-0.6重量%的2-氨基-2-甲基丙醇,0.1-0.6重量%的三乙醇胺,0.01-0.2重量%的硼酸,0.15-0.7重量%的十二烷二酸与三乙醇胺的约1:1摩尔比混合物,0.05-0.3重量%的3-氨基-4-辛醇,0.05-0.3重量%的羧酸的聚氧化乙烯,0.01-0.2重量%的二羧基脂肪酸,0.1-0.6重量%的聚合蓖麻油酸,0.1-0.6重量%的聚合酯,0.1-0.6重量%的作为非离子表面活性剂的乙氧基化脂肪醇,0.01-0.2重量%的3-碘-2-丙炔基丁基氨基甲酸酯,0.001-0.02重量%的消泡剂混合物和0.025-0.25重量%的油醇(条件是所有组分总计达100重量%)。
根据一个优选的实施方案,组合物是含水组合物,这意指超过50重量%的溶剂是水,例如当浓缩物主要用作为溶剂的水稀释时。组合物还可以包含合成油和/或矿物油作为溶剂,例如环烷油。由于额外使用该类油,组合物具有将良好润滑性与高冷却能力相结合的优点。
组合物的pH值优选在8.5-10.5的范围内,更优选在9.0-10.0的范围内,尤其优选在9.2-9.7的范围内。
本发明还包括一种用于制备本发明组合物的方法。在该方法中,
i)将至少一种胺官能化有机硅烷(涉及氨基)和至少一种脂肪酸以1.2:1-1:2的摩尔比在净反应中或在基本无水介质中混合,
ii)在搅拌下,使混合物经受至少室温的温度至少15分钟,使得至少5摩尔%(通过FT-IR光谱检测)的至少一种胺官能化有机硅烷与至少一种脂肪酸之间的链接是酰胺键,和
iii)然后将反应产物与其他组分混合,使得获得用于处理含铝表面的组合物或该组合物的浓缩物。
通过进行步骤ii),剩余的至少一种有机硅烷和/或相应有机硅烷结构部分的烷氧基基团至少部分地由酰胺键形成时产生的水水解,并且然后由此水解产生的硅烷醇基团至少部分缩合。
步骤ii)基于典型的放热酸/碱反应。离子与酰胺链接的比例以及组合物中低聚和聚合氨基官能化有机硅烷物质的量取决于放热程度。
根据一个实施方案,步骤ii)在室温下进行。在此过程中,步骤ii)中的反应时间优选超过30分钟,尤其优选超过40分钟。这样,在反应产物中没有得到可检测的低聚/聚合物质,因此后者表现出低等级的粘度。
反应温度越高,酰胺化等级越高。因此,根据另一个实施方案,步骤ii)在室温以上,优选40℃以上,尤其优选60℃以上的温度下进行。升高的温度导致增加量的低聚/聚合物质,并因此导致具有更高粘度等级的反应产物。
增强的酰胺化和水解均在大于约70℃的温度下进行。酰胺链接是有利的,但过量的水解是不利的。因此,有利的是不施用大于约90℃的反应温度,以防止太多的水解。
因此,根据一个尤其优选的实施方案,步骤ii)在约70℃和约90℃之间的温度下进行。在此过程中,步骤ii)中的反应时间优选大于4小时,更优选大于6小时,尤其优选约8小时。
因此,为了制备一致的产品,维持每批料的放热恒定是重要的。为了克服反应期间的粘度增加,建议强力的搅拌器装置。
此外,本发明还包括一种用于处理含铝表面的方法,其中使含铝表面与本发明组合物接触,然后任选冲洗。
本发明组合物优选作为基本上无污染的金属加工液和/或防锈剂用于含铝表面。
本发明应该通过以下实施例来指出,而非由此限制本发明的范围。
实施例
对比例1(C1):
通过混合15.6g去离子水,4.0g 2-氨基-2-甲基-丙醇,4.0g三乙醇胺,1.0g硼酸,5.0g的十二烷二酸与三乙醇胺的1:1摩尔比混合物,1.8g的3-氨基-4-辛醇,2.0g羧酸的聚氧化乙烯,1.1g二羧基脂肪酸,4.0g聚合蓖麻油酸,4.0g聚合酯,4.0g芥酸,4.0g作为非离子表面活性剂的乙氧基化脂肪醇,47.0g环烷油,1.0g的3-碘-2-丙炔基丁基氨基甲酸酯,0.1g消泡剂混合物和1.5g油醇而制备第一对比浓缩物(C1;金属加工液)。
对比例2(C2):
通过将0.8g的四乙氧基硅烷和1.7g的OcenolTM(>80重量%油醇和<20重量%鲸蜡醇;BASF,德国)分别滴入97.5g根据C1的浓缩物并在室温下搅拌所得混合物40分钟而获得第二对比浓缩物(C2)。
对比例3(C3):
通过混合0.8g的四乙氧基硅烷和1.7g的OcenolTM(>80重量%油醇和<20重量%鲸蜡醇;BASF,德国)并在75℃的温度下搅拌所得混合物8小时而获得第三对比浓缩物(C3)。冷却至室温后,将反应产物与97.5g根据C1的浓缩物混合,并将所得混合物在室温下搅拌40分钟。
本发明实施例1(E1):
通过i)混合0.8g的3-氨基丙基三乙氧基硅烷和1.2g的芥酸,ii)使所得混合物经受室温40分钟,和iii)将2.0g的反应产物(本发明腐蚀/污染抑制剂)滴入98g根据C1的浓缩物中,而制备本发明浓缩物(E1)。
在步骤ii)之后且在步骤iii)之前,通过FT-IR分析反应产物。根据1640cm-1处的酰胺键与1560cm-1处的羧酸/胺盐键的峰强度比,约10摩尔%的氨基丙基三乙氧基硅烷与芥酸之间的链接是酰胺键。
本发明实施例2(E2):
通过i)混合0.8g的3-氨基丙基三乙氧基硅烷和1.2g的芥酸,ii)使所得混合物经受75℃的温度8小时,和iii)将2.0g的反应产物(本发明腐蚀/污染抑制剂)滴入98g根据C1的浓缩物中,而制备本发明浓缩物(E1)。
在步骤ii)之后且在步骤iii)之前,通过FT-IR分析反应产物。根据1640cm-1处的酰胺键和1560cm-1处的羧酸/胺盐键的峰强度比,约15摩尔%的氨基丙基三乙氧基硅烷与芥酸之间的链接是酰胺键。
浓缩物稳定性测试:
借助TurbiscanTM装置(Formulaction Inc.,Worthington,OH)在50℃下6天内检测上述浓缩物的稳定性。在这五天内的几个时间点得到0-50mm范围内的后向散射(%)曲线。
对于每种浓缩物,下表显示了在0-50mm范围内的底部、中部以及顶部区域中以%(ΔBS%)表示的后向散射的最终值和初始值之间的差。
浓度 | ΔBS%(底部) | ΔBS%(中部) | ΔBS%(顶部) |
C1 | 6.99 | 10.35 | 7.70 |
C2 | 17.07 | 13.71 | 12.73 |
C3 | 10.09 | 10.54 | 11.19 |
E1 | 4.33 | 7.02 | 8.11 |
E2 | 2.15 | 0.08 | 0.39 |
ΔBS%越高,颗粒尺寸增长引起的颗粒沉淀越多,即相应浓缩物的稳定性越低。因此,与C1相比,C2和C3显示降低的浓缩物稳定性,而本发明的E1,尤其是E2,与C1相比表现出增强的稳定性。
相应地,可以肉眼看到在约50℃的温度下1天后浓缩物C2的分离,而在E1的情况下,即使7天后也不出现分离。
硬水稳定性测试:
将5体积份的浓缩物C1或E1加入去离子水中的95体积份的1200ppm乙酸钙,并混合。24小时后,所得组合物C1作为具有轻微分离和轻微小球形成的白色乳液出现,而在所得组合物E1的情况下,存在仅具有非常轻微分离和非常轻微小球形成的白色乳液(通过肉眼测定)。
泡沫测试:
由于泡沫将空气引入金属表面,因此起泡对MWF是不利的。这导致加速的腐蚀并且还阻止在金属表面上形成均匀的摩擦膜而导致低润滑性。
将5体积份的浓缩物C1或E1加入95体积份的去离子水(“DI”)或150ppm去离子水中的乙酸钙(“Ca”)中,并混合。借助Sunbeam搅拌器,将得到的组合物C1和E1在去离子水的情况下搅拌5分钟(泡沫破碎时间:18秒),在150ppm的去离子水中的乙酸钙的情况下搅拌5分钟(泡沫破碎时间:14秒)。这样获得了以下体积的泡沫(以ml计)。
组合物 | DI | Ca |
C1 | 850ml | 800ml |
E1 | 810ml | 750ml |
组合物E1的泡沫量显著低于C1。这可能被认为是E1的明显优势,因为由于不同原因,产生泡沫是不希望的。
微攻丝测试(micro tap test):
将8体积份的浓缩物C1或E1加入92体积份的75ppm去离子水中的乙酸钙中,并混合。将得到的组合物C1和E1分别施加到6061铝测试板上,并通过模拟螺纹攻丝机操作的专用测试装置进行所谓的微攻丝测试。所述装置测量攻丝金属加工所需的扭力:测得的力越低,润滑性越好。相对于使用C1,组合物E1的使用导致好18%的润滑性。
金属相容性测试:
将10体积份的浓缩物C1或E1加入90体积份的DI水中,并混合。将319铝、356-T6铝或6061-T6铝的测试板保持在所得组合物C1和E1中24小时。此后,测试板显示如下。
组合物 | 319铝 | 356-T6铝 | 6061-T6铝 |
C1 | 轻度污染 | 轻度污染 | 非常轻度污染 |
E1 | 无污染 | 无污染 | 无污染 |
总之,在所有测试的铝基材上,与C1相比,本发明的E1抑制剂导致增强的污染抑制。
Claims (17)
1.用于处理含铝表面的组合物,包含至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物与至少一种脂肪酸的反应产物,其特征在于至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物的氨基与至少一种脂肪酸的摩尔比为1.2:1-1:2,至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物通过至少一个羧酸/胺盐键和/或至少一个酰胺键与至少一种脂肪酸连接,并且至少一种脂肪酸具有至少20个碳原子,
其中至少一种脂肪酸具有显现出至少一个呈顺式构型的C=C双键的烃尾部;
且至少5摩尔%,优选至少10摩尔%,更优选至少15摩尔%的至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物与至少一种脂肪酸之间的链接(通过FT-IR光谱检测)是酰胺键,
其特征在于组合物是含水组合物且组合物的pH值在8.5-10.5的范围内。
2.根据权利要求1的组合物,其特征在于至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物是氨基烷基三烷氧基硅烷,优选3-氨基丙基三乙氧基硅烷和/或其低聚物和/或聚合物。
3.根据前述权利要求中任一项的组合物,其特征在于组合物包含至少一种胺官能化有机硅烷的低聚物和/或聚合物。
4.根据前述权利要求中任一项的组合物,其特征在于至少一种脂肪酸具有支化的烃尾部,具有的至少一个侧链具有至少2个碳原子,优选具有的至少一个侧链具有至少4个碳原子。
5.根据权利要求1的组合物,其特征在于至少一种脂肪酸是芥酸。
6.根据前述权利要求中任一项的组合物,其特征在于至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物以0.005-0.4重量%,优选0.01-0.2重量%,更优选0.03-0.1重量%的浓度包含,并且至少一种脂肪酸以0.005-0.4重量%,优选0.015-0.3重量%,更优选0.05-0.14重量%的浓度包含。
7.根据前述权利要求中任一项的组合物,其特征在于至少一种胺官能化有机硅烷和/或其低聚物和/或聚合物的氨基与至少一种脂肪酸的摩尔比为1.1:1-1:1.5,优选1.0:1-1:1.2。
8.根据前述权利要求中任一项的组合物,其特征在于组合物额外包含0.1-0.6重量%的2-氨基-2-甲基丙醇,0.1-0.6重量%的三乙醇胺,0.01-0.2重量%的硼酸,0.15-0.7重量%的十二烷二酸与三乙醇胺的约1:1摩尔比混合物,0.05-0.3重量%的3-氨基-4-辛醇,0.05-0.3重量%的羧酸的聚氧化乙烯,0.01-0.2重量%的二羧基脂肪酸,0.1-0.6重量%的聚合蓖麻油酸,0.1-0.6重量%的聚合酯,0.1-0.6重量%的芥酸,0.1-0.6重量%的作为非离子表面活性剂的乙氧基化脂肪醇,0.01-0.2重量%的3-碘-2-丙炔基丁基氨基甲酸酯,0.001-0.02重量%的消泡剂混合物和0.025-0.25重量%的油醇(条件是所有组分总计达100重量%)。
9.根据前述权利要求中任一项的组合物,其特征在于组合物的pH值在9.0-10.0的范围内,优选在9.2-9.7的范围内。
10.根据前述权利要求中任一项的组合物,其特征在于组合物中超过50重量%的溶剂是水。
11.浓缩物,其特征在于根据前述权利要求中任一项的组合物可通过稀释所述浓缩物并任选调节pH值而获得。
12.用于制备根据前述权利要求中任一项的组合物的方法,其特征在于:
i)将至少一种胺官能化有机硅烷和至少一种具有至少20个碳原子且具有显现出至少一个呈顺式构型的C=C双键的烃尾部的脂肪酸在基本无水的介质中以1.2:1-1:2的摩尔比混合,
ii)在搅拌下,使混合物经受至少室温的温度至少15分钟,使得至少5摩尔%(通过FT-IR光谱法检测)的至少一种胺官能化有机硅烷和至少一种脂肪酸之间的链接是酰胺键,和
iii)然后将反应产物与其他组分合并,使得获得用于处理含铝表面的组合物或该组合物的浓缩物。
13.根据权利要求12的方法,其特征在于步骤ii)在室温下进行大于30分钟,优选大于40分钟。
14.根据权利要求12的方法,其特征在于步骤ii)在约70℃至约90℃之间的温度下进行大于4小时,优选大于6小时,尤其优选约8小时。
15.用于处理含铝表面的方法,其特征在于使含铝表面与根据权利要求1-10中任一项的组合物接触。
16.根据权利要求1-10中任一项的组合物作为基本上无污染的金属加工液的用途。
17.根据权利要求1-10中任一项的组合物作为含铝表面的腐蚀抑制剂的用途。
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US5412011A (en) * | 1993-10-15 | 1995-05-02 | Betz Laboratories, Inc. | Composition and process for coating metals |
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2016
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- 2016-10-19 BR BR112018008001-2A patent/BR112018008001A2/pt not_active Application Discontinuation
- 2016-10-19 CN CN201680061510.7A patent/CN108137952A/zh active Pending
- 2016-10-19 CA CA3001866A patent/CA3001866A1/en active Pending
- 2016-10-19 RU RU2018117682A patent/RU2769064C2/ru active
- 2016-10-19 US US15/297,240 patent/US20170114229A1/en not_active Abandoned
- 2016-10-19 US US15/769,430 patent/US10927266B2/en active Active
- 2016-10-19 WO PCT/US2016/057589 patent/WO2017070140A1/en active Application Filing
- 2016-10-19 EP EP16794462.8A patent/EP3365395A1/en active Pending
- 2016-10-19 MX MX2018004913A patent/MX2018004913A/es unknown
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2021
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RU2769064C2 (ru) | 2022-03-28 |
US10927266B2 (en) | 2021-02-23 |
CN108137952A (zh) | 2018-06-08 |
US20170114229A1 (en) | 2017-04-27 |
MX2018004913A (es) | 2018-08-16 |
RU2018117682A (ru) | 2019-11-21 |
EP3365395A1 (en) | 2018-08-29 |
BR112018008001A2 (pt) | 2018-10-30 |
WO2017070140A1 (en) | 2017-04-27 |
RU2018117682A3 (zh) | 2020-01-30 |
CA3001866A1 (en) | 2017-04-27 |
US20210139715A1 (en) | 2021-05-13 |
US20180305559A1 (en) | 2018-10-25 |
US11535760B2 (en) | 2022-12-27 |
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