CN1079986A - 含有多羟基脂肪酸酰胺的流体组合物 - Google Patents
含有多羟基脂肪酸酰胺的流体组合物 Download PDFInfo
- Publication number
- CN1079986A CN1079986A CN93104563.0A CN93104563A CN1079986A CN 1079986 A CN1079986 A CN 1079986A CN 93104563 A CN93104563 A CN 93104563A CN 1079986 A CN1079986 A CN 1079986A
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- China
- Prior art keywords
- water
- fatty acid
- acid amide
- polyhydroxy fatty
- viscosity
- 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.)
- Granted
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- -1 carboxylate salt Chemical class 0.000 claims abstract description 16
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- 235000011090 malic acid Nutrition 0.000 claims abstract 2
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Abstract
高浓度多羟基脂肪酸酰胺表面活性剂贮备溶液
的特征在于在贮存中它们有稠化或胶化的不利倾
向。中等程度的加热及包含羧酸盐如羟基丁二酸氢
盐、柠檬酸盐或酒石酸-琥珀酸盐,在甚至30℃左右
的温度保持所述溶液的粘度低于约2,000厘泊。
Description
本发明涉及的是有关制造洗涤剂组合物,特别是洗衣和洗餐具用洗涤剂的改进方法。
制造者可发现,使用各种处理技术在现代洗衣洗涤剂组合物中添加任何数量的清洁性或美感性组分是有益的。例如,可通过干混合或在最终颗粒产物上喷雾来添加一些敏感组分如酶和香料。液体洗涤剂配方可包括各种不同的分批或连续的方法,它们可包括各种溶解、混合、调整PH等步骤。这类程序在洗涤剂工业中已是公知和普通的了,制造洗涤剂组合物的各种分批、连续以及连续/分批混合的方法目前都在应用。
根据制造方法、所制造的洗涤剂组合物的类型和可利用的设备,制造者采用各种组分做为呈流体状的储备溶液是有利的。当配制液体洗涤剂时尤为如此。典型的,流体形清洁性组分包括水或水-乙醇做为流体化介质,在该介质中所需组分可溶解或变成泥浆。
虽然清洁性表面活性剂大部分为水溶性的,但对洗涤剂领域的技术人员公知的是,当以高浓度加入到水中时,各种表面活性剂常形成非常粘的流体,或者甚至形成高粘度糊状团块或胶状物。这类高粘度物质在制造设备中难以操作。当然,避免操作难题的一个简单方法是用基本上干燥的、固态的这类表面活性剂来进行加工,以更稀、更易操作的流体形态来使用它们,或者对它们进行加热以产生流动性。
然而,在制造者希望采用稳定且较高浓度的流体形态的表面活性剂的情况下,一般有利的是对这类流体进行调整使得它们更易于操作,尤其是针对用普通泵设备对它们进行泵送的能力方面。另一方面,向这类含表面活性剂的流体中添加在最终洗涤剂组合物中不能包含的任何组分都是不利的,因为如果这样做在整体制造过程中就需要附加步骤以除去这些不需要的组分。
多羟基脂肪酸酰胺属于表面活性剂中的一类,该表面活性剂在洗涤剂组合物中的使用目前正在进行研究。对于这类表面活性剂的一个问题是,含有它们的浓缩水溶液在贮存时、甚至在升温(35-60℃)情况趋于常常沉淀和/或胶化。再有,这类酰胺表面活性剂的低温贮存有很大的重要性,因为在升温时它们易于降解,通过酰胺键的水解产生胺和脂肪酸。多羟基脂肪酸酰胺在低于35℃贮存这种降解是可忽略的,即每年低于5-10%,但在升温条件下分解变的很显著,在50℃升至每月约10%,在60℃为每月约20-25%。
当然,可采用各种有机溶剂来降低多羟基脂肪酸酰胺表面活性剂浓缩溶液的粘度是可能的。然而,使用溶剂如乙醇、或者甚至是高浓度乙醇/水混合物在商业规模上是成问题的,其原因包括政府规定、潜在易燃性和操作问题等。再有,甚至非易燃性溶剂的过量都可以产生问题,因为如载入最终液体洗涤剂组合物中,它们可将这种最终产物组合物的粘度降至不希望的程度。由此,高浓度有机溶剂的使用对于商业规模洗涤剂制造者来说还只是一种理论上的可能。出于前述的考虑,本发明提供一种制备可稳定贮存、能泵送的流体组合物的方法,该组合物中含有较高的多羟基脂肪酸酰胺表面活性剂。再有,本发明提供这样的流体组合物,所使用的组分或者在最终洗涤剂组合物中是无害的,或者可对所述最终组合物提供所期望的优点。因而,不需要将这类组分除去。
现有技术已公开了多羟基脂肪酸酰胺的制造。下述参考文献是制备方法的示例:1935年10月8日授予Flint等的U.S.专利2,016,962;1934年12月25日授予Piggott的US专利1,985,424;1955年3月8日授予Schwartz的U.S.专利2,703,798;1961年7月25日授予Zech的U.S.专利2,993,887;Hildreth,Biochem.J.,1982,207卷,363-366页;公开于1959年2月18日的Thomas Hedley & Co.Ltd.(现在Procter & Gamble)的英国专利809,060;公开于1988年12月10日的EP-A285,768(见U.S.5,009,814);以及H.Kelkenberg,Tenside Surfactants Detergents 25(1988)8-13。
本文的方法可简易的提供溶液或浆状物,其中方便的含有多达约44%(重量)的多羟基脂肪酸酰胺表面活性剂,并且所述方法可容易的用于将多羟基脂肪酸酰胺的这类溶液或浆状物的粘度由低于约2,000厘泊(CP)降至约1,200CP至约1,600CP的优选范围。
本发明因而包括用于制备本文后面更完全公开类型的多羟基脂肪酸酰胺表面活性剂的稳定、浓缩的、流体化混合物的方法,它包括:
(a)制备所述多羟基脂肪酸酰胺表面活性剂在含水溶剂中的原料混合物,所述溶剂包括水或含有少量有机、特别是带羟基的溶剂的水;
(b)预热所述原料混合物,以提供所述多羟基脂肪酸酰胺在所述含水溶剂的各向同性的溶液;
(c)与(b)步骤并行或在其后,向多羟基脂肪酸酰胺的所述各向同性溶液中添加有效、粘度控制量的羧酸盐官能化物质,由此所述溶液的粘度保持在低于约2,000厘泊的可泵送粘度,甚至当溶液可冷却至约30.6℃的温度。典型的,按前述方式制备的溶液在长达约7周、或更长的期间可保持为稳定,可泵送的液体。
在一优选方式中,可任选在这里采用的少量羟基溶剂包括选自以下物质组成的组中的一员,这些物质是水、甲醇、乙醇、1,2-丙二醇、及它们的混合物。这类溶剂在全部配制好的液体洗涤剂组合物中有良好的相溶性。水及水与1,2-丙二醇的混合物可在这里使用且是典型的溶剂。
这里采用的羧酸盐官能化物质可以是单羧酸盐例如乙酸盐(或者甚至是碳酸盐),但优选为水溶性二羧酸盐,或最优选的,是具有三个或更多羧基的聚羧酸盐脱垢助洗剂,它们可与多羟基脂肪酸酰胺保持在一起被包括在含有多羟基脂肪酸酰胺的全部配制好的洗涤剂组合物中。这类另外还具有助洗剂特性的羧酸盐官能化物质包括、但非仅限于:柠檬酸盐,氧基丁二酸氢盐(oxydisuccinate)、酒石酸盐、酒石酸单琥珀酸盐(tartrate monosuccinate)、酒石酸丁二酸氢盐(tartrate disuccinate)、葡糖酸盐、糖二酸盐、及它们的水溶性盐,特别是钠、钾和烷醇铵盐。可以使用羧酸盐的混合物。也可以使用它们对应的游离酸或部分中和的水溶性盐。优选柠檬酸盐和氧基丁二酸氢盐。取决于具体的多羟基脂肪酸酰胺、所需最终粘度和温度,其用量可变化,一般建议的约2%(wt)的任何前述的羧酸盐助洗剂可在40℃将高达约44%(wt)浓度的椰子烷基N-甲基葡糖酰胺(Coconutalkyl N-methylglucamide)的各向同性溶液的粘度保持在低于约1,700CP,柠檬酸盐可将该粘度保持在约1200CP。稳定性一般在30.6℃可保持至少7周,这时间对于将该溶液用于制造最终洗涤剂组合物之前的运输和/或贮存来说是充裕的。
除非另外指明,这里的所有百分比、比值和比例均以重量计。
以下更详细的对本发明的方法进行限定。
这里所说的“浓缩混合物”是指多羟基脂肪酸酰胺的重量百分比一般在约30%至约44%的范围内,或者甚至高达约55%-60%,如果这样高的浓度是配制者所需要的。
这里所说的“流体化”或“可泵送的”是指粘度低于约2,000CP,优选低于约1,600CP。
“粘度”由Thermosel System用Brookfield Viscometer Model DVII来测量。系统的粘度在贮存过程中于30.6℃进行测量以评价稳定性。
这里所说的“各向同性溶液”是指均一、流态、非双重折射的液体。这可以使用偏振光用视觉来估计,并可以使用显微镜在偏振光下进行确定。
这里所述对多羟基脂肪酸酰胺“加热以提供各向同性溶液”是指,加热所达到的温度为能提供所需各向同性溶液但不产生降解、或重要的是不使多羟基脂肪酸酰胺环化。一般可使用约50℃至约80℃的温度。如果使用的时间短,例如少于约10-15分钟,高于约120℃的温度也是可容许的。
这里所述“有效粘度控制量”的羧酸盐物质是指该用量可使溶液粘度在低于约2,000CP的期望范围内。一般,约1%至约3%的羧酸盐的量足够,虽然某些羧酸盐例如柠檬酸盐比其它的例如葡糖酸盐更有效,所以可通过常规实验来实现对用量的精确调整。如果还需要多羟基脂肪酸酰胺的浓度高达约60%,则羧酸盐物质的量可增至10-15%或更高,以得到1000CP和更低(在35℃)的粘度。
这里所述“少量有机溶剂”是指这类溶剂在水中的量为由它们本身不使通过本发明提供的在所需范围内的粘度降低。
当然,这根据溶剂的不同会有变化。由此,甲醇溶剂的“少量”典型的为约10%或更低;对乙醇,优选约5%或更低;对1,2-丙二醇,为约15%或更低。如果在35℃粘度为1000CP(最大值)的最终浆状物中需要浓度高达约60%的多羟基脂肪酸酰胺时。也可以使用更高的用量,例如10%乙醇,这些“少量”还可以根据多羟基脂肪酸酰胺烷基链长度、在酰胺中的具体糖部分及类似因素而进行变化。
本发明的一个主要优点是它允许多羟基脂肪酸酰胺表面活性剂在较低温度下以浓缩、相稳定的液体形态来贮存。这种相稳定性是很重要的,因为含水多羟基脂肪酸酰胺体系贮存中的主要问题之一就是它们在贮存中趋于沉淀和/或胶化,甚至在升至较高温度(35℃-60℃)。
脂肪链长度的选择也可以影响到这些体系可液化的容易程度。结构的减小由C12移至C12/14类似物使得它可略容易的产生液体并可提供将浓度升至60%范围的潜在途径,尤其是当较短时间的稳定性、如两周、对于配制者来说是可容许的情况下。然而,需加热至ca.75℃以形成初始“液体”态。这一更高的活性可构成一个重要的优点,尤其是对于重垢型液体洗涤剂的应用来说。
在实施本发明时,按照本申请“合成”部分的公开内容制备多羟基脂肪酸酰胺,按照后面“物质处理”部分所述的步骤改性成更易加工的,特别是可泵送的。
合成
这里的生成酰胺的反应可通过以下形成月桂酰N-甲基葡糖酰胺来说明。
其中R2是C11H23烷基。
更一般来说,这里的方法可用于制备下面结构的多羟基脂肪酸酰胺表面活性剂:
其中:R1是H、C1-C4烃基、2-羟基乙基、2-羟基丙基、或它们的混合物,优选C1-C4烷基,更优选C1或C2烷基,最优选C1烷基(即甲基);R2是C5-C31烃基部分,优选直链C7-C19烷基或链烯基,更优选直链C9-C17烷基或链烯基,最优选直链C11-C19烷基或链烯基,或它们的混合物;Z是多羟基烃基部分,它具有一个线性链烃基链,有至少3个羟基直接连接在该链上,或者Z是所述多羟基烷基部分的烷氧基化衍生物(优选乙氧基化或丙氧基化的)。Z优选在还原性胺化反应中自还原糖衍生;更优选Z是glycityl部分。适用的还原糖包括葡萄糖、果糖、麦芽糖、乳糖、半乳糖、甘露糖、木糖。除上面列举的单一糖外,高右旋糖玉米糖浆、高果糖玉米糖浆、和高麦芽糖玉米糖浆也可作为原料应用。这些玉米糖浆可产生用做Z的糖组分。应理解的是这决非要排除其它适用的原料。优选Z选自下述基团组成的组,-CH2-(CHOH)n-CH2OH、-CH(CH2OH)-(CHOH)n-1-CH2OH、-CH2-(CHOH)2(CHOR′)(CHOH)-CH2OH,其中n是3至5间的整数,包括3和5,R′是H或环单一或多一糖类及它们的烷氧基化衍生物。最优选的是glycityls,其中n是4,特别是-CH2-(CHOH)4-CH2OH。
在式(Ⅰ)中,R1可以是例如N-甲基、N-乙基、N-丙基、N-异丙基、N-丁基、N-异丁基、N-2-羟基乙基、或N-2羟基丙基。
R2-CO-N<可以是例如柯卡酰胺(Cocamide)、硬脂酰胺、油酰胺(Oleamide),月桂酰胺、肉豆蔻酰胺、癸酰胺、棕榈酸酰胺、牛脂酰胺(tallowamide)等。
Z可以是1-脱氧葡糖基(glucityl)、2-脱氧果糖基(fructityl)、1-脱氧麦芽糖基(maltityl)、1-脱氧乳糖基(lactityl)、1-脱氧半乳糖基(galactityl)、1-脱氧甘露糖基(mannityl)、1-脱氧麦芽三糖基(maltotriotyl)等。
化学领域的技术人员可理解,使用二-或更高的糖类如麦芽糖来制备这里的多羟基脂肪酸酰胺会导致生成的多羟基脂肪酸酰胺中的线性取代基Z被多羟基环结构“封闭(capped)”。这类物质可全部在本发明中应用,不超出所公开和要求保护的本发明的实质和范围。
以下的反应剂、催化剂和溶剂可方便的在这里使用,列举它们的目的仅是为了示例说明而非限定范围。
反应剂-各种脂肪酯可以在这里使用,包括单一、二和三-酯(即甘油三酯)。甲基酯、乙基酯、及类似物都是很适用的。多羟基胺反应剂包括N-烷基和N-羟基烷基多羟基胺,所述胺带有N-取代基基团如CH3-、C2H5-、C3H7-、HOCH2CH2-、及类似物。(多羟基胺常通过反应顺序制备,其中的一个或多个步骤包括在金属催化剂如镍存在下的氢化。优选在这里使用的多羟基胺是未被所存在的残余量的这类催化剂污染的,虽然可存在百分之几份[例如,10-20ppm])。酯的混合物和多羟基胺混合物反应剂也可以使用。
催化剂-这里所用的催化剂是碱性材料如醇盐(优选的)、氢氧化物(由于可能的水解反应是次优选的)、碳酸盐、及类似物。优选的醇盐催化剂包括碱金属C1-C4醇盐如甲醇钠、乙醇钾及类似物。催化剂可与反应混合物分开制备,或可使用碱金属如钠在现场制得。对于现场制备来说,例如钠金属在甲醇溶剂中,在催化剂制备结束之前优选不存在其它反应剂。催化剂的典型用量是酯反应剂(摩尔百分数)的0.1-10,优选0.5-5,最优选1-3。也可以使用催化剂的混合物。
溶剂-这里的羟基溶剂包括甲醇、乙醇、丙醇、异丙醇、丁醇类、丙三醇、1,2-丙二醇、1,3-丙二醇及类似物。甲醇是优选的醇溶剂,1,2-丙二醇是优选的二醇溶剂。也可以使用溶剂的混合物。
总的反应条件-这里的目的是在制备所需产物时使形成的环化副产物、酯酰胺和发色体的量最少。为了达到这一目的,使用的反应温度低于约135℃,典型的是在约40℃至约100℃的范围内,优选50℃至80℃,特别是在分批方法中是这样,所述分批方法中反应时间常用的为约15-30分钟,甚至长达一小时。在连续方法中略微更高的温度也是可容许的,在该方法中停留时间可更短一些。
实施例1
制备优选的未环化的多羟基脂肪酸酰胺的典型的工业规模反应程序包括:步骤1-由所需糖或糖混合物如葡萄糖浆、高果糖玉米糖浆、及类似物通过生成N-烷基胺与糖的加合物接着在催化剂存在下与氢反应来制备N-烷基多羟基胺衍生物;然后进行步骤2-使前述多羟基胺优选与脂肪酯反应生成酰胺键。可以使用各种现有技术公开的方法来制备在反应程序的步骤2中可采用的各种N-烷基多羟基胺,而以下的方法是简便的且利用了经济的糖浆做为原料。应理解,当使用这类糖浆作原料时为得到最佳效果,制造者应选择颜色相当浅或优选接近无色[“清水般(water-white)]的糖浆。
由从植物衍生的糖浆制备N-烷基多羟基胺
Ⅰ.生成加合物-以下是一标准方法,其中具有Gardner色度小于1的约420g的约55%的葡萄糖溶液(玉米糖浆-约231葡萄糖-约1.28摩尔)与约119g的约50%的含水甲基胺(59.5g甲基胺-1.92摩尔)溶液进行反应。甲基胺(MMA)溶液用N2清洗和保护,并冷却至约10℃或更低。玉米糖浆在约10-20℃的温度下用N2清洗和保护。在如表中所示的反应温度下将玉米糖浆缓慢添加至MMA溶液中。在所标出的以分钟计的大约时间测量Gardner色度。
表1
时间(分钟): 10 30 60 120 180 240
反应温度℃ Gardner色度(近似值)
0 1 1 1 1 1 1
20 1 1 1 1 1 1
30 1 1 2 2 4 5
50 4 6 10 - - -
如从上面数据可看出的,当温度升至高于约30℃和在50℃时,加合物的Gardner色度显著恶化,加合物Gardner色度值小于7的时间仅为约30分钟。对于更长时间的反应,和/或保持时间,温度应低于约20℃。对于颜色良好的还原葡糖胺Gardner色度值应小于约7,优选小于约4。
当一使用较低的温度来生成加合物时,通过使用胺与糖的更高的比值可使达到基本上平衡的加合物浓度所需的时间缩短。对于已提到的胺与糖的1.5∶1的摩尔比值,在约30℃的反应温度约两小时达到平衡。在1.2∶1的摩尔比值,在相同的条件下,所述时间至少为约3小时。为得到良好的颜色,选择胺∶糖比值,反应温度,和反应时间的组合以达到基本上平衡的转化,例如以糖为基计,超过约90%,优选超过约95%,更优选超过约99%,并使加合物的色度小于约7,优选小于约4,更优选小于约1。
在小于约20℃反应温度使用上面的方法及所标出的不同Gardner色度值的玉米糖浆,MMA加合物的色度(在至少约两小时基本达到平衡后)如下表所示。
表2
Gardner色度(近似值)
玉米糖浆 1 1 1 1+ 0 0 0+
加合物 3 4/5 7/8 7/8 1 2 1
如从上面可看出的,起始的糖原料必须是接近无色的以使得加合物持续为可接受的。当糖的Gardner色度值为约1时,加合物有时是可接受的,有时是不可接受的。当Gardner色度值高于1时,所得到的加合物是不可接受的。糖的初始颜色越好,加合物的颜色越佳。
Ⅱ.加氢反应-由上面得到的Gardner色度值为1或更低的加合物按照以下的步骤进行加氢。
在1升高压釜中添加在水中的约539g的加合物和约23.1g的联合催化剂(United Catalyst)G49B Ni催化剂,并在约20℃用200psig的H2清洗两次。将H2压力升至约1400psig和将温度升至约50℃。然后将压力升至约1600psig,并将温度在约50-55℃保持约3小时。在这点上该产物约95%是氢化的。然后将温度升至约85℃保持约30分钟,将反应混合物轻轻倒出,并将催化剂滤出。在通过蒸发除去水和MMA后,产物约95%是N-甲基葡糖胺,一种白色粉末。
在使用约23.1g Raney Ni催化剂并进行如下改动的情况下重复上面的步骤。将催化剂洗涤三次,装有催化剂的反应器用200psig H2清洗2次,并用H2在1600psig对反应器加压两小时,接着释放压力一小时并重新将反应器加压至1600psig。然后将加合物泵入处于200psig和20℃的反应器中,并如上述用200psig H2等清洗反应器。
在各种情况下所得到的产物中超过约95%是N-甲基葡糖胺;具有少于约10ppm的Ni;以葡糖胺为基计;并具有低于约Gardner 2的溶液色度。
粗制N-甲基葡糖胺在约140℃短时间内颜色是稳定的。
对于优良加合物重要的是具有低的糖含量(少于约5%,优选少于约1%)和具有优良的色度(低于约7,优选低于约4 Gardner,更优选低于约1)。
在另一反应中,由约151g在水中的约50%的甲基胺作起始物质来制备加合物,在约10-20℃用N2对该起始物质进行清洗和保护。约330g的约70%的玉米糖浆(接近清水色)在50℃用N2进行脱气,并在低于约20℃的温度将其缓慢添加到甲基胺溶液中。该溶液混合约30分钟得到约95%的加合物,该加合物为很浅的黄色溶液。
在200ml的高压釜中添加190g在水中的加合物和约9g的联合催化剂(United Catalyst)G49B Ni催化剂,并在约20℃下用H2清洗三次。H2压力升至约200psig并将温度升至约50℃。将压力升至250psig并将温度在约50-55℃保持约3小时。产物在这点约95%被氢化的,然后将其温度升至约85℃保持约30分钟,在除去水和蒸发后,该产物约95%是N-甲基葡糖胺,一种白色粉末。
为使在葡糖胺中Ni的含量最小,当H2压力低于约1000psig时使加合物与催化剂间的接触是最小值也是重要的。在这种反应中N-甲基葡糖胺中的镍含量为约100ppm,而在前面的反应中与之相对应的值为少于10ppm。
为直接对比反应温度的影响以下进行与H2的反应。
按照与上面所述步骤相似的下列典型步骤使用200ml高压釜反应器制备加合物并在各种温度下进行加氢反应。
通过将约420g的约55%的葡萄糖(玉米糖浆)溶液(231g葡萄糖;1.28摩尔)(该溶液由使用来自CarGill的99DE玉米糖浆来制造,其色度值低于Gardner 1)与约119g的55%甲基胺(59.5gMMA;1.92摩尔)(来自空气产物)混合来制备用于制造葡糖胺的加合物。
反应步骤如下:
1.将约119g的50%甲基胺溶液添加到用N2清洗过的反应器中,该反应器用N2保护并冷却至低于约10℃。
2.在10-20℃用N2时玉米糖浆溶液脱气和/或清洗以除去溶液中的氧。
3.将玉米糖浆溶液缓慢添加到甲基胺溶液中,并保持温度低于约20℃。
4.一旦全部玉米糖浆溶液添加完毕,搅拌约1-2小时。
加合物在制备后立即用于加氢反应,或在低温下贮存以防止进一步分解。
葡糖胺加合物反应按如下进行:
1.向200ml的高压釜中添加约134g加合物(色度低于约Gardner 1)和约5.8g G49B Ni。
2.用约200psi H2在约20-30℃清洗反应混合物两次。
3.用H2加压至约400psi并将温度升至约50℃。
4.升压至约500psi,反应约3小时。将温度保持在约50-55℃。取试样1。
5.升温至约85℃保持约30分钟。
6.滗析并滤出Ni催化剂。取试样2。
恒定温度的反应条件为:
1.在200ml的高压釜中添加约134g的加合物和约5.8g G49B Ni。
2.用约200psi的H2在低温下清洗两次。
3.用H2加压至约400psi并升温至约50℃。
4.升压至约500psi,反应约3.5小时。将温度保持在指出的温度。
5.滗析并滤出Ni催化剂。试样3是约50-55℃的;试样4是约75℃的;试样5是约85℃的。(约85℃的反应时间为约45分钟)。
所有运行方式得到的是纯度相近的N-甲基葡糖胺(约94%);试验的Gardner色度在反应刚结束后相近,但仅有两阶段加热处理得到了良好的颜色稳定性;85℃试验在反应刚结束后得到了临界颜色。
实施例Ⅱ
按如下所述制备用于洗涤剂组合物的N-甲基麦芽糖胺(maltamine)的牛脂(硬化)脂肪酸酰胺。
步骤1-反应剂:麦芽糖单氢化物(Aldrich,批号01318KW);甲基胺(在水中浓度40wt%)(Aldrich,批号03325TM);Raney Ni,50%浆状物(UAD52-73D,Aldrich,批号12921LW)。
将反应剂添加到玻璃套管内(250g麦芽糖,480g甲基胺溶液,100g催化剂浆状物-50g Raney Ni)并放入3L摇摆式高压釜中,用氮气(3×500psig)和氢气(2×500psig)对该高压釜进行清洗,并在H2中室温下摇动,在28℃至50℃的温度范围内经过一个周末。该粗制反应混合物通过带有柱形硅胶的玻璃微纤维过滤器真空过滤2X。滤液浓缩至成粘性物质。最后的水迹通过将该粘性物质溶于甲醇然后在旋转蒸发器除去甲醇/水而共沸蒸发掉。之后在高度真空中进行最后的干燥,该粗产物溶于回流甲醇中,过滤,冷却至再结晶,过滤并将滤饼在真空中于35℃下干燥。这是馏分#1。滤液浓缩至开始形成沉淀,并在冰箱中贮存过夜。将该固体滤出并在真空中干燥。这是馏分#2。滤液再次浓缩至其体积的一半并进行再结晶。形成很少的沉淀物。添加少量乙醇,将该溶液在冷却器中放置一个周末。将固体物质滤出并在真空中干燥。混合的固体中含有N-甲基麦芽糖胺,它可用于整体合成的步骤2中。
步骤2-反应剂:N-甲基麦芽糖胺(来自步骤1):硬化牛脂甲基酯;甲醇钠(25%在甲醇中);纯甲醇(溶剂);摩尔比1∶1的胺∶酯;初始催化剂用量10摩尔%(w/r麦芽糖胺),升至20摩尔%;溶剂用量50%(wt)。
在密封的瓶中,将20.36g牛脂甲基酯加热至其熔点(水浴)并将其装入带有机械搅拌的250ml3颈圆底烧瓶中。烧瓶加热至ca.70℃以防止酯固化。将25.0gN-甲基麦芽糖胺单独地与45.36g甲醇混合,在进行良好搅拌的条件下把产生的浆状物添加到牛脂酯中。添加1.51g溶于甲醇的25%甲醇钠。在4小时后反应混合物还未澄清。于是添加附加的10摩尔%的催化剂(过总量20摩尔%)并使反应继续进行一夜(ca.68℃),这之后该混合物是清彻的。然后将反应烧瓶改用于蒸馏。将温度升至110℃。在大气压下的蒸馏连续进行60分钟。然后开始高真空蒸馏并持续14分钟,这时产物是很稠的。在110℃(外部温度)使产物在反应烧瓶中停留60分钟。将产物从烧瓶中刮出并在乙醚中研磨经过一个周末。在旋转蒸发器上除去乙醚,将产物贮存在烘箱中过夜,并研磨成粉末。用硅胶从产物中除去任何残余的N-甲基麦芽糖胺。将在100%甲醇中的硅胶浆状物装入漏斗中并用100%甲醇洗涤数次。把该产物的浓缩样品(20g在100ml100%甲醇中)装入硅胶上用真空洗脱数次并用甲醇洗涤数次。将收集的洗脱液蒸发至干(旋转蒸发器)。通过在乙酸乙酯中研磨一夜接着过滤除去任何残余的牛脂酯。滤饼在真空中干燥一夜。该产物是牛脂烷基N-甲基麦芽糖酰胺。
在另一种方式中,前述反应程序的步骤1可以使用市售含葡萄糖或葡萄糖与如5%或更多麦芽糖的混合物的玉米糖浆来进行。所得到的多羟基脂肪酸酰胺及混合物可以在这里的任何洗涤剂组合物中使用。
在再另一种方式中,前述反应程序的步骤2可以在1,2-丙二醇或NEODOL中进行。在产物用于配制洗涤剂组合物之前可不必从反应产物中除去丙二醇或NEODOL,由配制者随意决定。再有,按照配制者的需要,甲醇盐催化剂可以用柠檬酸中和来提供柠檬酸钠,它可保留在多羟基脂肪酸酰胺中。
制备N-烷基胺多羟基化合物的以下步骤在适于进行加氢反应的任何带有良好搅拌装置的压力容器中进行。在简便的实施方式中,采用了有分立贮存仓的压力反应器。该仓(其本身可加压)通过适当管路或类似物与该反应器相连通。在使用中,先用氢对镍催化剂的搅拌的浆状物进行处理以除去痕量的镍氧化物。这可以方便的在反应器中实现。(也可以,如制造者有得到镍催化剂的不含氧化物来源的途径,可不必用H2进行预处理。然而,对大多数制造方法来说不可避免的要存在一些痕量的氧化物,所以H2处理是优选的。)在除去过量的浆状物介质(水)后,将N-烷基胺引入反应器中。之后,将糖从贮存仓在氢气压力下或通过高压泵送系统引入到反应器中,并使反应开始进行。
通过定期地从反应混合物中移出试样并使用气相色谱(“g.c.”)分析可还原的组分可对反应的进程进行监测,或者通过在管形瓶中将试样加热至约100℃达30-60分钟来检测颜色稳定性而对反应进程进行监测。典型的,对于约8升(c.a.2加仑)的反应规模初始阶段(消耗掉达95%的可还原组分)需要约60分钟,略取决于催化剂的量和温度。然后可升高反应混合物的温度使反应结束(消耗掉达99.9%的可还原组分)。
实施例Ⅲ
催化剂的处理-约300ml的RANEY镍4200(Grace Chemicals)用去离子水(1升总容积,3次洗涤)洗涤并滗析。固体催化剂的总量可以通过由Grace Chemicals提供的体积-重量公式来确定,即,[(催化剂+水总重量)-(以体积计的水重量)]×7/6=镍固体量。
将以Ni固体计308.21g的催化剂装入带有4升水的2加仓反应器(由Autoclave Engineers提供的带有DISPERSIMAX空心轴多叶片高速搅拌机的316不锈钢隔板式高压釜)中。反应器在1400-1600psig氢气中加热至130℃达50分钟。将混合物在1500psig氢气中冷却至室温并放置一夜。然后使用内汲管(internal dip tube)除去达反应器体积10%的水。
反应-反应剂有如下这些。881.82mls.50%含水单甲基胺(Air Products,Inc.;批号060-889-09);2727.3g 55%葡萄糖浆(Cargill;71%葡萄糖;99右旋糖当量;批号99M501)。将含有H2O和按上述制备的Raney镍的反应器冷却至室温,并向大气压下用H2覆盖的反应器中装入冰冷的单甲基胺。反应器加压至1000psig氢气并加热至50℃达数分钟。维持搅拌以确保H2在溶液中吸收。
葡萄糖保持在分立的仓中,该仓与反应器的联通处于关闭状态。用H2将该仓加压至4000psig。然后,葡萄糖(水溶液)在H2压力下经过一定时间转移至反应器中。(通过在糖溶液由仓向主反应器转移过程中糖溶液在仓中体积减少而导致的仓的压力的变化可对这一转移进行监测。糖可以按各种不同速率进行转移,但每分钟压降为Ca.100psig的转移速率是方便的,按这种方法转移所使用的体积需约20分钟。)当含水糖溶液引入反应器时发生放热;内部温度由50℃升至ca.53℃。
一旦全部葡萄糖转移至反应器后,将温度保持在50℃达30分钟。氢气的摄取通过压力计进行监测。搅拌在整个过程中持续在800-1,100rpm或更高。
反应器的温度升至60℃达40分钟,然后升至85℃达10分钟,然后升至100℃达10分钟。之后反应器冷却至室温并保持压力一夜。溶于含水反应介质中的反应产物可通过使用内汲管由氢气压力方便的进行回收。通过过滤可除去镍颗粒。优选,使用内过滤器以避免暴露于空气,如暴露可造成镍溶解。通过蒸发水从反应产物中回收固体N-甲基葡糖胺。
重复上述步骤使用果糖作为糖来制备N-甲基果糖胺。
用脂肪酯酰胺化-在方法的这一步骤,上面制备的N-甲基葡糖胺与混合的牛脂脂肪酸甲基酯反应来制备对应的N-甲基葡糖胺的牛脂酰胺。应理解,可用椰子脂肪酸甲基酯代替牛脂反应剂,以及可用各种N-烷基多羟基化合物如N-甲基果糖胺代替N-甲基葡糖胺。
反应剂-N-甲基葡糖胺;硬化牛脂甲基酯;甲醇钠(25%在甲醇中);纯甲醇(溶剂);摩尔比约1∶1的胺∶酯;初始催化剂为10摩尔%(w/r葡糖胺),升至20摩尔%;溶剂量为50%(wt)。
在一密封的瓶中,将20.36g牛脂甲基酯加热至其熔点(水浴)并装入带机械搅拌的250ml3-颈圆底烧瓶中。将烧瓶加热至ca.70℃以防止酯固化。另外,将12.5g干燥的N-甲基葡糖胺与45.36g甲醇混合,把产生的浆状物在进行良好搅拌的条件下添加到牛脂酯中。添加1.51g在甲醇25%的甲醇钠。如约4小时后反应混合物还未变澄清,可添加附加的10摩尔%催化剂(达到总量20摩尔%)并使反应持续一夜,在一定时间之后,该混合物是清彻的。然后将反应烧瓶变为用于蒸馏。将浴温度升至110℃。在大气压下连续蒸馏60分钟。然后开始高真空蒸馏。使产物在110℃(外部温度)保持在反应烧瓶中60分钟。把产物从烧瓶中刮出并可任选的乙醚中经过一个周未时间的研磨。在旋转蒸发器上除去乙醚,并将产物在烘箱中贮存一夜,之后研碎成粉末。反应产物可按如下任选进行纯化以用于分析。使用硅胶任选的从产物中除去任何残存的N-甲基葡糖胺。把在100%甲醇中的硅胶浆状物装入漏斗中并用100%甲醇洗涤数次。产物的浓缩试样(20g在100ml 100%甲醇中)装在硅胶上并用真空和数份甲醇洗涤液洗脱数次。收集的洗脱液蒸发至干(旋转蒸发器)。通过在乙酸乙酯中研磨一夜之后进行过滤任选除去任何残存的牛脂酯。然后将滤饼真空干燥一夜。产物是纯化的牛脂烷基N-甲基葡糖酰胺。注:对于牛脂烷基N-甲基葡糖酰胺在洗涤剂组合物中的贯常使用来说,这样的高度纯化过程不是必需的,因为依靠直接的方法制备的N-烷基葡糖胺的质量所得产物一般具有可接受的Gardner色度。对应的,这一纯化步骤由配制者随意决定。
在另一种实施方式中,前述反应程序可在1,2-丙二醇或NEODOL中进行。反应产物在用于配制洗涤剂组合物前不必将丙二醇或NEODOL除去,由配制者随意决定。
N-甲基果糖胺的酰胺按相似方式进行制备。
材料的操作
在上面这样较详细的公开了多羟基脂肪酸酰胺的制备,以下叙述实施本发明来强化操作性能,即特别是其粘度,以下实施例主要说明使用羧基助洗剂物质以实现这一所期目的,应理解本文上面提到的其它羧基物质也可用于这一目的。对应的,以下给出的实施例是为了进行举例说明,不是对本发明进行限定。在实施例中,未处理的对照物粘度在2,000cp的范围。在最终溶液中PH典型的在5-9的范围,优选PH7-9。
实施例Ⅳ
将在水溶剂中含40%(wt)椰子烷基N-甲基葡糖酰胺的组合物加热至约60℃以形成各向同性溶液。将2%(重量)的柠檬酸(钠盐形式,PH7-9;用NaOH调整)与各向同性溶液混合。该溶液在30.6℃至少在7周的时间保持稳定;粘度ca.1,200cp。
实施例Ⅴ
使用2%氧基丁二酸氢盐(oxydisuccinate)(钠)代替柠檬酸钠重复实施例Ⅳ的步骤。在30.6℃达到了7周的稳定性,粘度为ca.1,450cp。
实施例Ⅵ
分别使用2%糖二酸钠NaO2C(CHOH)4CO2Na、酒石酸钠及酒石酸钠单琥珀酸盐/酒石酸钠丁二酸氢盐(Sodium tartrate disuccinate)的混合物重复实施例Ⅵ的步骤。在各种情况下达到了良好的稳定性,粘度为ca.1,500-1,600cp的范围。在相似的试验中,葡糖酸钠在略高于约1,600cp的粘度提供了稳定性。
实施例Ⅶ
使用含有多达约10%1,2-丙二醇或多达约5%甲醇溶剂的水重复任何前述实施例Ⅳ、Ⅴ、或Ⅵ,取得了基本相当的结果。
实施例Ⅷ
使用牛脂烷基N-甲基葡糖酰胺和果糖酰胺表面活性剂及所列举的羧酸盐或次氮基三乙酸酯重复任何前述的实施例,实现了粘度的降低。
前面举例说明了本发明的实施,应注意的是,还可对其做出进一步改变,这些都不超出其范围和实质。这样,在PHca.5-9、优选约7条件下,还可在该体系中添加各种通用水溶助长剂如枯烯磺酸钠。其用量典型的多达约10%、优选6%-8%,以提供稳定、低粘度的体系。对于低链长度的酰胺如C12烷基来说尤为如此。
实施例Ⅸ
通过添加PH为7的6%枯烯磺酸钠对实施例Ⅳ进行改变。所得溶液在20-25℃保持低粘度。
可以制备含有多羟基脂肪酸酰胺表面活性剂,所述表面活性剂高达约60%(wt)的所需、流体、可泵送浆状物。这可以通过使用按上面所提到的略高含量的1,2-丙二醇或乙醇溶剂来实现。柠檬酸可以在这类流体化混合物中使用,其它多羧酸盐官能化物质如马来酸和苹果酸也同样。以下实施例进一步说明这种类型的这类可泵送浓缩物。
实施例Ⅹ
含有5.1±0.5%丙二醇在35±5℃粘度为1000厘泊(最大值)的50±1%多羟基脂肪酸酰胺(R1甲基;R2=C12-C18)的可泵送浆状物通过向其中添加以下物质进行制备:水[最终浆状物的30-35%(重量)],1,2-丙二醇(最终浆状物重量的10±1%),柠檬酸(最终浆物重量的10±1%)。
实施例Ⅺ
含6.2±0.6%丙二醇的包含55±2%多羟基脂肪酸酰胺表面活性剂(R1=甲基;R2=C12-C18)的可泵送浆状物使用如下物质进行制备,柠檬酸(浆状物重量的10±0.2%),乙醇(浆状物重量的10±0.5%),水(平衡量;浆状物重量的ca20-25%)。这类浆状物在35℃粘度为约1000厘泊(最大值)。
Claims (10)
1、一种制备多羟基脂肪酸酰胺表面活性剂的稳定、浓缩、流体化混合物的改进方法,其特征在于它包括:
(a)制备所述多羟基脂肪酸酰胺表面活性剂在含水溶剂中的贮备混合物,所述含水溶剂包含水或含少量有机溶剂的水;
(b)预热所述贮备混合物以提供所述多羟基脂肪酸酰胺在所述含水溶剂中的各向同性溶液;
(c)与步骤(b)并行或在其后,向多羟基脂肪酸酰胺的所述各向同性溶液中添加有效、粘度控制量的羧酸盐官能化物质,由此使所述溶液的粘度保持为可泵送的粘度。
2、如权利要求1所述的方法,其中当在约30.6℃的温度测量时,粘度降至低于约2,000厘泊。
3、如权利要求2所述的方法,其中所述有机溶剂是选自以下物质组成的组中的一种,所述物质为水、甲醇、乙醇、1,2-丙二醇、及它们的混合物。
4、如权利要求3所述的方法,其中所述溶剂选自水、水/乙醇和水/1,2-丙二醇。
5、如权利要求1所述的方法,其中羧酸盐官能化物质是具有三个或更多羧基的多羧酸盐助洗剂。
6、如权利要求5所述的方法,其中所述助洗剂是选自以下物质组成的组中的一种,所述物质为柠檬酸盐、羟基丁二酸氢盐、酒石酸盐、酒石酸盐单琥珀酸盐、酒石酸盐丁二酸氢盐、葡糖酸盐、糖二酸盐,所述助洗剂呈酸或水溶性盐形式、及它们的混合物。
7、如权利要求6所述的方法,其中采用约2%(重量)的羧酸盐助洗剂。
8、如权利要求7所述的方法,其中采用了柠檬酸盐助洗剂和浓度多达约60%(重量)的椰子烷基N-甲基葡糖酰胺在水中的各向同性溶液。
9、如权利要求1所述的方法,其中所述羧酸盐官能化物质选自苹果酸盐或马来酸盐。
10、如权利要求1所述的方法,其中另外还采用了水溶助长剂。
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- 1993-03-08 WO PCT/US1993/002066 patent/WO1993019146A1/en active IP Right Grant
- 1993-03-08 ES ES93907300T patent/ES2089807T3/es not_active Expired - Lifetime
- 1993-03-08 CA CA002131173A patent/CA2131173C/en not_active Expired - Fee Related
- 1993-03-08 DE DE69303708T patent/DE69303708T2/de not_active Expired - Fee Related
- 1993-03-08 JP JP5516583A patent/JPH07504703A/ja active Pending
- 1993-03-08 EP EP93907300A patent/EP0631608B1/en not_active Expired - Lifetime
- 1993-03-15 TR TR00178/93A patent/TR27593A/xx unknown
- 1993-03-16 MX MX9301476A patent/MX9301476A/es unknown
- 1993-03-16 CN CN93104563A patent/CN1040996C/zh not_active Expired - Fee Related
-
1996
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CN110327235A (zh) * | 2019-08-19 | 2019-10-15 | 广州环亚化妆品科技有限公司 | 一种弹密绵柔洁面慕斯及其制备方法 |
CN110327235B (zh) * | 2019-08-19 | 2022-05-03 | 广州环亚化妆品科技股份有限公司 | 一种弹密绵柔洁面慕斯及其制备方法 |
CN111235619A (zh) * | 2020-01-15 | 2020-06-05 | 东莞市四辉表面处理科技有限公司 | 铝材阳极封孔后高效除镍清洗粉及其制备方法 |
CN111235619B (zh) * | 2020-01-15 | 2022-05-31 | 东莞市四辉表面处理科技有限公司 | 铝材阳极封孔后高效除镍清洗粉及其制备方法 |
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EP0631608B1 (en) | 1996-07-17 |
MX9301476A (es) | 1994-07-29 |
CN1040996C (zh) | 1998-12-02 |
CA2131173C (en) | 1998-12-15 |
DE69303708D1 (de) | 1996-08-22 |
US5620952A (en) | 1997-04-15 |
CA2131173A1 (en) | 1993-09-30 |
WO1993019146A1 (en) | 1993-09-30 |
ES2089807T3 (es) | 1996-10-01 |
PH31409A (en) | 1998-10-29 |
AU3795193A (en) | 1993-10-21 |
EP0631608A1 (en) | 1995-01-04 |
TR27593A (tr) | 1995-06-13 |
JPH07504703A (ja) | 1995-05-25 |
DE69303708T2 (de) | 1997-02-27 |
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