CN108530307A - 官能团型腰果酚阳离子表面活性剂及其制备方法与应用 - Google Patents

官能团型腰果酚阳离子表面活性剂及其制备方法与应用 Download PDF

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CN108530307A
CN108530307A CN201810478813.XA CN201810478813A CN108530307A CN 108530307 A CN108530307 A CN 108530307A CN 201810478813 A CN201810478813 A CN 201810478813A CN 108530307 A CN108530307 A CN 108530307A
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王利民
赵雪华
车飞
张景清
康文倩
黄中瑞
韩建伟
田禾
赵敏
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SHANGHAI BANGGAO CHEMICAL CO Ltd
East China University of Science and Technology
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Abstract

本发明公开了一种官能团型腰果酚阳离子表面活性剂，结构如式I、II、III所示：其中：R1、R2、R3分别独立地选自烷基、烷基氨基、支链上带有羟基或羧基的烷基、R4、R5、R6分别独立选自烷基、烷基氨基、支链上带有羟基或羧基的烷基、芳基；X为卤素；R7、R8、R9分别独立地选自烷基、烷基氨基、支链上带有羟基或羧基的烷基；m为1～20的正整数。本发明选用天然原料，绿色环保，且产物的水溶性好，Krafft点低，临界胶束浓度低，最低表面张力低，表面活性好。

Description

官能团型腰果酚阳离子表面活性剂及其制备方法与应用
技术领域
本发明涉及表面活性剂技术领域，具体涉及一种含有羟基和酯基的官能团型腰果酚阳离子表面活性剂及其制备方法与应用。
背景技术
季铵盐型表面活性剂是一种重要的阳离子型表面活性剂，但由于疏水长碳链的存在，部分季铵盐型表面活性剂水溶性并不是很好，且其Krafft点较高，给其在洗涤剂或水性乳胶漆中的应用带来一定隐患。腰果酚是从腰果壳液中提炼出来，是一种丰富、廉价的可再生资源。从天然原料出发，在季铵盐型表面活性剂分子中引入羟基，可增加其水溶性；在季铵盐型表面活性剂分子中引入酯基，可增加其生物降解性。因此对腰果酚衍生的表面活性剂的研究极具市场价值。
发明内容
本发明的目的是提供一种官能团型腰果酚阳离子表面活性剂。
本发明的另一个目的是提供一种所述官能团型腰果酚阳离子表面活性剂的制备方法。
本发明的目的是提供一种所述官能团型腰果酚阳离子表面活性剂的应用。
为了实现上述目的，本发明采用的技术方案如下：
本发明的第一方面提供了一种官能团型腰果酚阳离子表面活性剂，结构如式I、II、III所示：
其中：
R1、R2、R3分别独立地选自烷基、烷基氨基、支链上带有羟基或羧基的烷基、
R4、R5、R6分别独立选自烷基、烷基氨基、支链上带有羟基或羧基的烷基、芳基；
X为卤素；
R7、R8、R9分别独立地选自烷基、烷基氨基、支链上带有羟基或羧基的烷基；
m为1～20的正整数。
优选的，结构式I、II、III中：
R1、R2、R3分别独立地选自C1-C4烷基、-CH2CH2OH、-CH2CH2N(CH3)2、-CH2CH2N(CH3)3；
R4、R5、R6分别独立选自C1-C4烷基、-CH2CH2OH、-CH2CH2COOH、苄基；
X为卤素。
优选的，结构式I、II、III中：
R1、R2、R3分别独立地选自-CH3、-CH2CH3、-CH2CH2CH2CH3、-CH2CH2OH、-CH2CH2N(CH3)2、-CH2CH2N(CH3)3；
R4，R5和R6分别独立地选自-CH3、-CH2CH3、-CH2CH2OH、-CH2CH2COOH、苄基；
X为Cl、Br或I。
最优选的，官能团型腰果酚阳离子表面活性剂的结构如下：
上面给出的结构式I、II、III的定义中，汇集所用术语一般定义如下：
烷基是指含1至7个碳原子的直链或支链饱和脂肪烃基团，例如：甲基、乙基、丙基、异丙基、丁基、叔丁基、甲硫基、乙硫基等。
烷基氨基是指N原子上被一个或两个烷基取代，例如：NHCH3、NHCH2CH3、N(CH3)2或CH3NCH2CH3。
卤素是指氟、氯、溴或碘。
芳基是指单、二或三环烃化合物，其中至少一个环为芳香环，每个环含最多7个碳原子，例如，苯基、苄基、萘基、蒽基、联苯基或茚基。
本发明的第二个方面提供了一种官能团型腰果酚阳离子表面活性剂的制备方法，包括以下步骤：
第一步，向腰果酚(4)中逐滴加入环氧氯丙烷(5)，腰果酚与环氧氯丙烷的摩尔比为1:(1～3)，于50℃～150℃反应1h～24h，然后加入碱的溶液，腰果酚与碱的摩尔比为1:(1～3)，于50℃～150℃反应1h～24h，获得中间体化合物(6)；
第二步，化合物(6)溶于溶剂中，加入胺盐(7)或(8)，化合物(6)与胺盐(7)或(8)的摩尔比为1:(0.5～2)，调节pH＝8～9，于20℃～100℃反应4h～24h，分别获得化合物I或II。
所述第一步中腰果酚与环氧氯丙烷的摩尔比为1:(1～2)。
所述第一步中碱选自NaOH、KOH、K2CO3、Na2CO3、NaHCO3、NaH中的至少一种。
所述第一步中碱的溶液选用溶剂为水、丙酮、N,N-二甲基甲酰胺、甲醇中的至少一种。
所述第一步中腰果酚与碱的摩尔比为1:(1～2)。
所述第二步中胺盐选自三甲胺的盐酸盐、三乙胺的盐酸盐、N,N-二甲基丁胺的盐酸盐、N,N-二甲基乙醇胺的盐酸盐、四甲基乙二胺的盐酸盐、吡啶盐酸盐中的至少一种。
所述第二步中化合物(6)与胺盐(7)或(8)的摩尔比为1:(1～1.5)。
所述第二步中调节pH采用碱的溶液来进行；所述碱选自叔胺(具体如三甲胺、三乙胺、吡啶等叔胺)、NaOH、KOH、K2CO3、Na2CO3、NaHCO3；所述碱的溶液采用溶剂选自甲醇、乙醇、乙腈中的至少一种。
本发明的第二个方面提供了一种官能团型腰果酚阳离子表面活性剂的制备方法，包括以下步骤：
羧酸(9)中加入亚胺，腰果酚与亚胺的摩尔比为1:(1～1.5)，冰浴条件下加入腰果酚(4)，腰果酚与羧酸的摩尔比为1:(1～3)，控制反应温度在0℃～50℃，反应时间为1h～48h，获得中间体(10)；
将中间体(10)溶于溶剂中，加入季铵化试剂(11)搅拌，中间体与季铵化试剂的摩尔比为1:(0.5～2)，控制反应温度为10℃～100℃，反应时间为1h～48h，获得化合物III。
所述腰果酚与羧酸的摩尔比为1:(1～1.5)。
所述羧酸为N,N-二甲基甘氨酸。
所述亚胺选自碳二亚胺(EDC)、二环己基碳二亚胺(DCC)、N,N-二异丙基碳二亚胺(DIC)，优选EDC。
所述溶剂选自二氯甲烷、二氯乙烷、氯仿、丙酮、乙腈。
所述中间体与季铵化试剂的摩尔比为1:(1～1.5)。
所述季铵化试剂为卤代烷，优选为碘甲烷。
本发明的第三个方面提供了一种所述官能团型腰果酚阳离子表面活性剂与非离子表面活性剂腰果酚聚氧乙烯醚的二元复配体系。
本发明的第四个方面提供了一种所述官能团型腰果酚阳离子表面活性剂在洗涤剂、涂料中的应用。
由于采用上述技术方案，本发明具有以下优点和有益效果：
本发明的官能团型腰果酚阳离子表面活性剂，含有羟基和酯基，以天然物质腰果酚为原料，合成含有1个或2个羟基的腰果酚型季铵盐类表面活性剂，羟基的引入，使阳离子表面活性剂的水溶性大大增强；以氨基酸为原料，酯基的引入，使阳离子表面活性剂的生物降解性增强；选用天然原料，绿色环保，且产物的水溶性好，Krafft点低，临界胶束浓度低，最低表面张力低，表面活性好。
本发明的含有羟基和酯基的官能团型腰果酚阳离子表面活性剂，化合物A～H中CMC值最大的化合物F的CMC值也比市售阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)低1-2个数量级，该类腰果酚型阳离子表面活性剂具有很好的表面活性。
本发明的含有羟基和酯基的官能团型腰果酚阳离子表面活性剂，化合物A～H中尤其是化合物B，与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)的二元复配体系中，当化合物B摩尔分数为0.2时，CMC增效20.59％，γCMC增效1.97％；当化合物B摩尔分数为0.4时，CMC增效12.11％，γCMC增效4.83％。
附图说明
图1为化合物A的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图2为化合物B的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图3为化合物C的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图4为化合物D的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图5为化合物E的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图6为化合物F的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图7为化合物G的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图8为化合物H的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图9为市售阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)表面张力(γ)与浓度(c)的关系示意图。
图10为摩尔分数为0.2的化合物B与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)复配的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图11为摩尔分数为0.4的化合物B与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)复配的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图12为摩尔分数为0.6的化合物B与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)复配的水溶液的表面张力(γ)与浓度(c)的关系示意图。
图13为摩尔分数为0.8的化合物B与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)复配的水溶液的表面张力(γ)与浓度(c)的关系示意图。
具体实施方式
为了更清楚地说明本发明，下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。
以下实施例中所制备的化合物中：
实施例1
化合物A
(1)中间体(6)的制备
将腰果酚(1eq)加入反应器中，控制反应温度在70℃～120℃，机械搅拌，并逐滴加入环氧氯丙烷(1.6eq)，反应时间为2h～4h；再加入质量分数为30％的NaOH(1.6eq)水溶液，控制反应温度在70℃～120℃，反应时间为2h～4h。反应结束后，用乙酸乙酯萃取，旋除滤液中有机溶剂后，经柱层析提纯(淋洗剂为石油醚：乙酸乙酯＝75:1)，得到无色油状液体，即中间体(6)。
中间体(6)的1H NMR如下：
1H NMR(400MHz,CDCl3)δ7.21–7.15(m,1H),6.82–6.77(m,1H),6.77–6.70(m,2H),5.87–5.77(m,0.3H),5.45–5.26(m,3H),5.07–4.97(m,0.7H),4.21–4.18(m,1H),3.99–3.95(m,1H),3.37–3.33(m,1H),2.92–2.89(m,1H),2.84–2.78(m,1.6H),2.77–2.75(m,1H),2.57(t,J＝7.6Hz,2H),2.06–1.99(m,3.3H),1.62–1.58(m,2H),1.39–1.25(m,13.4H),0.91-0.86(m,2.3H).
(2)化合物A的制备
将中间体(6)(1eq)溶在甲醇中，加入三甲胺的盐酸盐(1eq)，并用三甲胺的甲醇溶液调节pH＝8～9，磁力搅拌，控制反应温度为20℃～50℃，反应时间为5h～15h。反应结束后，旋除溶剂和三甲胺，黄色膏状固体用正己烷洗，得到白色膏状固体化合物A。
化合物A的1H NMR如下：
1H NMR(400MHz,CDCl3)δ7.19–7.12(m,1H),6.80–6.75(m,1H),6.74–6.68(m,2H),5.86–5.77(m,0.3H),5.47–5.30(m,3H),5.07–4.96(m,0.7H),4.71(s,1H),4.15–4.11(m,1H),3.96–3.92(m,1H),3.78–3.73(m,1H),3.61–3.58(m,1H),3.47(s,9H),2.84–2.76(m,1.6H),2.54(t,J＝7.6Hz,2H),2.06–1.99(m,3.3H),1.62–1.51(m,2H),1.39–1.25(m,13.6H),0.92–0.86(m,2.2H).
化合物A的MS如下：
HRMS(ESI-TOF):m/z[M-Cl]+calculated for C27H50NO2 +,C27H48NO2 +,C26H46NO2 +,C26H44NO2 +:420.3836,418.3680,416.3523,414.3367；Found:420.3802,418.3686,416.3530,414.3369。
实施例2
化合物B
中间体(6)和化合物B的合成步骤参照实施例1。
中间体(6)的1H NMR同实施例1中间体(6)的1H NMR。
化合物B的1H NMR如下：
1H NMR(400MHz,CDCl3)δ7.19–7.14(m,1H),6.81–6.77(m,1H),6.71–6.66(m,2H),5.87–5.77(m,0.2H),5.47–5.30(m,2.8H),5.08–4.97(m,0.4H),4.81–4.68(m,1H),4.19–4.16(m,1H),3.91(t,J＝9.2Hz,1H),3.67–3.55(m,7H),3.38–3.34(m,1H),2.84–2.76(m,1.2H),2.55(t,J＝7.6Hz,2H),2.05–1.98(m,3.9H),1.60–1.56(m,2H),1.40(t,J＝7.2Hz,9H)1.35–1.25(m,13.6H),0.93–0.86(m,2.5H).
化合物B的MS如下：
HRMS(ESI-TOF):m/z[M-Cl]+calculated for C30H56NO2 +,C30H54NO2 +,C30H52NO2 +,C30H50NO2 +:462.4306,460.4149,458.3993,456.3836；Found:462.4297,460.4156,458.3996,456.3846。
实施例3
化合物C
中间体(6)和化合物C的合成步骤参照实施例1。
中间体(6)的1H NMR同实施例1中间体(6)的1H NMR。
化合物C的1H NMR如下：
1H NMR(400MHz,CDCl3)δ7.18–7.14(m,1H),6.82–6.74(m,1H),6.74–6.66(m,2H),6.36(s,1H),5.86–5.77(m,0.2H),5.47–5.30(m,2.8H),5.07–4.96(m,0.4H),4.67(s,1H),4.17–4.13(m,1H),3.93(t,J＝8.8Hz,1H),3.73–3.68(m,1H),3.65–3.53(m,3H),3.43(s,3H),3.39(s,3H),2.84–2.74(m,1.7H),2.54(t,J＝7.6Hz,2H),2.08–1.97(m,3.4H),1.81–1.64(m,2H),1.62–1.52(m,2H),1.45–1.35(m,2H),1.36–1.22(m,13.6H),0.98(t,J＝7.6Hz,3H),0.92–0.86(m,2.7H).
化合物C的MS如下：
HRMS(ESI-TOF):m/z[M-Cl]+calculated for C30H56NO2 +,C30H54NO2 +,C30H52NO2 +,C30H50NO2 +:462.4306,460.4149,458.3993,456.3836；Found:462.4307,460.4149,458.3993,456.3840。
实施例4
化合物D
中间体(6)和化合物D的合成步骤参照实施例1。
中间体(6)的1H NMR同实施例1中间体(6)的1H NMR。
化合物D的1HNMR如下：
1H NMR(400MHz,CDCl3)δ7.08-7.00(m,1H),6.69–6.60(m,3H),5.79–5.68(m,0.9H),5.37–5.22(m,3.2H),5.00–4.88(m,0.7H),4.54(s,1H),4.03(s,2H),3.90–2.80(m,2H),3.66–3.57(m,2H),3.50(s,1H),3.28(s,6H),3.24–3.17(m,1H),2.77–2.66(m,1.7H),2.42(t,J＝7.6Hz,2H),2.00–1.99(m,3.1H),1.52–1.41(m,2H),1.34–1.13(m,13.4H),0.85–0.77(m,2.1H).
化合物D的MS如下：
HRMS(ESI-TOF):m/z[M-Cl]+calculated for C28H52NO3 +,C28H50NO3 +,C28H48NO3 +,C28H46NO3 +:450.3942,448.3785,446.3629,444.3472；Found:450.3911,448.3780,446.3603,444.3447。
实施例5
化合物E
中间体(6)和化合物E的合成步骤参照实施例1。
中间体(6)的1H NMR同实施例1中间体(6)的1H NMR。
化合物E的1HNMR如下：
1H NMR(400MHz,CDCl3)δ7.11–7.07(m,1H),6.74–6.68(m,1H),6.68–6.57(m,2H),5.96–5.69(m,0.3H),5.39–5.23(m,3H),5.00–4.89(m,0.7H),4.67–4.58(m,1H),4.08–4.05(m,1H),3.87–3.61(m,5H),3.44(s,6H),2.90–2.82(m,1.6H),2.76–2.69(m,2H),2.47(t,J＝7.6Hz,2H),2.24(s,6H),2.02–1.88(m,3.2H),1.58–1.42(m,2H),1.36–1.11(m,13H),0.85–0.79(m,2.1H).
化合物E的MS如下：
HRMS(ESI-TOF):m/z[M-Cl]+calculated for C30H57N2O2 +,C30H55N2O2 +,C30H53N2O2 +,C30H51N2O2 +:477.4415,475.4258,473.4102,471.3945；Found:477.4375,475.4262,473.4109,471.3955。
实施例6
化合物F
化合物F的合成是在化合物E的基础上增加一步反应过程，中间体(6)和化合物E的合成步骤参照实施例1，中间体(6)和化合物E的1HNMR参照实施例5。化合物F的合成步骤如下：
将化合物E(1eq)加入反应器中，加入溶剂丙酮，加入碘甲烷(2eq)，磁力搅拌，控制反应温度在10℃～50℃，反应时间为5h～15h。反应结束后，旋除溶剂，黄色膏状固体用正己烷洗，得到黄色膏状固体化合物F。
化合物F的1HNMR如下：
1H NMR(400MHz,DMSO)δ7.23–7.19(m,1H),6.81–6.77(m,3H),5.96–5.85(m,1H),5.84–5.73(m,0.3H)，5.43–5.26(m,3H),5.07–4.94(m,0.7H),4.57–4.44(m,1H),4.16–4.85(m,6H),3.64–3.53(m,2H),3.28(s,3H),3.25(s,3H),3.18(s,9H),2.84–2.71(m,2.2H),2.54(t,J＝7.6Hz,2H),2.05–1.94(m,3.2H),1.61–1.48(m,2H),1.37–1.20(m,13.2H),0.90–0.81(m,2H).
化合物F的MS如下：
HRMS(ESI-TOF):m/z[M-Cl]+calculated for C31H60N2O2 +,C31H58N2O2 +,C31H56N2O2 +,C31H54N2O2 +:619.3694,617.3537,615.3381,613.3224；Found:619.3677,617.3537,615.3385,613.3228。
实施例7
化合物G
中间体(6)和化合物G的合成步骤参照实施例1。
中间体(6)的1H NMR同实施例1中间体(6)的1H NMR。
化合物G的1HNMR如下：
1H NMR(400MHz,CDCl3)δ9.18(d,J＝5.6Hz,2H),8.45–8.34(m,1H),8.07–7.93(m,2H),7.18–7.09(m,1H),6.82–6.75(m,1H),6.74–6.64(m,2H),5.88–5.75(m,0.3H),5.49–5.29(m,2.4H),5.27–5.12(m,1H),5.09–4.98(m,0.5H),4.98–4.87(m,1H),4.58–4.47(m,1H),4.19(dd,J＝10,4.4Hz,1H),3.88(dd,J＝9.6,7.6Hz,1H),2.87–2.71(m,1.3H),2.53(t,J＝7.6Hz,2H),2.10–1.94(m,2.8H),1.63–1.52(m,2H),1.37–1.18(m,13.8H),0.93–0.84(m,2.1H).
化合物G的MS如下：
HRMS(ESI-TOF):m/z[M-Cl]+calculated for C29H46NO2 +,C29H44NO2 +,C29H42NO2 +,C29H40NO2 +:440.3523,438.3367,436.3210,434.3054；Found:440.3490,438.3373,436.3214,434.3062。
实施例8
化合物H
(1)中间体H-1的制备
将N,N-二甲基甘氨酸(1.5eq)加入反应器中，冰浴下加入碳二亚胺EDC(1.5eq)，保持冰浴0.5h～2h，加入腰果酚(1eq)，控制反应温度在10℃～50℃，反应时间为5h～15h。反应结束后，用去离子水萃取，旋除有机溶剂后，经柱层析提纯(淋洗剂为二氯甲烷：甲醇＝50:1)，得到油状液体，即中间体H-1。
中间体H-1的1HNMR如下：
1H NMR(400MHz,CDCl3)δ7.30–7.24(m,1H),7.07–7.01(m,1H),6.95–6.97(m,2H),5.87–5.76(m,0.4H),5.46–5.29(m,3.5H),5.08–4.95(m,0.9H),3.44(s,2H),2.85–2.75(m,2.3H),2.60(t,J＝7.6Hz,2H),2.46(s,6H),2.08–1.98(m,3.4H),1.64–1.56(m,2.4H),1.38–1.27(m,13.6H),0.93–0.85(m,2.2H).
(2)化合物H的制备
将中间体H-1(1eq)加入反应器中，加入溶剂丙酮，加入碘甲烷(1.5eq)，磁力搅拌，控制反应温度在10℃～70℃，反应时间为5h～15h。反应结束后，旋除溶剂，黄色膏状固体用乙醚洗，得到黄色膏状固体化合物H。
化合物H的1HNMR如下：
1H NMR(400MHz,CDCl3)δ7.24–7.16(m,1H),7.04–6.98(m,1H),6.94–6.84(m,2H),5.80–5.69(m,0.5H),5.38–5.24(m,3.3H),5.01–4.89(m,0.9H),3.72–3.59(s,9H),2.80–2.65(m,2H),2.51(t,J＝7.6Hz,2H),2.01–1.91(m,3.6H),1.56–1.47(m,2.6H),1.29–1.16(m,13.9H),0.86–0.78(m,2.6H).
化合物H的MS如下：
HRMS(ESI-TOF):m/z[M-I]+calculated for C26H46NO2 +,C26H44NO2 +,C26H42NO2 +,C26H40NO2 +:404.3523,402.3367,400.3210,398.3054；Found:404.3493,402.3373,400.3215,398.3063。
实施例9
化合物A～H的表面活性的性能测试
配制不同浓度的化合物A～H的水溶液，利用吊片法在25℃下通过JK99C全自动张力仪测定化合物A～H水溶液的表面张力。绘制γ-lgc的曲线，从溶液浓度继续增大而表面张力不变化的突变点读取CMC值。
具体结果如下：
结果如图1～8所示，图1为化合物A的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图1可知，化合物A的临界胶束浓度为CMC＝5.62×10-5mol/L，最低表面张力γCMC＝21.25mN/m；图2为化合物B的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图2可知，化合物B的临界胶束浓度为CMC＝1.32×10-5mol/L，最低表面张力γCMC＝20.71mN/m；图3为化合物C的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图3可知，化合物C的临界胶束浓度为CMC＝1.29×10-5mol/L，最低表面张力γCMC＝21.75mN/m；图4为化合物D的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图4可知，化合物D的临界胶束浓为度CMC＝4.27×10-5mol/L，最低表面张力γCMC＝22.54mN/m；图5为化合物E的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图5可知，化合物E的临界胶束浓度为CMC＝1.38×10-5mol/L，最低表面张力γCMC＝20.17mN/m；图6为化合物F的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图6可知，化合物F的临界胶束浓度为CMC＝5.62×10-4mol/L，最低表面张力γCMC＝36.88mN/m；图7为化合物G的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图7可知，化合物G的临界胶束浓度为CMC＝2.40×10-5mol/L，最低表面张力γCMC＝19.71mN/m；图8为化合物H的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图8可知，化合物H的临界胶束浓度CMC＝6.31×10-6mol/L，最低表面张力γCMC＝19.96mN/m。图9为市售阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)表面张力(γ)与浓度(c)的关系示意图，从图9可知，CTAB的临界胶束浓度为CMC＝8.67×10-4mol/L，最低表面张力γCMC＝25.79mN/m。由图1～8可知，化合物A～H具有较低的表面张力，最低的临界胶束浓度CMC值能达到6.31×10-6mol/L，最低表面张力能达到19.71mN/m。化合物A～H中CMC值最大的化合物F的CMC值也比市售阳离子表面活性剂CTAB低，说明该类腰果酚型阳离子表面活性剂具有很好的表面活性，且在用量很少的情况下就能降低溶液的表面张力，应用价值显著。
实施例10
化合物B的复配应用体系
1)复配体系的理论CMC
由王正武等(王正武,李干佐,李英,等.皂荚素及其复配体系表面活性的研究[J].日用化学工业,2000,30(6):1-4.)采用的单组分CMC1、CMC2及γCMC1、γCMC2的加权平均值来进行理论上的复配效果计算，见式(1)和(2)。
CMC理论＝w1·CMC1+w2·CMC2 (1)
γCMC理论＝w1·γCMC1+w2·γCMC2 (2)
式中，w1和w2分别为单组分1和2的质量分数；CMC理论为复配物的CMC理论计算值；γCMC理论为复配物的γCMC理论值。在实际复配体系中，当CMC实际或γCMC实际小于CMC理论或γCMC理论时，表示复配体系增效，反之则复配体系减效。
2)复配体系的实际CMC
将化合物B与BGF-10分别按摩尔分数为0.2、0.4、0.6和0.8比例配制不同浓度的水溶液，按照实施例9所述表面性能测试方法，测试各复配溶液在25℃时的CMC和γCMC。如图10～13所示，图10为摩尔分数为0.2的化合物B与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)复配的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图10可知，0.2配比下二元复配体系的实际临界胶束浓度为CMC＝5.13×10-6mol/L，实际最低表面张力γCMC＝36.57mN/m；图11为摩尔分数为0.4的化合物B与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)复配的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图11可知，0.4配比下二元复配体系的实际临界胶束浓度为CMC＝6.17×10-6mol/L，实际最低表面张力γCMC＝34.25mN/m；图12为摩尔分数为0.6的化合物B与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)复配的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图12可知，0.6配比下二元复配体系的实际临界胶束浓度为CMC＝1.70×10-4mol/L，实际最低表面张力γCMC＝36.63mN/m；图13为摩尔分数为0.8的化合物B与非离子表面活性剂腰果酚聚氧乙烯醚(BGF-10)复配的水溶液的表面张力(γ)与浓度(c)的关系示意图，从图13可知，0.8配比下二元复配体系的实际临界胶束浓度为CMC＝1.79×10-4mol/L，实际最低表面张力γCMC＝32.00mN/m。
具体结果如表1所示，由表1可知，化合物B与非离子表面活性剂腰果酚聚氧乙烯醚BGF-10的二元复配体系中，当化合物B摩尔分数为0.2时，复配体系增效，CMC增效20.59％，γCMC增效1.97％；当化合物B摩尔分数为0.4时，复配体系增效，CMC增效12.11％，γCMC增效4.83％，说明化合物B与非离子表面活性剂具有良好的复配增效效果，可与非离子表面活性剂混合应用到洗涤剂中。
表1化合物B与BGF-10的复配结果
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等同物界定。

Claims (10)

1.一种官能团型腰果酚阳离子表面活性剂，其特征在于：结构如式I、II、III所示：
其中：
R1、R2、R3分别独立地选自烷基、烷基氨基、支链上带有羟基或羧基的烷基、
R4、R5、R6分别独立选自烷基、烷基氨基、支链上带有羟基或羧基的烷基、芳基；
X为卤素；
R7、R8、R9分别独立地选自烷基、烷基氨基、支链上带有羟基或羧基的烷基；
m为1～20的正整数。
2.根据权利要求1所述的官能团型腰果酚阳离子表面活性剂，其特征在于：结构式I、II、III中：
R1、R2、R3分别独立地选自C1-C4烷基、-CH2CH2OH、-CH2CH2N(CH3)2、
R4、R5、R6分别独立选自C1-C4烷基、-CH2CH2OH、-CH2CH2COOH、苄基；
X为卤素。
3.根据权利要求2所述的官能团型腰果酚阳离子表面活性剂，其特征在于：结构式I、II、III中：
R1、R2、R3分别独立地选自-CH3、-CH2CH3、-CH2CH2CH2CH3、-CH2CH2OH、-CH2CH2N(CH3)2、
R4，R5和R6分别独立地选自-CH3、-CH2CH3、-CH2CH2OH、-CH2CH2COOH、苄基；
X为Cl、Br或I。
4.根据权利要求3所述的官能团型腰果酚阳离子表面活性剂，其特征在于：所述官能团型腰果酚阳离子表面活性剂的结构如下：
5.一种权利要求1至4任一项所述的官能团型腰果酚阳离子表面活性剂的制备方法，其特征在于：包括以下步骤：
第一步，向腰果酚中逐滴加入环氧氯丙烷，腰果酚与环氧氯丙烷的摩尔比为1:(1～3)，于50℃～150℃反应1h～24h，然后加入碱的溶液，腰果酚与碱的摩尔比为1:(1～3)，于50℃～150℃反应1h～24h，获得中间体化合物(6)；
第二步，化合物(6)溶于溶剂中，加入胺盐，化合物(6)与胺盐的摩尔比为1:(0.5～2)，调节pH＝8～9，于20℃～100℃反应4h～24h，获得化合物I或II。
6.根据权利要求5所述的官能团型腰果酚阳离子表面活性剂的制备方法，其特征在于：所述第一步中腰果酚与环氧氯丙烷的摩尔比为1:(1～2)；
所述第一步中碱选自NaOH、KOH、K2CO3、Na2CO3、NaHCO3、NaH中的至少一种；
所述第一步中碱的溶液选用溶剂为水、丙酮、N,N-二甲基甲酰胺、甲醇中的至少一种；
所述第一步中腰果酚与碱的摩尔比为1:(1～2)；
所述第二步中胺盐选自三甲胺的盐酸盐、三乙胺的盐酸盐、N,N-二甲基丁胺的盐酸盐、N,N-二甲基乙醇胺的盐酸盐、四甲基乙二胺的盐酸盐、吡啶盐酸盐中的至少一种；
所述第二步中化合物(6)与胺盐(7)或(8)的摩尔比为1:1～1.5；
所述第二步中调节pH采用碱的溶液来进行；所述碱选自叔胺、NaOH、KOH、K2CO3、Na2CO3、NaHCO3；所述碱的溶液采用溶剂选自甲醇、乙醇、乙腈中的至少一种。
7.一种权利要求1至4任一项所述的官能团型腰果酚阳离子表面活性剂的制备方法，其特征在于：包括以下步骤：
羧酸(9)中加入亚胺，腰果酚与亚胺的摩尔比为1:(1～1.5)，冰浴条件下加入腰果酚，腰果酚与羧酸的摩尔比为1:(1～3)，控制反应温度在0℃～50℃，反应时间为1h～48h，获得中间体(10)；
将中间体(10)溶于溶剂中，加入季铵化试剂搅拌，中间体与季铵化试剂的摩尔比为1:(0.5～2)，控制反应温度为10℃～100℃，反应时间为1h～48h，获得化合物III。
8.根据权利要求7所述的官能团型腰果酚阳离子表面活性剂的制备方法，其特征在于：所述腰果酚与羧酸的摩尔比为1:(1～1.5)；
所述羧酸为N,N-二甲基甘氨酸；
所述亚胺选自碳二亚胺、二环己基碳二亚胺、N,N-二异丙基碳二亚胺；
所述溶剂选自二氯甲烷、二氯乙烷、氯仿、丙酮、乙腈；
所述中间体与季铵化试剂的摩尔比为1:(1～1.5)；
所述季铵化试剂为卤代烷，优选为碘甲烷。
9.一种权利要求1至4任一项所述的官能团型腰果酚阳离子表面活性剂与非离子表面活性剂腰果酚聚氧乙烯醚的二元复配体系。
10.一种权利要求1至4任一项所述的官能团型腰果酚阳离子表面活性剂在洗涤剂、涂料中的应用。
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