十二醇邻苯二甲酸单酯钠的合成与性能研究

doi:10.3969/j.issn.1001-1803.2020.09.001

摘要/Abstract

摘要：

采用十二醇和邻苯二甲酸酐经酯化和中和反应得到十二醇邻苯二甲酸单酯钠（PAS12）,并通过 ¹H NMR确定了其分子结构。PAS12的Krafft温度为16.4 ℃,与十二酸钠（SL,15.5 ℃）相近,明显低于十六酸钠（SP,57.4 ℃）;与SL相比,cmc（PAS12）＜ cmc（SL）,γ_cmc（PAS12）＜ γ_cmc（SL）,σ_cmc（PAS12）＜ σ_cmc（SL）,PAS12的乳液稳定性、耐受Ca ²⁺、发泡力和泡沫稳定性更好,其原因可能是PAS12分子结构中位于亲水基（-COONa）和疏水基（C₁₂H₂₅-）之间的苯环和酯键片段增加了PAS12疏水基的有效长度,且苯环和酯键片段同时兼具部分亲水性和疏水性,为PAS12分子本身的极性从强极性（-COONa）向弱极性（C₁₂H₂₅-）转换提供过渡,有利于PAS12有效地降低气-液和液-液界面张力;再加上苯环上二羧酸邻位取代结构使得PAS12更好地耐受Ca ²⁺。因此,PAS12具有较好的低温水溶性、较低的表（界）面张力、良好的乳化性能、泡沫性能和一定的耐硬水性质。

Abstract: Sodium dodecyl phthalate monoester （PAS12） was synthesized by esterification of dodecyl alcohol and phthalic anhydride and then neutralization, and its molecular structure was confirmed by ¹H NMR. The Krafft temperature of PAS12 was 16.4 ℃, which was similar to sodium laurate （SL, 15.5 ℃） and significantly lower than that of sodium palmitate （SP, 57.4 ℃）. Compared with SL, results of cmc（PAS12）＜ cmc（SL）, γ_cmc（PAS12）＜ γ_cmc （SL）, σ_cmc（PAS12）＜ σ_cmc（SL）, better emulsion stability, Ca ²⁺-tolerance to foaming performance and foam stability for PAS12 were observed. The segment of benzene ring and ester between the hydrophilic group （-COONa） and the hydrophobic group （C₁₂H₂₅-） might increase the effective length of hydrophobic chain. And this segment had both partial hydrophilicity and hydrophobicity, which could provide a transition from strong polarity （-COONa） to weak polarity （C₁₂H₂₅-） for the PAS12. It was therefore beneficial for PAS12 to reduce gas-liquid and liquid-liquid interfacial tensions; furthermore the structure of the ortho-substituted benzene ring might give PAS12 a better Ca ²⁺-tolerance. Therefore, PAS12 exhibited better low-temperature water solubility, lower surface/interfacial tension, better emulsifying properties, foam properties and hard water resistance.

关键词: 十二醇邻苯二甲酸单酯钠, 耐受Ca²⁺, 泡沫, 乳化

Key words: sodium dodecyl phthalate monoester, Ca²⁺-tolerance, foam, emulsification

中图分类号:

TQ423

张志东,方银军,刘雪锋. 十二醇邻苯二甲酸单酯钠的合成与性能研究[J]. 日用化学工业, 2020, 50(9): 581-587.

ZHANG Zhi-dong,FANG Yin-jun,LIU Xue-feng. Synthesis and properties of sodium dodecyl phthalate monoester[J]. China Surfactant Detergent & Cosmetics, 2020, 50(9): 581-587.

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表面活性剂	K_T/℃
PAS12	16.4±0.2
SL	15.5±0.3
SP	57.4±0.3

表面活性剂	cmc/（mmol·L^-1）	γ_cmc/（mN·m^-1）	Π_cmc/（mN·m^-1）	pc₂₀	cmc/c₂₀	Г_m×10⁶/（mol·m²）	A_min/nm²
PAS12	0.76	29.36	42.54	4.50	23.73	2.96	0.56
SL	20.01	35.05	36.86	2.07	2.35	7.40	0.22

c/（mmol·L^-1）	t_1/2 （PAS12）/min	t_1/2 （SDS）/min	t_1/2 （SL）/ min
1	31.5±0.2	24.2±0.5	0
8	93.5±0.6	94.4±0.6	71.8±0.8
23	98.2±0.6	99.1±0.4	66.6±0.4