马来酸酯磺酸盐型活性聚合物的合成及性能研究

doi:10.3969/j.issn.1001-1803.2019.02.003

摘要/Abstract

摘要：

根据分子结构与性能的关系,用马来酸酐（MA）、聚乙二醇（PEG）、辛醇合成了活性单体（MOPn）,再与2-丙烯酰胺基-2-甲基丙磺酸（AMPS）、丙烯酰胺（AM）通过自由基胶束共聚法合成含有-SO₃ ^-、-CONH₂、EO醚等极性基团的二元和三元活性聚合物,并对其结构进行红外表征和热重分析。评价了聚合物在蒸馏水和无机盐介质中的表面性能,讨论了影响溶液表面活性的各因素以及单体摩尔比对其性质的影响。结果表明：合成的二元聚合物（PMOPnS）具有较好的水溶性和表面活性,活性单体MOP1000与AMPS摩尔比为1∶2的二元聚合物比1∶4的二元聚合物的表面活性更强。三元聚合物在高于258 ℃下开始分解。考察了三元聚合物单体摩尔比、无机盐质量浓度对聚合物黏度的影响。n（MOP1000）∶n（AMPS）∶n（AM）=0.5∶1∶98.5的三元聚合物PMOPSA-1具有较好的增黏效果和表/界面活性,2%三元聚合物PMOPSA-1在蒸馏水和2%NaCl介质中30 ℃黏度分别为1 108和1 157 mPa·s,在2%NaCl和0.1%CaCl₂混合盐水中30 ℃表面张力和45 ℃下与煤油的界面张力分别为30.43和2.09 mN/m,表明合成的活性型聚合物具有较好的热稳定性、稠化性能和表/界面活性。

关键词: 马来酸酯, 2-丙烯酰胺基-2-甲基丙磺酸/丙烯酰胺共聚物, 胶束聚合, 表面活性, 黏度

Abstract:

Based on the relationship between the molecular structure and the properties of polymers, maleic anhydride （MA） , polyethylene glycol （PEG） and octanol were used as main raw materials to synthesize active monomers （MOPn） . The active monomers then reacted with 2-acrylamido-2-methylpropane sulfonic acid （AMPS） and acrylamide （AM） to obtain binary and ternary polymers containing -SO₃ ^-, -CONH₂ and oxethyl （EO） groups by free radical micellar copolymerization. The structure and thermal stability of terpolymers were characterized by IR and differential thermal analysis （DTA）, respectively. The surface activities of polymers in distilled water and in the presence of inorganic salt in aqueous medium were evaluated. The effects of the monomer ratio on properties were also discussed. The results show that the synthesized bipolymer （PMOPnS） has good water solubility and surface activity, and the bipolymer with molar ratio of active monomers （MOP1000∶AMPS） of 1∶2 has a lower surface tension than the one with a molar ratio of 1∶4. The terpolymer becomes to decompose above 258 ℃. The effects of the molar ratio of monomers and the salt mass concentration on the viscosity of terpolymer solution were investigated. PMOPSA-1, a terpolymer of n（MOP1000） ∶n（AMPS） ∶n（AM）=0.5∶1∶98.5, has good thickening effect and surface/interfacial activity. The viscosities of 2% terpolymer in distilled water and in 2% NaCl solution at 30 ℃ are 1 108 and 1 157 mPa·s, respectively. The surface tension at 30 ℃ and the interfacial tension against kerosene at 45 ℃ for 2% aqueous terpolymer solution in the presence of 2%NaCl+0.1%CaCl₂ are 30.43 and 2.09 mN/m, respectively, indicating that PMOPSA-1 has good thermal stability, thickening property and surface/interfacial activity.

Key words: maleate, 2-acrylamido-2-methylpropane sulfonic acid /acrylamide copolymer, micellar polymeri-zation, surface activity, viscosity

中图分类号:

TQ423

许格,郑延成,元平南,郑恒. 马来酸酯磺酸盐型活性聚合物的合成及性能研究[J]. 日用化学工业, 2019, 49(2): 76-82.

Ge XU,Yan-cheng ZHENG,Ping-nan YUAN,Heng ZHENG. Synthesis and solution properties of polymeric sulfomaleate surfactants[J]. China Surfactant Detergent & Cosmetics, 2019, 49(2): 76-82.

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PEG分子量	cmc/（mg·L^-1）		γ_cmc/（mN·m^-1）
PEG分子量	蒸馏水	1% NaCl	蒸馏水	1% NaCl
600	4 918	4 884	31.21	31.13
1 000	2 747	2 654	35.18	34.65
2 000	6 310	5 248	43.14	41.64

PEG分子量	cmc/（mg·L^-1）		γ_cmc/（mN·m^-1）
PEG分子量	蒸馏水	1% NaCl	蒸馏水	1% NaCl
600	4 468	3 763	30.27	30.21
1 000	1 435	1 371	31.64	31.05
2 000	6 510	6 233	41.11	39.74

聚合物	n（MOP1000）∶n（AMPS）∶n（AM）	表观黏度/（mPa·s）	特性黏度/（mL·g^-1）
HPAM		4 181	968
PMOPSA-1	0.5∶1∶98.5	1 108	2 145
PMOPSA-2	0.5∶1∶23.0	222	1 671
PMOPSA-3	0.5∶1∶4.8	66	1 091
PMOPSA-4	0.5∶1∶3.5	59	1 161
PMOPSA-5	0.5∶1∶1.8	10	490

聚合物	表面张力/（mN·m^-1）	界面张力/（mN·m^-1）
PMOPSA-1	30.43	2.09
PMOPSA-2	30.40	2.02
PMOPSA-3	30.58	1.84
PMOPSA-4	30.48	1.70
PMOPSA-5	30.91	1.68
HPAM	58.73	5.85