Kinetics of acrylamide and 2-methylacryloylxyethyltrimethyl ammonium chloride in inverse emulsion polymerization

doi:10.11949/j.issn.0438-1157.20170870

Abstract

Abstract:

Inverse emulsion polymerization kinetics of acrylamide (AM) and 2-methylacryloylxyethyltrimethyl ammonium chloride (DMC) has been investigated by using the mixture of sorbitan monooleate (Span 80) and polyethylene glycol sorbitan monooleate (Tween 80) as the composite emulsifier, liquid paraffin as the oil phase and 2,2'-azobis[2-(2-imidazolin-2-yl) propane]-dihydrochloride as the initiator. The rate equation of AM and DMC inverse emulsion polymerization could be represented as R_p=k[M]^2.12[I]^0.55[E]^0.65, and the apparent activation energy of AM and DMC inverse emulsion polymerization was 80.65 kJ·mol^-1. Relationship of reaction rate change in AM and DMC inverse emulsion polymerization with time indicated that the nucleation mechanism tended to droplet nucleation. Monomer reactivity ratios of AM and DMC were determined as r_AM=0.23,r_DMC=1.93 by Fineman-Ross methods. The results showed that random copolymerization of AM and DMC occurred on the polymer chains. The intrinsic viscosity of copolymer could be increased by enhancing the content of monomer, decreasing the dose of initiator, increasing the amount of emulsifier and reducing the reaction temperature.

Key words: kinetics, inverse emulsion, polymerization, nucleation mechanism, intrinsic viscosity

摘要：

以丙烯酰胺（AM）和甲基丙烯酰氧乙基三甲基氯化铵（DMC）为单体，失水山梨糖醇脂肪酸酯（Span 80）和失水山梨醇单油酸酯聚氧乙烯醚（Tween 80）为乳化剂，液体石蜡为油相，2，2'-偶氮二异丙基咪唑啉二盐酸盐（VA-044）为引发剂，研究AM与DMC反相乳液聚合动力学，反相乳液聚合速率方程为R_p=k[M]^2.12[I]^0.55[E]^0.65，AM与DMC反相乳液聚合表观活化能为80.65 kJ·mol^-1。通过反相乳液聚合速率随时间的变化关系得出其成核机理倾向于单体液滴成核。用Fireman-Ross法研究了共聚单体竞聚率，分别为r_AM=0.23、r_DMC=1.93，AM与DMC在聚合物链上发生无规共聚反应。单体量增大、引发剂量减少、乳化剂量增大、聚合温度降低均使共聚产物的特性黏数增大。

关键词: 动力学, 反相乳液, 聚合, 成核机理, 特性黏数

CLC Number:

TQ326.4

CHEN Yong, SHAN Guorong. Kinetics of acrylamide and 2-methylacryloylxyethyltrimethyl ammonium chloride in inverse emulsion polymerization[J]. CIESC Journal, 2018, 69(2): 563-569.

陈勇, 单国荣. 丙烯酰胺与甲基丙烯酰氧乙基三甲基氯化铵反相乳液聚合动力学[J]. 化工学报, 2018, 69(2): 563-569.

References 30

[1]	ABDOLLAHI Z, FROUNCHI M, DADBIN S. Synthesis, characterization and comparison of PAM, cationic PDMC and P(AM-co-DMC) based on solution polymerization[J]. Journal of Industrial Engineering Chemistry, 2011, 17(3):580-586.
[2]	CAPEK I. Photopolymerization of acrylamide in the very low monomer concentration range[J]. Designed Monomers and Polymers, 2016, 19(4):290-296.
[3]	TAMSILIAN Y, SA A R, SHABAN M, et al. High molecular weight polyacrylamide nanoparticles prepared by inverse emulsion polymerization:reaction conditions-properties relationships[J]. Colloid and Polymer Science, 2016, 294(3):513-525.
[4]	FAN W X, SHANG K X, SHAN G R, et al. Role of salt in the aqueous two-phase copolymerization of acrylamide and cationic monomers:from screening to anion-bridging[J]. RSC Advances, 2016, 6(64):59352-59359.
[5]	LÜ T, SHAN G R. Mechanism of the droplet formation and stabilization in the aqueous two-phase polymerization of acrylamide[J]. Journal of Applied Polymer Science, 2009, 112(5):2859-2867.
[6]	MOODY G. The use of polyacrylamides in mineral processing[J]. Minerals Engineering, 1992, 5(3/4/5):479-492.
[7]	VACHER C A, LOCH R J, RAINE S R. Effect of polyacrylamide additions on infiltration and erosion of disturbed lands[J]. Australian Journal of Soil Research, 2003, 41(8):1509-1520.
[8]	LU S J, LIU R X, SUN X M. A study on the synthesis and application of an inverse emulsion of amphoteric polyacrylamide as a retention aid in papermaking[J]. Journal of Applied Polymer Science, 2002, 84(2):343-350.
[9]	NGO Y H, LI D, SIMON G P, et al. Effect of cationic polyacrylamide dissolution on the adsorption state of gold nanoparticles on paper and their surface enhanced Raman scattering properties[J]. Colloids and Surfaces A, 2013, 420:46-52.
[10]	GOH S L, MURTHY N, XU M C, et al. Cross-linked microparticles as carriers for the delivery of plasmid DNA for vaccine development[J]. Bioconjugate Chemistry, 2004, 15(3):467-474.
[11]	LIU Z F, BROOKS B W. Inverse dispersion polymerisation of acrylic acid initiated by a water-soluble redox pair:the role of drop mixing[J]. Polymer, 1999, 40(9):2181-2188.
[12]	VANDERHOFF J W, BRADFORD E B, TARKOWSKI H L, et al. Inverse Emulsion Polymerization[M]. Washington DC:Wiley, 1962.
[13]	PENG X H, PENG X C. Water-soluble copolymers(Ⅱ):Inverse emulsion terpolymerization of acrylamide, sodium acrylate, and acryloyloxyethyl trimethylammonium chloride[J]. Journal of Applied Polymer Science, 2006, 101(3):1381-1385.
[14]	SHANG H Z, LIU J P, ZHENG Y B, et al. Synthesis, characterization, and flocculation properties of poly(acrylamide-methacryloxyethyltrimethyl ammonium chloride-methacryloxypropyltrimethoxy silane)[J]. Journal of Applied Polymer Science, 2009, 111(3):1594-1599.
[15]	PABON M, SELB J, CANDAU F, et al. Polymerization of acrylamide in solution and inverse emulsion:number molecular weight distribution with chain transfer agent[J]. Polymer, 1999, 40(11):3101-3106.
[16]	BARARI M, ABDOLLAHI M, HEMMATI M. Synthesis and characterization of high molecular weight polyacrylamide nanoparticles by inverse-emulsion polymerization[J]. Iranian Polymer Journal, 2011, 20(1):65-76.
[17]	BENDA D, SNUPAREK J, CERMAK V. Inverse emulsion polymerization of acrylamide and salts of acrylic acid[J]. European Polymer Journal, 1997, 33(8):1345-1352.
[18]	CHEN L W, YANG B Z, WU M L. Synthesis and kinetics of microgel in inverse emulsion polymerization of acrylamide[J]. Progress in Organic Coatings, 1997, 31(4):393-399.
[19]	HERNANDEZ-BARAJAS J, HUNKELER D J. Inverse-emulsion polymerization of acrylamide using block copolymeric surfactants:mechanism, kinetics and modeling[J]. Polymer, 1997, 38(2):437-447.
[20]	LIU L Y, YANG W T. Photoinitiated, inverse emulsion polymerization of acrylamide:some mechanistic and kinetic aspects[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2004, 42(4):846-852.
[21]	ABDI A, SHAHROKHI M, RAMAZANI A S A, et al. Theoretical and experimental investigations of the inverse emulsion polymerization of acrylamide[J]. Journal of Applied Polymer Science, 2015, 132(22):41916.
[22]	SONG L, WANG M, CONG Y, et al. The mechanism of 60Co γ-ray radiation induced interfacial redox reaction in inverse emulsion and its application in the synthesis of polymer microcapsules[J]. Polymer, 2007, 48(1):150-157.
[23]	ASUA J M. Emulsion polymerization:from fundamental mechanisms to process developments[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2004, 42(5):1025-1041.
[24]	CAPEK I, FIALOVÁ L, BEREK D. On the kinetics of inverse emulsion polymerization of acrylamide[J]. Designed Monomers and Polymers, 2008, 11(2):123-137.
[25]	OUYANG L, WANG L S, SCHORK F J. Synthesis and nucleation mechanism of inverse emulsion polymerization of acrylamide by RAFT polymerization:a comparative study[J]. Polymer, 2011, 52(1):63-67.
[26]	VANDERHOFF J W, DISTEFANO F V, ELAASSER M S, et al. Inverse emulsion polymerization of acrylamide-polymerization kinetics and process-development[J]. Journal of Dispersion Science and Technology, 1984, 5(3/4):323-363.
[27]	刘莲英, 杨万泰. UV光引发的丙烯酰胺反相乳液聚合[J]. 高分子学报, 2004, (4):545-550. LIU L Y, YANG W T. Inverse emulsion polymerization of acrylamide initiated by UV radiation[J]. Acta Polymer Sinica, 2004, (4):545-550.
[28]	赵亮, 单国荣, 翁志学. (2-甲基丙烯酰氧乙基)三甲基氯化铵-丙烯酰胺双水相共聚合[J]. 高分子学报, 2006, (8):944-947. ZHAO L, SHAN G R, WENG Z X. Aqueous two-phase copolymerization of (2-methacrylaloyloxyethyl) trimethylammonium chloride and acrylamide[J]. Acta Polymer Sinica, 2006, (8):944-947.
[29]	毕可臻, 张跃军. 二甲基二烯丙基氯化铵与丙烯酰胺的共聚动力学[J]. 高分子材料科学与工程, 2012, 28(3):53-56. BI K Z, ZHANG Y J. Polymerization kinetics of dimethyldiallylammonium chloride and acrylamide[J]. Polymer Materials Science and Engineering, 2006, (8):944-947.
[30]	GE X W, YE Q, XU X L, et al. Kinetics of emulsion copolymerization of (2-methacryloyloxyethyl) trimethyl ammonium chloride and acrylamide with gamma rays[J]. Radiation Physics and Chemistry, 1997, 50(3):253-258.