RAFT无皂乳液聚合制备衣康酸改性聚苯乙烯乳液
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摘要
采用一种RAFT活性聚合的新方法制备衣康酸改性聚苯乙烯纳米粒子。首先合成用于活性聚合的小分子可逆加成-断裂链转移剂三硫代碳酸酯(DBTTC)。然后采用无皂乳液聚合的方法,以生物质原料衣康酸为共聚单体,过硫酸铵为引发剂,在丙酮/水溶液中进行苯乙烯共聚反应,合成了粒径分布窄的聚苯乙烯乳液。分别研究了苯乙烯(St)/衣康酸(IA)单体配比、丙酮/水配比、反应温度以及DBTTC用量等对乳液粒径的影响。用激光粒度分布仪、透射电子显微镜(TEM)、凝胶渗透色谱(GPC)、表面张力仪和电导率仪对乳液进行表征。结果表明,当温度为78℃,n(St)/n(IA)为10,n(DBTTC)/n(St)为0.064,n(丙酮)/n(水)为4∶6,可获得平均粒径为98 nm的聚苯乙烯纳米乳胶粒。
A new method for preparation of polystyrene nanoparticles by using a method of RAFT living polymerization was studied. Firstly, small molecular reversible addition-fragmentation chain transfer agent, three thiocarbonate(DBTTC), was synthesized for active polymerization. Then the emulsifier free emulsion polymerization method was used to prepare styrene polystyrene latex with narrow particle size distribution using itaconic acid as the monomer and ammonium persulfate as initiator.Effects of the molar ratio of St/IA,molar ratio of acetone/water,reaction temperature and amount of DBTTC on the latex particle size were studied respectively. The latices were characterized by Malvern nanosizer, TEM, GPC, surface tension and conductometric titration.The results show that when the temperature is 78 ℃,the molar ratio of St/IA is 10,and the molar ratio of DBTTC/St is 0.064,the molar ratio of acetone/water is 4∶6,the polystyrene nanometer latex particles with average particle size of98 nm can be obtained.
A new method for preparation of polystyrene nanoparticles by using a method of RAFT living polymerization was studied. Firstly, small molecular reversible addition-fragmentation chain transfer agent, three thiocarbonate(DBTTC), was synthesized for active polymerization. Then the emulsifier free emulsion polymerization method was used to prepare styrene polystyrene latex with narrow particle size distribution using itaconic acid as the monomer and ammonium persulfate as initiator.Effects of the molar ratio of St/IA,molar ratio of acetone/water,reaction temperature and amount of DBTTC on the latex particle size were studied respectively. The latices were characterized by Malvern nanosizer, TEM, GPC, surface tension and conductometric titration.The results show that when the temperature is 78 ℃,the molar ratio of St/IA is 10,and the molar ratio of DBTTC/St is 0.064,the molar ratio of acetone/water is 4∶6,the polystyrene nanometer latex particles with average particle size of98 nm can be obtained.
引文
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[3] Li L Z,Tian Y Z,Hai B F,et al. Polystyrene sphere-assisted one-dimensional nanostructure arrays:Synthesis and applications[J].Journal of Materials Chemistry,2010,21(1):40-56.
[4] Wu J Y,Jan Y Y,Liu K C,et al. Preparation of polystyrene/clay nanocomposite by bulk polymerization and its characterization[J].Annals of the New York Academy of Sciences,1998,446(1):282-295.
[5] Tang B T,Zhao J,Zhang S F.Synthesis of styrene-maleic anhydride alternating copolymers by solution polymerization[J].Fine Chemicals,2010,6(2):56-61.
[6] Cho C G,Lee K.Preparation of starch-g-polystyrene copolymer by emulsion polymerization[J].Carbohydrate Polymers,2002,48(2):125-130.
[7] Qi D M,Zhao X L,Chen Z J,et al.Preparation of submicron polystyrene particles by micro-suspension polymerization with ultrasonic homogenization[J].Ciesc Journal,2014,65(2):744-751.
[8] Xie W H,Wu J M,Jiang G J,et al.A Study of the effect of surfactants on the properties of polystyrene-montmorillonite nanocomposites[J].Polymer Engineering&Science,2003,43(1):214-222.
[9] Chiu W Y,Shih C C.A study of the soap-free emulsion polymerization of styrene[J].Journal of Applied Polymer Science,2010,31(7):2117-2128.
[10] Kong X F,Wu Q H,Wan C W,et al. Monodisperse ultrafine polystyrene nanoparticles prepared by a semicontinuous microemulsion polymerization[J].Polymer Science Part A:Polymer Chemistry,2008,46(13):4522-4528.
[11] Okubo M,Yamada A,Shibao S,et al.Studies on suspension and emulsion.XLVI.Emulsifier-free emulsion polymerization of styrene in acetone–water[J].Journal of Applied Polymer Science,1981,26(5):1675-1679.
[12] Yang L,Luo Y W,Li B G.Reversible addition fragmentation transfer(RAFT)polymerization of styrene in a miniemulsion:A mechanistic investigation[J].Polymer,2006,47(2):751-762.
[13] Roshan T A,Jeffery M J,Moad G,et al. Living free radical polymerization with reversible addition-fragmentation Chain transfer(RAFT polymerization):Approaches to star polymers[J].Macromolecules,2003,36(1):1505-1513.
[14] Yang P C,Armes R L,Armes S P.Efficient synthesis of poly(methacrylic acid)-block-poly(styrene-alt-N-phenylmaleimide)diblock copolymer lamellae using RAFT dispersion polymerization[J].Macromolecules,2013,46(21):8545-8556.
[15]孙鹏飞,王阳,张欢,等.丙烯酰胺在乙醇/水介质中的RAFT分散聚合[J].石油化工高等学校学报,2018,31(4):7-12.Sun P F,wang Y,Zhang H,et al. RAFT dispersion polymerization of acrylamide in ethanol/water[J]. Journal of Petrochemical Universites,2018,31(4):7-12.
[16] Wang R G,Zhou X X,Lei W W,et al. Production of itaconic acid and its applications in polymer materials[J]. Materials China,2012,31(12):48-52.
[17] Fréal-Saison S,Save M,Bui C,et al.Emulsifier-free controlled free-radical emulsion polymerization of styrene via RAFT using dibenzyltrithiocarbonate as a chain transfer agent and acrylic acid as an ionogenic comonomer:Batch and spontaneous phase inversion processes[J].Macromolecules,2006,39:8632-8638.
[18] John H. Determination of surface carboxyl groups in styrene/itaconic acid copolymer latexes[J]. Colloid and Interlace Science,1974,49(3):425-432.
[19] Ngai T,Wu C.Double roles of stabilization and destabilization of initiator potassium persulfate in surfactant-free emulsion polymerization of styrene under microwave irradiation[J].Langmuir,2005,21:8520-8525.
[20] Hu J F,Cai Y L,Shan X,et al.Effect of surfactant on zeta potential and rheology behavior of methylene bis(thiocyanate)suspension concentrate[J].Chinese Journal of Chemical Engineering,2017,25(5):541-546.
[21] Ho C H,Chen S A,Amiridis M D,et al. Dispersion polymerization of styrene in alcohol media:Effect of initiator concentration,solvent polarity,and temperature on the rate of polymerization[J]. Polymer Science Part A:Polymer ChemiStry,2015,35(14):2907-2915.