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1. 浙江理工大学先进纺织材料与制备技术教育部重点实验室 浙江理工大学材料与纺织学院,杭州,310018
2. 浙江理工大学生态染整技术教育部工程研究中心,杭州,310018
纸质出版日期:2014-3-20,
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杨雷, 孙鹏, 戚栋明, 沈一峰. 含惰性烯双键RAFT试剂调控的苯乙烯溶液与细乳液聚合[J]. 高分子学报, 2014,(3):316-325.
Lei Yang, Peng Sun, Dong-ming Qi, Yi-feng Shen. Styrene Solution Polymerization and Mini-emulsion Polymerization Mediated by Amphiphilic RAFT Agent Containing Inert Alkenyl Vinylic Bonds[J]. Acta Polymerica Sinica, 2014,(3):316-325.
杨雷, 孙鹏, 戚栋明, 沈一峰. 含惰性烯双键RAFT试剂调控的苯乙烯溶液与细乳液聚合[J]. 高分子学报, 2014,(3):316-325. DOI: 10.3724/SP.J.1105.2014.13245.
Lei Yang, Peng Sun, Dong-ming Qi, Yi-feng Shen. Styrene Solution Polymerization and Mini-emulsion Polymerization Mediated by Amphiphilic RAFT Agent Containing Inert Alkenyl Vinylic Bonds[J]. Acta Polymerica Sinica, 2014,(3):316-325. DOI: 10.3724/SP.J.1105.2014.13245.
以可逆加成-断裂-链转移(RAFT)试剂顺序控制丙烯酸和不对称双烯化合物4-(3-丁烯氧基-甲基)苯乙烯(BEOMSt)的溶液聚合反应,得到了两亲结构的大分子RAFT试剂,同时将BEOMSt分子中的惰性烯双键定量地悬垂于试剂的亲水与亲油嵌段间.以该试剂分别调控苯乙烯(St)溶液和细乳液聚合,着重考察了聚合方法对惰性烯双键链增长反应特性的影响.溶液聚合中,惰性烯双键链增长反应速率极低,St转化率68.6%时,产物链中烯双键数目仍维持初值,产物分子量与理论值吻合,分子量分布较窄,聚合反应呈现典型活性聚合的特征.但细乳液聚合反应初期,烯双键已与St共聚合,并引起分子链间偶联和分子量与理论值的正偏差,产物分子量分布也很宽.初步推测,导致细乳液聚合时惰性烯双键链增长反应受到强化作用的原因是两亲结构RAFT试剂吸附于单体细液滴表面,引起液滴油水界面层内自由基浓度以及烯双键与St浓度比值增高.
An amphiphilic reversible addition-fragmentation chain transfer (RAFT) agent containing alkenyl vinylic bonds was synthesized by the sequential RAFT polymerization of acrylic acid and asymmetric divinyl monomer 4-((but-3-en-1-yloxy)methyl) styrene
where the pendent inert alkene bonds were embedded between hydrophilic and hydrophobic block.Styrene(St) solution polymerization and mini-emulsion polymerization mediated by the amphiphilic RAFT agent were implemented
aiming at investigating the effects of polymerization methods on the reactivity of the pendent alkene groups.During solution polymerization
the alkene groups show extremely low reactivity and remained intact in the studied St conversion range(68.6%).The resulting polymers retained quantitative alkenyl groups and had predictable molecular weights together with narrowed molecular weight distributions.These findings proved the living characters of the solution polymerization.A different case was found for RAFT mini-emulsion polymerization that copolymerization of alkenyl group with St occurred since the early stage of reaction
leading to the coupling between polymer chains or RAFT agents.As a result
experimental molecular weights positively deviated from theoretical values
and polymers had rather high polydispersity index.It was speculated that the reaction of alkenyl groups was enhanced as a result of the adsorption of amphiphilic RAFT agent onto the surface of monomer mini-droplets
since it could cause an increase in either the concentration of propagation radicals or the concentration ratio of alkene group to St in the oil-water interface layer of droplets.
可逆加成-断裂-链转移聚合溶液聚合细乳液聚合不对称双烯化合物
Reversible addition-fragmentation chain transferSolution polymerizationMini-emulsion polymerizationAsymmetric divinyl monomer
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