可逆加成—断裂链转移自由基聚合研究

可逆加成-断裂链转移(Reversible addition-fragmentation chain transfer,RAFT)自由基聚合是最近发展起来的一种活性可控自由基聚合技术。该技术对聚合调控效果好、聚合条件相对温和、适用单体范围广等优点而备受关注,已成为一种有效的聚合物分子设计手段,文章介绍了RAFT聚合的机理、优点及应用。     

可逆加成-断裂链转移自由基聚合的新进展

可逆加成-断裂链转移(RAFT)自由基聚合的适用单体范围广,反应条件温和,没有聚合实施方法如本体、溶液、乳液和悬浮聚合的限制,因而引起了研究者的广泛兴趣,取得了许多新的研究成果。主要对近年来RAFT聚合中使用的最新链转移剂、单体及相关合成与使用情况以及几种新型RAFT反应体系进行了介绍。     

苯乙烯可逆加成-断裂链转移聚合动力学

为了实现可逆加成-断裂链转移(RAFT)聚合过程中,苯乙烯均聚、高分子量聚苯乙烯的合成及苯乙烯与其他单体共聚时,对苯乙烯转化率、共聚时组成和分子量大小的控制,进行了二硫代苯乙酸-1-苯基乙酯(PEPDTA)调控苯乙烯本体和细乳液聚合动力学分析。在本体聚合中,反应速率慢,链增长自由基与"中间态"自由基的终止反应对聚合速率影响较小,很难合成窄分布、高转化率、高分子量的聚苯乙烯;在细乳液聚合中,反应速率快、转化率高,随着PEPDTA含量增加,乳胶粒数量减少、粒径分布变宽,诱导期和缓聚现象明显;聚合物的数均分子量随转化率线性增长,RAFT试剂浓度越高,分子量分布越窄,反应时间越长,分布越宽。以Smith-Ewart方程为基础,建立了苯乙烯RAFT细乳液聚合动力学模型,模型动力学曲线与实验数据相符合,能较好地预测实验过程。     

可逆加成-断裂链转移(RAFT)聚合的研究进展

自可逆加成-断裂链转移自由基聚合技术在1998年发明以来,就逐渐成为聚合研究者的一种非常强大的合成工具,并在研究与应用领域得到很快的发展。文章综述了可逆加成-断裂链转移聚合的RAFT试剂的分类、聚合机理及聚合中的阻滞现象,简要说明了RAFT技术应用的研究进展。     

可逆加成-裂解链转移聚合研究进展

可逆加成-裂解链转移(RAFT)自由基聚合技术自20世纪末提出以来,已成为活性自由基聚合最重要的方法之一,并在研究与应用领域得到很快的发展。简要综述了RAFT技术应用的研究进展。     

丙烯酰胺在聚乙二醇水溶液中可逆加成-断裂链转移聚合

结合双水相聚合和可逆加成-断裂链转移(RAFT)聚合,提出在聚乙二醇(PEG)水溶液中进行丙烯酰胺(AM)的RAFT双水相聚合,考察反应条件对聚合反应速率和产物分子量及分布的影响。结果表明:高引发剂浓度、单体浓度和聚合温度可以提高初始聚合速率和最终转化率,PEG和RAFT试剂浓度的增加会导致聚合速率减慢和最终转化率降低;峰值聚合速率随引发剂浓度、单体浓度和聚合温度的增加而增大,同时峰值聚合速率对应的时间提前;RAFT试剂浓度增加会推迟峰值聚合速率对应的时间,但可制得分子量分布较窄的产物;PEG浓度的增加会导致产物的分子量分布变宽。     

活性自由基聚合研究的新动态──可逆加成-断裂链转移自由基聚合

介绍了基于可逆链转移思想的“活性”／控制自由基聚合。着重介绍澳大利亚Ｒｉｚｚａｒｄｏ研究小组的最新研究成果：以双硫酯类化合物为链转移剂的可逆加成－断裂链转移自由基聚合。分析其活性特征,并阐明其反应机理     

可逆加成断裂链转移聚合及 链转移剂的制备进展

20世纪以来国内外学者使用可逆加成-断裂链转移(RAFT)聚合法进行了有机合成和分子设计,并探索了满足RAFT聚合条件的RAFT试剂,成功得到了RAFT聚合产物。本文介绍了RAFT聚合法的机理、优势与缺陷,并在对RAFT聚合成果进行系统总结的基础上,简要综述了整体的国内外研究现状,介绍了RAFT试剂的合成案例,并提出了水溶性RAFT试剂的合成思路,展望了RAFT聚合体系未来的发展方向。     

可逆加成 -断裂链转移聚合制备 水性丙烯酸酯乳液及其性能研究

以 N-咔唑二硫代甲酸异丙苯酯（ CCBD）为链转移剂,以 N-胺基甲酰马来酸（ NCMA）、丙烯酸丁酯（ BA）、丙烯酸（ AA）为单体,通过可逆加成 -断裂链转移聚合（ RAFT）制备了水性丙烯酸酯类乳液（ PA）,并对 PA的结构进行了表征。考察了 CCBD用量、过硫酸铵（ APS）用量和反应时间等因素对耐冲击性的影响,并对最优条件下制备的 PA进行应用性能测试。结果表明：最优条件为反应时间 4.0 h、CCBD用量 0.5%（摩尔分数）、 APS用量为 5%（摩尔分数）。以最优反应条件制得的 PA具有优异的综合性能。     

采用可逆加成-断裂链转移化学剪切法制备细乳液和纳米胶囊

以含羧基的双亲性可逆加成-断裂链转移(RAFT)试剂为乳液稳定剂前体,探索化学剪切法与双亲性RAFT试剂相结合制备细乳液并进而制备纳米胶囊的可行性。研究发现,通过化学剪切法可制备液滴大小为亚微米的细乳液,乳化效果与双亲性RAFT试剂的结构密切相关。在本研究范围内,以poly(AAm-b-Stn)RAFT和poly(MAAm-co-Stn)RAFT为试剂的乳化效果较好,采用这两种RAFT试剂,经细乳液界面聚合均可得到核壳结构的纳米胶囊粒子,前者聚合过程的稳定性较好。     

Photo-responsive block copolymer containing azobenzene group: Synthesis by reversible addition-fragmentation chain transfer polymerization and characterization

The design and synthesis of a new azobenzene-based methacrylate monomer (Azo-IEM) was demonstrated, and its polymerization behavior during reversible addition-fragmentation chain transfer (RAFT) polymerization was investigated. Well-defined homopolymer and amphiphilic block copolymer containing Azo-IEM monomeric units were successfully prepared as evidenced by NMR and GPC analysis. Moreover, the photo-triggered reversible isomerization of polymer products in selected solvents was investigated. Finally, TEM analysis showed that there were significant differences in the nanoparticle morphologies when the block copolymer samples were irradiated with different wavelengths of light (i.e., UV and visible). The size and shapes of the p(HEMA-b-Azo-IEM) polymer capable of transitions upon changes in Vis/UV light exposure which prepared from MeOH/CHCl₃ mixture solvent. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47870.     

Preparation of molecularly imprinted polymer microspheres via reversible addition-fragmentation chain transfer precipitation polymerization

The first combined use of reversible addition-fragmentation chain transfer (RAFT) polymerization and precipitation polymerization in the molecular imprinting field is described. The new polymerization technique, namely RAFT precipitation polymerization (RAFTPP), provides MIP microspheres with obvious molecular imprinting effects towards the template, fast template binding process and an appreciable selectivity over structurally related compounds, while only irregular MIP aggregates were obtained via traditional radical precipitation polymerization (TRPP) under similar reaction conditions. The MIP microspheres prepared via RAFTPP have proven to show improved binding capacity, larger binding constant and apparent maximum number for high-affinity sites, and significantly higher high-affinity binding site density in comparison with the MIP prepared via TRPP.     

Characterization of pH-dependent micellization of polystyrene-based cationic block copolymers prepared by reversible addition-fragmentation chain transfer (RAFT) radical polymerization

A series of block copolymers composed of a fixed length of an (ar-vinylbenzyl)trimethylammonium chloride (Q) block (the number average degree of polymerization of the Q block, DP_n,Q=57) and varying lengths of an N,N-dimethylvinylbenzylamine (A) block (the number average degrees of polymerization of the A blocks, DP_n,A, ranging 11-50) were prepared by reversible addition-fragmentation chain transfer (RAFT) radical polymerization, and their pH-dependent micellization was characterized by potentiometric titration, ¹H NMR spectroscopy, dynamic and static light scattering, and fluorescence techniques as a function of the A block length. At pH<5.5, the A block is fully protonated, and hence the block copolymers act as a simple polyelectrolyte, dissolving molecularly in acidic water. At pH>7, the A block becomes deprotonated, and thereby the block copolymers aggregate into a micelle composed of hydrophobic microdomains formed from the deprotonated A blocks. Results of light scattering and fluorescence measurements indicated that the micellization behavior depended strongly on the length of the A block. The number of polymer chains comprising one micelle (i.e. mean aggregation number, N_agg) increased from 3 to 12 as DP_n,A increased from 11 to 50 at pH 10.0. In the case of a random copolymer of Q and A with an A/Q molar ratio similar to that of a block copolymer with DP_n,A=50, N_agg∼1 (i.e. unimolecular micelle) was confirmed by static light scattering at pH 10.0.     

黄原酸酯调控的氯乙烯的可逆-加成断裂链转移聚合

以三种不同结构的黄原酸酯为调控剂,进行氯乙烯（VC）溶液和细乳液可逆加成-断裂链转移（RAFT）聚合,发现O-乙基黄原酸丙酸乙酯对VC聚合的调控效果良好,氯乙烯RAFT细乳液聚合速率明显大于溶液聚合,VC聚合12 h转化率大于90%,但聚氯乙烯（PVC）的分子量分布宽于溶液聚合产物。核磁共振和紫外可见吸收光谱分析证明合成的PVC具有黄原酸酯基端基结构,结构缺陷少。含黄原酸酯基PVC可进一步调控VC及醋酸乙烯酯聚合,进行扩链或得到嵌段共聚物。结合聚合动力学,说明黄原酸酯调控的氯乙烯聚合具有活性特征。     

Kinetic study on reversible addition-fragmentation chain transfer (RAFT) process for block and random copolymerizations of styrene and methyl methacrylate

The degenerative (exchange) chain transfer constant C_ex was determined for the dithioacetate-mediated living radical block and random copolymerizations of styrene (St) and methyl methacrylate (MMA) at 40 °C. The addition of the polystyrene (PSt) radical to a polymer-dithioacetate adduct (P-X) to form the intermediate radical (PSt-(X)-P) was (about twice) faster than that of the poly(methyl methacrylate) (PMMA) radical to form the intermediate radical PMMA-(X)-P. The fragmentation (release) of the PMMA radical from the PSt-(X)-PMMA intermediate formed at the initiating stage of block copolymerization was much (about 100 times) faster than the release of the PSt radical, explaining why the block copolymerization of MMA from a PSt-dithiocarbonate adduct is not so satisfactory as that of St from a PMMA-dithiocarbonate adduct. In the random copolymerization, there was implicit penultimate unit effect on the exchange chain transfer process, which appeared in the addition process but not in the fragmentation process.     

几种不可逆加成-断裂型链转移剂在苯乙烯乳液聚合中的研究

研究了基于不可逆加成-断裂链转移机理的3种分子质量调节剂对苯乙烯乳液聚合的影响.主要考察了3种链转移剂对乳液聚合速率、乳胶粒子大小以及聚苯乙烯数均相对分子质量的影响.链转移剂的内在动力学、扩散和自由基解吸附行为决定了其分子质量调节效率、对聚合速率的影响程度和乳胶粒子大小.链转移常数高的α-苯磺酰甲基丙烯酸乙酯使苯乙烯乳液聚合速率下降明显,乳胶粒子粒径分布较宽,且聚合后期不能有效调节聚苯乙烯分子质量 ;而链转移常数相对较小的2,3-二氯丙烯对聚合速率和乳胶粒子粒径的影响轻微,并能全程控制聚苯乙烯分子质量 ;分子质量较大的正十二烷基-2-苯基烯丙基硫则因在乳液体系中的扩散较慢,难以调节聚苯乙烯的分子质量.     

Synthesis of poly(cyclohexene oxide)‐block‐polystyrene by combination of radical‐promoted cationic polymerization,atom transfer radical polymerization and click chemistry

The combination of radical‐promoted cationic polymerization, atom transfer radical polymerization (ATRP) and click chemistry was employed for the efficient preparation of poly(cyclohexene oxide)‐block‐polystyrene (PCHO‐b‐PSt). Alkyne end‐functionalized poly(cyclohexene oxide) (PCHO‐alkyne) was prepared by radical‐promoted cationic polymerization of cyclohexene oxide monomer in the presence of 1,2‐diphenyl‐2‐(2‐propynyloxy)‐1‐ethanone (B‐alkyne) and an onium salt, namely 1‐ethoxy‐2‐methylpyridinium hexafluorophosphate, as the initiating system. The B‐alkyne compound was synthesized using benzoin photoinitiator and propargyl bromide. Well‐defined bromine‐terminated polystyrene (PSt‐Br) was prepared by ATRP using 2‐oxo‐1,2‐diphenylethyl‐2‐bromopropanoate as initiator. Subsequently, the bromine chain end of PSt‐Br was converted to an azide group to obtain PSt‐N₃ by a simple nucleophilic substitution reaction. Then the coupling reaction between the azide end group in PSt‐N₃ and PCHO‐alkyne was performed with Cu(I) catalysis in order to obtain the PCHO‐b‐PSt block copolymer. The structures of all polymers were determined. Copyright © 2010 Society of Chemical Industry     

Polymer-layered silicate nanocomposites prepared through in situ reversible addition-fragmentation chain transfer (RAFT) polymerization

Reversible addition-fragmentation chain transfer (RAFT) polymerizations were performed in the presence of organically modified clays and successfully prepared polystyrene-, poly(methyl methacrylate)-, and poly(n-butyl acrylate)-layered silicate nanocomposites. The polymers had well-defined molecular weights and low polydispersities, as expected from RAFT polymerizations. The morphology of polystyrene-, and poly(n-butyl acrylate)-nanocomposites were found to be exfoliated using montmorillonite modified with N,N-dimethyl-n-hexadecyl-(4-vinylbenzyl) ammonium (MMT-VB16). In the case of PMMA nanocomposite, the structure was a mixture of intercalated and exfoliated when MMT-VB16 was used, while the use of montmorillonite modified with 2-methacryloyloxyethyl-hexadecyldimethyl ammonium (MMT-MA16) resulted in exfoliation.