共查询到20条相似文献,搜索用时 15 毫秒
1.
Jeff Tonnar Patrick Lacroix‐Desmazes Bernard Boutevin 《Macromolecular rapid communications》2006,27(20):1733-1738
Summary: Controlled radical polymerization of n‐butyl acrylate by reverse iodine transfer polymerization (RITP) was achieved in ab initio emulsion polymerization to yield a stable and uncolored latex (particle diameter dp = 106 nm). Hydrolysis of iodine, I2, was responsible for an upward deviation from the targeted molecular weight = 10 400 g · mol−1. The iodide concentration [I−] was followed by an iodide selective electrode and the amount of efficient iodine (33%) was successfully correlated with the experimental molecular weight = 31 000 g · mol−1. Finally, a simplified mechanism of RITP in ab initio emulsion polymerization taking into account the iodine hydrolysis was proposed.
2.
原子转移自由基聚合(ATRP)应用于乳液聚合体系的主要挑战在于如何同时保证乳液的稳定性和聚合反应的可控性。本文主要对乳液ATRP体系中影响聚合反应可控性和乳液稳定性的各种因素、乳液ATRP的机理和乳液ATRP的应用等方面进行了综述。表面活性剂亲水亲油性及其亲水亲油基团的化学性质、催化剂/配体在油/水两相之间的分配行为、引发剂的溶解性、反应温度以及各组分的浓度是影响反应可控性和乳液稳定性的主要因素。各组分在油/水两相中的分配行为使得乳液ATRP的机理比传统乳液聚合更加复杂。乳液原子转移自由基聚合结合了活性自由基聚合和乳液聚合的优点,在理论研究和工业生产上具有很大的应用前景。 相似文献
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采用具有增稠和抗电解质作用的丙烯酸聚氧乙烯酯活性单体和具有聚合稳定作用的高分子表面活性剂,通过反相乳液聚合法合成了涂料印花用丙烯酸系增稠剂.研究了活性单体、交联剂、反应时间等因素对产物性能的影响.得出活性单体用量占共聚单体摩尔数的0.5%,交联剂占共聚单体质量的0.3%,反应时间为1.5h时,增稠剂的综合效果最好. 相似文献
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This communication describes the potential advantages of using a miniemulsion rather than an emulsion process for the polymerization of synthetic rubbers in which the polymerization is ended (short‐stopped) considerably before full conversion in order to limit excessive branching brought on by a high polymer‐to‐monomer ratio in the polymer particles. Because the polymer‐to‐monomer ratio in the particle at low monomer conversion is much lower in a miniemulsion, a miniemulsion can be polymerized to a significantly higher conversion than a conventional emulsion while maintaining an equivalent degree of branching. Short‐stopping at a higher monomer conversion will result in substantially reduced processing costs associated with recovery and recycle of unpolymerized monomer. 相似文献
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Jeff Tonnar Emmanuel Pouget Patrick Lacroix-Desmazes Bernard Boutevin 《Macromolecular Symposia》2009,281(1):20-30
Summary: Iodine transfer polymerization of vinyl acetate in aqueous miniemulsion, initiated by UV radiation in the presence of an α,ω-diiodo-poly(dimethylsiloxane) macrophotoiniferter has been performed. The formation of a triblock copolymer latex PVAc-b-PDMS-b-PVAc has been evidenced by 1H-NMR and size exclusion chromatography. The size of the PDMS and PVAc blocks were modulated thus opening the way to a wide range of copolymers with different properties. A detailed study of the reaction mechanism showed the importance of the aqueous dispersed medium to achieve a controlled polymerization. 相似文献
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以卤化亚铜(CuX)/1,10-邻二氮菲(phen)配合物为催化剂、2-溴代异丁酸 乙酯(EBiB)为引发剂、十二烷基磺酸钠(SLS)为乳化剂,进行了甲基丙烯酸甲 酯(MMA)的原子转移自由基乳液聚合(ATRP)反应。结果表明,与较高温度(70 - 90 ℃)下的聚合反应相比,室温(25 ℃)时聚合反应有更好的可控性,通过 外加钝化剂的复合催化引发体系CuBr/CuBr_2/phen/EBiB或利用CuCl/phen/EBiB催 化引发体系的“卤素交换反应”,可进一步改善聚合反应的可控性。紫外发光谱测 定结果表明,CuBr/phen配合物在MMA相中的分配倾向随着温度的降低而增大,使得 室温下MMA的乳液ATRP保持了较好的可控性和较快的反应速度。 相似文献
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原子转移自由基细乳液聚合* 总被引:2,自引:0,他引:2
本文从正向、反向、同时正向/反向、电子转移活化剂等不同原子转移自由基聚合(ATRP)细乳液引发体系的角度,综述了近年来国内外关于ATRP细乳液聚合的研究进展。在细乳液体系中进行正向ATRP,聚合可控性不理想,反向ATRP相对适合于细乳液体系,其缺点是表面活性剂用量较大。同时正向/反向引发体系的ATRP中催化剂用量大为减少,并且聚合具有良好的可控性;电子转移活化剂(AGET)ATRP是通过电子转移反应来还原过渡金属的氧化态,克服了同时正向/反向ATRP中需要引入自由基引发剂的缺点。 相似文献
9.
Gaohua Zhu Lifen Zhang Xiangqiang Pan Wei Zhang Zhenping Cheng Xiulin Zhu 《Macromolecular rapid communications》2012,33(24):2121-2126
A facile soap‐free miniemulsion polymerization of methyl methacrylate (MMA) was successfully carried out via a reverse ATRP technique, using a water‐soluble potassium persulfate (KPS) or 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride (V‐50) both as the initiator and the stabilizer, and using an oil‐soluble N,N‐n‐butyldithiocarbamate copper (Cu(S2CN(C4H9)2)2) as the catalyst without adding any additional ligand. Polymerization results demonstrated the “living”/controlled characteristics of ATRP and the resultant latexes showed good colloidal stability with average particle size around 300–700 nm in diameter. The monomer droplet nucleation mechanism was proposed. NMR spectroscopy and chain‐extension experiments under UV light irradiation confirmed the attachment and livingness of UV light sensitive S C(S) N(C4H9)2 group in the chain end. 相似文献
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乳液聚合的最新进展(下) 总被引:3,自引:0,他引:3
乳液聚合的最新进展(下)王群,府寿宽,于同隐(复旦大学高分子科学系,上海,200433)2.5单分散聚合物微球的制备和应用自从50年代,Vanderhoff等人首次成功地制备单一尺寸的聚合物胶乳以来,对聚合物微球的兴趣日渐增长。乳液聚合是最早用于生产... 相似文献
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The reverse atom transfer radical polymerization(RATRP)of (-)-menthyl methacrylate ((-)-MnMA) with AIBN(AIBM/CuCl2/bipyridine(bipy) or (-)sparteine((-)Sp)=1/2/4 initiating system in THF has been studied.The dependence of the specific rotation on molecular weight was investigated. 相似文献
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Yasuyuki Kagawa Per B. Zetterlund Hideto Minami Masayoshi Okubo 《Macromolecular theory and simulations》2006,15(8):608-613
Summary: Compartmentalization in atom transfer radical polymerization (ATRP) in dispersed systems at low conversion (<10%) has been investigated by means of a modified Smith–Ewart equation focusing on the system n‐butyl acrylate/CuBr/4,4′‐dinonyl‐2,2′‐dipyridyl at 110 °C. Compartmentalization of both propagating radicals and deactivator was accounted for in the simulations. As the particle diameter (d) decreases below 70 nm, the polymerization rate (Rp) at 10% conversion increases relative to the corresponding bulk system, goes through a maximum at 60 nm, and thereafter decreases dramatically as d decreases further. This behavior is caused by the separate effects of compartmentalization (segregation and confined space effects) on bimolecular termination and deactivation. The very low Rp for small particles (d < 30 nm) is due to the pseudo first‐order deactivation rate coefficient being proportional to d−3.
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John W. Ma Michael F. Cunningham Kim B. McAuley Barkev Keoshkerian Michael K. Georges 《Macromolecular theory and simulations》2002,11(9):953-960
A mathematical model has been developed to describe the interfacial mass transfer of TEMPO in a nitroxide‐mediated miniemulsion polymerization (NMMP) system in the absence of chemical reactions. The model is used to examine how the diffusivity of TEMPO in the aqueous and organic droplet phases, the average droplet diameter and the nitroxide partition coefficient influences the time required for the nitroxide to reach phase equilibrium under non‐steady state conditions. Our model predicts that phase equilibrium is achieved quickly (< 1 × 10−4 s) in NMMP systems under typical polymerization conditions and even at high monomer conversions when there is significant resistance to molecular diffusion. The characteristic time for reversible radical deactivation by TEMPO was found to be more than ten times greater than the predicted equilibration times, indicating that phase equilibrium will be achieved before TEMPO has an opportunity to react with active polymer radicals. However, significantly longer equilibration times are predicted, when average droplet diameters are as large as those typically found in emulsion and suspension polymerization systems, indicating that the aqueous and organic phase concentrations of nitroxide may not always be at phase equilibrium during polymerization in these systems.
14.
Francesca Lorandi Yi Wang Marco Fantin Krzysztof Matyjaszewski 《Angewandte Chemie (International ed. in English)》2018,57(27):8270-8274
Stable latexes of poly(meth)acrylates with predetermined molecular weights, narrow molecular‐weight distributions, and controlled architecture were prepared by true ab initio emulsion atom‐transfer radical polymerization. Water‐soluble (macro)initiators in combination with a hydrophilic catalyst, Cu/tris(2‐pyridylmethyl)amine, initiated the polymerization in the aqueous phase. The catalyst strongly interacted with the surfactant sodium dodecyl sulfate (SDS), thereby tuning the polymerization within nucleated hydrophobic polymer particles. Long‐term stable latexes were obtained, even with SDS loading below 3 wt % relative to monomer. Block and gradient copolymers were prepared in situ. The reaction volume and solid content were successfully increased to 100 mL and 40 vol %, respectively, thus suggesting facile scale‐up of this technique. The proposed setup could be integrated in existing industrial plants used for emulsion polymerization. 相似文献
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高分子材料性能追本朔源主要由分子链微结构决定。以RAFT聚合为代表的"活性"/可控自由基聚合结合了传统自由基聚合和活性阴离子聚合各自的优点,提供了一种有效调控聚合物分子链微结构的聚合方法。RAFT乳液聚合作为"活性"/可控自由基聚合中具有工业应用前景的聚合方法,在过去二十年受到了学术界的广泛关注。本文总结了RAFT乳液聚合乳液失稳机理、聚合动力学、链结构的可控性等方面的进展。在此基础上,介绍了通过RAFT乳液聚合这一可控制备聚合物新材料的平台制备得到的新型嵌段共聚物、梯度共聚物,并展望了RAFT乳液聚合在高分子合成材料领域的应用前景。 相似文献
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Niels M.B. Smeets Ujwal S. Meda Johan P.A. Heuts Jos T.F. Keurentjes Alex M. van Herk Jan Meuldijk 《Macromolecular Symposia》2007,259(1):406-415
Summary: For the application of catalytic chain transfer in (mini)emulsion polymerization, catalyst partitioning and deactivation are key parameters that govern the actual catalyst concentration at the locus of polymerization and consequently the final molecular weight distribution. A global model, based on the Mayo equation, catalyst partitioning and deactivation was developed. The influence of several reaction parameters on the instantaneous number average molecular weight was quantified. 相似文献
18.
Stuart W. Prescott Mathew J. Ballard Ezio Rizzardo Robert G. Gilbert 《Macromolecular theory and simulations》2006,15(1):70-86
Summary: Means of improving rates in RAFT‐mediated radical emulsion polymerizations are developed, by setting out strategies to minimize the inhibition and retardation that always are present in these systems. These effects arise from the RAFT‐induced exit of radicals, the desorption of the RAFT‐reinitiating radical from the particles, and the specificity of the reinitiating radical to the RAFT agent. Methods for reducing the inhibition period such as using a more hydrophobic reinitiating radical are predicted to show a significant improvement in the inhibition periods. The time‐dependent behavior of the RAFT adduct to the entering radical and the RAFT‐induced exit (loss) of radicals from particles are studied using a previously described Monte Carlo model of RAFT/emulsion particles. It is shown that an effective way of reducing the rate coefficient for the exit of radicals from the particles is to use a less active RAFT agent. Techniques for improving the rate of polymerization of RAFT/emulsion systems are suggested based upon the coherent understanding contained in these models: the use of an oligomeric adduct to the RAFT agent, a less water‐soluble RAFT re‐initiating group, and a less active RAFT agent.
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核壳乳液聚合法制备含氟硅丙烯酸酯乳液 总被引:3,自引:0,他引:3
以氟醇RfCH2CH2OH和乙烯基硅氧烷VTES为原料合成的氟硅单体,与甲基丙烯酸甲酯、丙烯酸丁酯在复合乳化体系中通过核壳乳液聚合制备了稳定的氟硅共聚乳液。对氟硅单体和氟硅丙烯酸酯共聚物的结构用红外光谱进行了表征,结果表明,得到了目标单体和共聚物。共聚物的TEM形态观察发现,乳胶粒子具有明显的核壳结构,平均粒径在125 nm左右。与丙烯酸酯共聚物相比,氟硅丙烯酸酯共聚物乳胶膜的吸水率降低至8.32%,热分解温度提高了23℃,耐溶剂性与氟硅单体的含量关系不大。 相似文献
20.
Tian Ying GUO Dong Lin TANG Jing Wei ZHU Mou Dao SONG Bang Hua ZHANG 《中国化学快报》2006,17(9):1247-1250
As a kind of living free radical polymerizations, reversible addition-fragmentation chain transfer (RAFT) has been proved to be an important technique nowadays as it is applicable to a wide range of monomers at a wide range of temperature below 100oC. In … 相似文献