丙烯酸乙酯在炭黑表面的阴离子接枝聚合研究

丙烯酸乙酯在炭黑表面的阴离子接枝聚合研究蒋子铎，刘长生，刘安华，吴璧耀（武汉化工学院精细化工系武汉４３００７３）关键词炭黑，丙烯酸乙酯，阴离子聚合，接枝聚合由于炭黑粒子自聚力强，存在难分散、易絮凝的特点，影响其在高分子材料中的分散和分散稳定性．对此国...     

丙烯酰胺在炭黑表面接枝聚合研究

利用Ｃｅ＾４＋和羟甲基化炭黑组成的氧化还原引发体系，探讨了丙烯酰胺在炭黑表面的自由基水溶液接枝聚合机理。研究表明：单体浓度、硝酸浓度和铈盐用量直接影响丙烯酰胺在炭黑表面的接枝聚合，ＦＴＩ和ＴＥＭ分析证明：改性炭黑表面存在着聚丙烯酰胺。改性炭黑粒子的Ｚｅｔａ电位值与未改性炭黑粒子相同，但它与水组成的分散体具有极好的分散稳定性。     

苯乙烯,丙烯腈在炭黑表面的阴离子接枝聚合

反应型炭黑;苯乙烯;丙烯腈在炭黑表面的阴离子接枝聚合     

乙烯基单体在炭黑表面上的接枝聚合

讨论了分别在铈离子体系，正丁基锂体系，过渡金属离子乙酰丙酮铜（Ⅱ）以及焦磷酸络锰（Ⅲ）体系的作用下，炭黑与乙烯基单体的接枝聚合．研究了引发剂浓度、单体浓度、反应时间对接枝聚合反应的影响．利用ＦＴ ＩＲ分析确证了炭黑表面的接枝反应，利用ＴＥＭ表征了接枝炭黑的形态．结果表明，在所研究的多种炭黑表面接枝聚合体系中，正丁基锂体系的接枝率最高，可达２００％．而各种氧化还原体素的接枝率只能达到３０％左右．表面接枝后的炭黑在介质中的分散稳定性明显改善．     

苯乙烯在炭黑表面的阴离子接枝聚合研究

利用正丁基锂（ｎ－ＢｕＬｉ）与炭黑（ＣＢ）表面含氧基团反应制得了表面含－ＯＬｉ基团的反应型炭黑，以该炭黑与聚氧乙烯－聚氧丙烯－聚苯乙烯（ＰＥＯ－ＰＰＯ－ＰＳ）多嵌段聚合物组成的阴离子引发体系作活性中心，研究了苯乙烯在炭黑表面的阴离子接枝聚合。ＦＴ－ＩＲ，ＴＥＭ和ＤＳＣ分析表明在接枝炭黑表面存在苯乙烯的聚合物。接枝炭黑在甲苯中有良好的分散稳定性。     

炭黑对乙烯基单体自由基聚合反应的影响

用悬浮聚合法制备静电复印用增色剂时，着色剂炭黑在反应体系中具有明显的阻聚作用。研究了炭黑对反应活性不同的乙烯基单体和不同引发剂体系聚合反应的影响。通过在炭黑表面进行接枝，以降低炭黑对聚合反应的干扰。     

丙烯酸甲酯在炭黑表面的接枝聚合及水解

在炭黑表面接枝聚合物 ,可提高其在相应介质中的分散性[1] .乙酰丙酮合锰可以有效地引发羊毛、纤维素、淀粉等天然高分子的接枝聚合 [2～ 4 ] ,季君晖 [5]将其与羟甲基化炭黑组成引发体系 ,引发了甲基丙烯酸甲酯、丙烯酸丁酯、苯乙烯等单体在炭黑表面进行接枝聚合 .但该体系难以引发水溶性的单体 ,因此得到的接枝炭黑只能用于油性体系 .目前制备亲水性接枝炭黑大多采用 Ce4 +/羟甲基化炭黑引发体系 ,该体系对 O2 特别敏感 ,反应条件相当苛刻 .本文采用乙酰丙酮合锰与羟甲基化炭黑组成引发体系 ,引发丙烯酸甲酯在炭黑表面的接枝聚合 .在 Na…     

炭黑接枝方法与接枝炭黑应用的研究进展

炭黑接枝是常用的炭黑表面改性方法。讨论了最新的炭黑接枝方法，主要包括二次接枝法、γ-射线辐射接枝、三氯乙酰基团与六羰基钼引发乙烯基单体聚合接枝，偶联接枝与聚合物交联及其它方法；并对接枝炭黑在新材料领域的臆用作了介绍。     

超声引发自由基聚合制备聚苯乙烯磺酸钠接枝炭黑

通过在超声环境下,单体苯乙烯磺酸钠发生自由基聚合,生成的聚合物长链自由基被炭黑表面捕获,制备聚合物接枝炭黑.借助红外光谱、热重、粒度、透射电镜和zeta电位分析对该接枝炭黑进行表征.同时研究超声条件对接枝率的影响.结果表明,单体聚合并接枝到炭黑表面,同时炭黑的附聚体和一些大的聚集体结构被超声破碎,平均粒径大为减小;在300W超声波输出功率下,反应1h后,接枝率达到12.8%并趋于稳定.由于接枝分子链上磺酸基的存在,接枝炭黑在水中的分散稳定性显著改善.     

对苯乙烯磺酸钠改性炭黑对天然橡胶胶乳力学性能的影响

在Haake转矩流变仪的热机械作用下,用对苯乙烯磺酸钠(NASS)对炭黑进行预处理,制备了在水介质中具有优异的分散稳定性的亲水性纳米炭黑粒子(PNASS-CB),并将其直接用于天然橡胶胶乳的补强研究.1HNMR和FT-IR结果表明NASS在炭黑表面成功聚合包覆,用热重分析方法计算其包覆率为8.1 wt%,接枝率为2.5 wt%.亲水性炭黑的表面自由能降低,同时,Payne效应和结合胶含量表明亲水性炭黑粒子与橡胶的相互作用强于亲水性炭黑粒子之间的相互作用.因此,亲水性炭黑/天然橡胶胶乳复合材料的硫化时间变短,转化速度加快,硫化胶的撕裂强度提高了85%,拉伸强度提高了30%,断裂伸长率提高了20%.     

Graft Polymerization of Vinyl Monomers Onto Carbon Black by Use of the Redox System Consisting of Ceric Ions and Carbon Black Carrying Alcoholic Hydroxyl Groups

The radical graft polymerization of vinyl monomers onto carbon black initiated by a redox system consisting of ceric ion and carbon black having alcoholic hydroxyl groups was investigated. The introduction of alcoholic hydroxyl groups onto the carbon black surface was achieved by the reaction of carbon black with alcoholic hydroxyl radicals, formed by the reaction of alcohol with benzoyl peroxide. The rate of the polymerization of acrylamide (AAm) initiated by the redox system was found to increase in the following order of hydroxyl groups: 1-hydroxyoctyl < 1-hydroxypropyl < 1-hydroxyethyl < hydroxymethyl < 1-hydroxy-1-methylethyl. In the redox polymerization, poly-AAm was effectively grafted onto carbon black by propagation of the polymer from the radical formed by the reaction of ceric ions with the alcoholic hydroxy groups. The percentage of grafting increased with increasing conversion. By use of this redox system, poly(acrylic acid), polyacrylonitrile, and poly(N-vinyl-2-pyrrolidone) could be grafted onto carbon black, but poly(methyl methacrylate) and polystyrene could not be so grafted. The graft polymerization of AAm by use of a redox system consisting of ceric ion and PVA-grafted carbon black was also investigated.     

Radical Graft Polymerization of Vinyl Monomers Initiated by A20 Groups Introduced Onto a Carbon Black Surface: Effect of azo Groups on Graft Polymerization

The radical graft polymerization of vinyl monomers from carbon black initiated by azo groups introduced onto the surface was investigated. The introduction of azo groups onto carbon black surface was achieved by three methods: the reaction of 2,2′-azobis[2-(2-imidazolin-2-yl)propane] (AIP) with (1) epoxide groups, which were introduced by the reaction of carbon black with chlorometh-yloxirane; (2) acyl chloride groups, which were introduced by the reaction of carboxyl groups on the surface with thionyl chloride; and (3) 3-chloroformyl-1-cyano-1-methylpropyl groups, which were introduced by the reaction of carbon black with 4,4′-azobis(4-cyanovaleric acid) and then thionyl chloride. The amount of azo groups introduced onto the surface by the above methods was determined to be 0.07-0.19 mmol/g. The graft polymerization of methyl methacrylate was found to be initiated by azo groups introduced onto the carbon black surface. During the polymerization, poly(methyl methacrylate) was effectively grafted onto carbon black through propagation of the polymer from the radical produced on the surface by the decomposition of the azo groups. The percentage of grafting using carbon black having azo groups introduced by method 1 increased to 40%. It was also found that the graft polymerization of several vinyl monomers such as styrene, acrylonitrile, and acrylic acid was initiated by the azo groups introduced onto the surface and the corresponding polymer was effectively grafted onto the surface. Furthermore, the effect of the amount of carbon black having azo groups on the graft polymerization was investigated.     

Crystallinity in Free Radical Polymerized Polyvinyl p-t-butylbenzoate)

The photoinduced graft polymerization of acrylic acid and n-butyl acrylate on polyvinyl chloride or carbon monoxide-vinyl chloride copolymer by using benzophenone as a sensitizer was carried out. In graft polymerization of acrylic acid, the degree of grafting was low. However, graft polymerization of n-butyl acrylate or acrylic acid-n-butyl acrylate were higher than that of acrylic acid. Turbidimetry, DTA, and TGA of the graft polymer were examined. As the graft polymer was a weak polyacid, the pK_a was estimated according to the Henderson equation, and the relationship between pK_a and the acrylic acid unit content in the graft polymer was derived.     

Covalently attached graft polymer monolayer on organic polymeric substrate via confined surface inhibition reaction

A grafting technique was proposed for the preparation of polymer monolayer on polymeric substrate. On the basis of our recent work on polymer‐supported inhibitor (PSI), hydroquinone (HQ) was first implanted onto polypropylene (PP) surface through UV‐initiated grafting. The resulting immobilized HQ was used as PSI for the thermal‐induced free radical polymerization (FRP) of acrylic acid (AA). The inhibition mechanism was similar to that of free HQ molecule, that is, polymer chain‐carrying radical or peroxy radical could be deactivated by abstracting hydrogen atom from hydroxyl group of immobilized HQ, and the resulting oxyradical (semiquinone radical) combined with another active chain free radical. According to this mechanism, a devised redox initiator consisting of sodium hydrogen sulfite and ammonium persulfate was used to initiate FRP of AA in water at low temperature (50 °C). High crystalline biaxial oriented PP film with HQ immobilized was deliberately laid in this system as a radical trap to capture poly(acrylic acid) (PAA) short chain radical. Through X‐ray photoelectron spectra (XPS) analysis it was found that the atom ratio of C_HQ (carbon in HQ) to C_COOH (carbon in COOH) decreased with prolonging polymerization time and became stable after about 30 min. The formed PAA short chain on the surface showed a distribution of monolayer, and the saturated thickness was calculated as 5–7 Å. The degree of polymerization of graft chain in PAA monolayer was estimated as 15–20 through three different models. Relating to surface coverage being 100% in ideal densely packed PAA monolayer, real monolayer surface coverage in such reaction system was estimated as 12.3–18.5%. This method was expected to give us a general approach for constructing kinds of graft polymer monolayer on polymeric substrate, because the involved chemistry was only common inhibition reaction between immobilized inhibitor (HQ) and FRP system in solution (herein redox initiating system of AA). We named this grafting chemistry as confined surface inhibition reaction. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 745–755, 2007     

Photo-grafting Poly(acrylic acid) onto Poly(lactic acid) Chains in Solution

Poly(lactic acid)(PLA)is one of the most important bio-plastics,and chemical modification of the already-polymerized poly(lactic acid)chains may enable optimization of its material properties and expand its application areas.In this study,we demonstrated that poly(lactic acid)can be readily dissolved in acrylic acid at room temperature,and acrylic acid can be graft-polymerized onto poly(lactic acid)chains in solution with the help of photoinitiator benzophenone under 254 nm ultraviolet(UV)irradiation.Similar photo-grafting polymerization of acrylic acid(PAA)has only been studied before in the surface modification of polymer films.The graft ratio could be controlled by various reaction parameters,including irradiation time,benzophenone content,and monomer/polymer ratios.This photo-grafting reaction resulted in high graft ratio(graft ratio PAA/PLA up to 180%)without formation of homopolymers of acrylic acid.When the PAA/PLA graft ratio was higher than 100%,the resulting PLA-g-PAA polymer was found dispersible in water.The pros and cons of the photo-grafting reaction were also discussed.     

聚合物基板表面状态对异相接枝的影响研究

研究了对于羟丙基纤维素（HPC）基板进行表面修饰时,基板表面状态的调控 对基板表面化学接枝的影响。用双官能团化合物2,4-甲苯二异氰酸酯（TDI）作为 接枝桥梁,其对位的异氰酸酯基先和基板上的羟基反应,保留的邻位异氰酸酯基进 一步再与丙烯酸的羟基反应,让接枝在基板上的活性丙烯酸分子继续和丙烯酸溶液 聚合,通过这种途径在基板表面修饰聚丙烯酸。基板制备时,由于不同介质对HPC 基板表面的不同诱导作用,导致表面组成各异,大大影响了接枝反应的效果。红外 光谱和二次离子飞行时间质谱均证明了可以用2,4-甲苯-二异氰酸酯（TDI）分子 做接枝桥梁在基板表面异相接枝上羟基并进一步接枝聚丙烯酸,从而达到修饰基板 的目的。     

含磺酸基单体在炭黑表面接枝共聚合

近年来,炭黑粒子在水性体系中的分散稳定性倍受人们关注。研究认为影响炭黑分散稳定的主要因素为炭黑颗粒之间的相互作用力（包括电磁力、静电排斥力和空间位阻力等）和炭黑粒子与分散介质之间的相互作用力。目前,实现炭黑在水性体系中良好分散所采用的方法主要有炭黑氧化法、分散剂法和炭黑高分子接枝法,其中以炭黑高分子接枝方法效果最佳。     

Patterned immobilization of biomolecules by using ion irradiation‐induced graft polymerization

A new method for biomolecular patterning based on ion irradiation‐induced graft polymerization was demonstrated in this study. Ion irradiation on a polymer surface resulted in the formation of active species, which was further used for surface‐initiated graft polymerization of acrylic acid. The results of the grafting study revealed that the surface graft polymerization using 20 vol % of acrylic acid on the poly(tetrafluoroethylene) (PTFE) film irradiated at the fluence of 1 × 10¹⁵ ions/cm² for 12 h was the optimum graft polymerization condition to achieve the maximum grafting degree. The results of the fluorescence microscopy also revealed that the optimum fluence to achieve the maximum fluorescence intensity was 1 × 10¹⁵ ions/cm². The grafting of acrylic acid on the PTFE surfaces was confirmed by a fluorescence labeling method. The grafted PTFE films were used for the immobilization of amine‐functionalized p‐DNA, followed by hybridization with fluorescently tagged c‐DNA. Biotin‐amine was also immobilized on the acrylic acid grafted PTFE surfaces. Successful biotin‐specific binding of streptavidin further confirmed the potential of this strategy for patterning of various biomolecules. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6124–6134, 2009