Some novel accelerating agents for nitroxide‐mediated living free‐radical polymerization

Malononitrile (MN), trifluoroacetic acid anhydride, acetylacetone, acetoacetic ester, and diethyl malonate have been identified as novel rate‐accelerating additives for nitroxide‐mediated living free‐radical polymerization. Among these additives, MN has the greatest accelerating effect. Adding MN at an MN/2,2,6,6‐tetramethylpiperidine‐oxyl (TEMPO) molar ratio of 4.0 results in a nearly 20 times higher rate of polymerization of styrene (St), and adding MN at an MN/TEMPO molar ratio of 2.5 results in a nearly 15 times higher rate of copolymerization of St and methyl methacrylate. The polymerization of St proceeds in a living fashion, as indicated by the increase in the molecular weight with time and conversion and the relatively low polydispersity. The polymerization rate of St is so quick that the conversion reaches 70% within 1 h at 125 °C when the molar ratio of MN to TEMPO is 4:1. Moreover, the reaction temperature can be reduced to 110 °C. A possible explanation for this effect is that the formation of hydrogen bonds between the MN and TEMPO moiety weakens the C? ON bond at the end of the polymer chain. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5246–5256, 2005     

Free-Radical Copolymerizations of N-Phenyl Maleimide

Free radical-initiated copolymerization of N-phenyl maleimide (NPMI) with styrene (St), vinyl acetate (VAc) and methyl meth-acrylate (MMA) at 35°C in benzene solution initiated by AIBN was studied. The copolymerization of NPMI and St yields a “nearly equimolecular” alternating copolymer, irrespective of monomer feed. Reactivity ratios of NPMI with St, VAc, and MMA were determined by a curve-fitting method which has the advantage of delivering values not involving personal judgement. Q₁ and e₁ values of NPMI were also calculated. Tentative explanations have been proposed to Interpret the “nearly alternating” copolymerization between NPMI and St. In addition, thermal stabilities of copolymers were studied by using a programmed thermo-gravimetric analysis technique. Copolymers of St, VAc, and MMA show a considerable increase in thermal stability with increasing content of NPMI. The glass transition temperatures of copolymers of NPMI with MMA and St were measured by differential scanning calorimetry. In both series of copolymers the glass transition temperature increases markedly with increasing in NPMI content. In the case of NPMI-St copolymers, the relative thermal stability as well as glass transition temperature also corroborated the nearly alternating behavior observed.     

水分散体系中苯乙烯和甲基丙烯酸甲酯梯度共聚物的合成与表征

以2-溴代异丁酸乙酯(EBiB)为引发剂,CuBr/CuBr₂/1,10-邻二氮菲(phen)为复合催化剂,十二烷基磺酸钠(SLS)为乳化剂,考察了水分散体系中苯乙烯(St)和甲基丙烯酸甲酯(MMA)的原子转移自由基共聚合的可控性和相对反应活性.在此基础上,通过反应进料法在水分散体系中进行了St和MMA的梯度共聚合,反应表现出“活性”聚合的特征,即所得共聚物的数均分子量随着单体转化率的增加而增大,分子量分布较窄(M_w/M_n<1.50).用¹HNMR跟踪分析了聚合反应过程中共聚物微观组成的变化规律,结果表明,共聚物链中MMA链节的累积含量和瞬时含量都随着共聚物相对链长的增加而增加,即随着聚合物相对链长的增加共聚物的微观组成从St链节占主导地位逐渐变化为以MMA链节占主导地位,表明确实形成了St和MMA的梯度或渐变共聚物.     

Reversible addition–fragmentation transfer (RAFT) copolymerization of methyl methacrylate and styrene in miniemulsion

In the reversible addition–fragmentation transfer (RAFT) copolymerization of two monomers, even with the simple terminal model, there are two kinds of macroradical and two kinds of polymeric RAFT agent with different R groups. Because the structure of the R group could exert a significant influence on the RAFT process, RAFT copolymerization may behave differently from RAFT homopolymerization. The RAFT copolymerization of methyl methacrylate (MMA) and styrene (St) in miniemulsion was investigated. The performance of the RAFT copolymerization of MMA/St in miniemulsion was found to be dependent on the feed monomer compositions. When St is dominant in the feed monomer composition, RAFT copolymerization is well controlled in the whole range of monomer conversion. However, when MMA is dominant, RAFT copolymerization may be, in some cases, out of control in the late stage of copolymerization, and characterized by a fast increase in the polydispersity index (PDI). The RAFT process was found to have little influence on composition evolution during copolymerization. The synthesis of the well‐defined gradient copolymers and poly[St‐b‐(St‐co‐MMA)] block copolymer by RAFT miniemulsion copolymerization was also demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6248–6258, 2004     

乙烯基单体与含氮氧稳定自由基单体的原子转移自由基共聚合研究

通过苯乙烯或甲基丙烯酸甲酯与含氮氧稳定自由基的单体进行原子转移自由基共聚合 ,研究了共聚合反应的条件及动力学 ,成功地合成出侧链含TEMPO基团的氮氧稳定自由基聚合大分子引发剂 .大分子引发剂的结构通过核磁共振谱图进行确证 ,并对共聚合反应的历程进行了探讨     

Amphoteric initiators suitable for emulsifier-free emulsion polymerization and the properties of the resulting latices

The soap-free emulsion polymerizations of styrene (St) and acrylamide (AAm) or methyl methacrylate (MMA) were carried out in the presence of three kinds of amphoteric initiators, and the polymerization kinetics and the colloidal properties of the latices produced were emphatically investigated. It was found that the number of carbon atoms between the amidino and carboxyl groups in each initiator exhibited an appreciable effect on the dissociation as well as on the solubility of the initiator in water, and therefore, that the properties of the colloidal particles depended on the structure of the initiators used. All the copolymerization runs, except for the polymerization using 2,2′-azobis(N-(2-caboxyethyl)-2-methylpropionamidine) under a strongly alkali condition, gave amphoteric latices, which indicated higher critical flocculation concentrations at lower or higher pHs than at a medium pH. The surface charge density measured by titration for poly(St/MMA) particles was about 3–10 times as high as that for the poly(St/AAm) ones, though these were prepared under the same conditions other than the monomer composition. The influence of the polymerization pH on both the polymerization rate and the surface charge density of the resulting latices was negligible even if the constants of the decomposition rate and the dissociation of the amphoteric initiators strongly depended on the pH of the medium. Received: 28 July 2000 Accepted: 1 November 2000     

Effects of solvent as an electron-pair acceptor on propagation reactions during radical polymerization and copolymerization of polar vinyl monomers

We carried out radical homopolymerization and copolymerization in various kinds of solvents at 60°C by using diisopropyl fumarate (DiPF) and methyl methacrylate (MMA) as electron-accepting polar monomers and styrene (St) and vinyl benzoate (VB) as electron-donating monomers. The highest polymerization rate was observed in the polar and electron-pair accepting solvents, such as 2,2,2-trifluoroethanol for the homopolymerization and copolymerization of these monomers. It has been revealed that the polymerization rate is correlated to the electron-pair–accepting property of the solvent used, rather than the polarity in the linear free energy relationship. We have demonstrated the validity of the acceptor number as the index for interpreting the interaction of the solvent with the monomer and the propagating chain end. The monomer reactivity ratios were determined for the St–DiPF, VB–DiPF, and St–MMA copolymerizations. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2803–2814, 1999     

Polymerization of vinyl monomers by alkali metal–thiobenzophenone complexes

The polymerization of vinyl monomers by use of alkali metal (Li, Na, K)–thiobenzophenone complexes was studied. Monoalkali metal complexes of thiobenzophenone (thioketyls) induced the polymerization of vinyl monomers such as acrylonitrile (AN) and methyl methacrylate (MMA), and dialkali metal complexes of thiobenzophenone (dianion) induced the polymerization of styrene (St), butadiene (Bd), and isoprene (Ip) as well as AN and MMA. The polymerization of MMA with the dianion was initiated by both the mercaptide and the carbanion of the dianion, but that of styrene was initiated by the carbanion alone. In the case of polymerization of MMA by the thioketyl, the initial rate of polymerization depended on the catalyst concentration and the square of the monomer concentration. Similar results were obtained in the case of the dianion. The polymer yield increased with increasng polarity of sovents. In the copolymerization of AN with MMA, the copolymer obtained consisted almost of AN units. From these results, it was concluded that the polymerization proceeded by anionic mechanisms.     

Mechanism of alternating copolymerization of methyl methacrylate with styrene in the presence of diethylaluminum chloride

A kinetic study of the propagation mechanism of the alternating copolymerization of styrene (St) with methyl methacrylate (MMA) in the presence of a complexing agent (diethylaluminum chloride, DEAC) in bulk and in tetrachloroethylene solutions at a molar ratio DEAC/MMA = 0.5 has been carried out. It has been shown that the copolymerization is a chain radical process characterized by a short active-center lifetime, bimolecular termination, and high rate of chain transfer to the complexed MMA. A kinetic scheme has been proposed for the propagation mechanism of alternating copolymerization in the presence of a complexing agent not requiring independent measurements of the equilibrium constant of complexation. It has been found that spontaneous and UV-initiated copolymerizations in the system have different mechanisms of initiation and a common mechanism of propagation. The propagation proceeds by addition of single monomers as well as donor-acceptor complexes of the comonomers to the propagation radicals, with the first mechanism being predominant. Inclusion of the monomers in the complex leads to an increase of the St reactivity and to a decrease of the MMA reactivity in propagation to the corresponding macroradicals in comparison with the reactivity of the free monomers. A number of kinetic and statistical parameters of the propagation reaction have been calculated.     

Effect of triphenyl phosphite on the radical polymerization of styrene and methyl methacrylate

The effects of triphenyl phosphite (TPP) on the radical polymerization of styrene (St) and methyl methacrylate (MMA) initiated with α,α,-azobisisobutyronitrile (AIBN) was investigated at 50°C. The rate of polymerization of St and MMA at a constant concentration of TPP was found to be proportional to the monomer concentration and the square root of the initiator concentration. The rate of polymerization and the degree of polymerization of both St and MMA increased with increasing TPP concentration. The accelerating effect was shown to be due to the decrease of the termination rate constant k_t with an increase in the viscosity of the polymerization systems. The chain transfer constant C_tr of TPP in St and MMA systems was determined from the degree of polymerization system. The C_tr of TPP was almost zero in the St system and 6.5 × 10^?5 in the MMA system.     

Copolymerization kinetics of methyl methacrylate-styrene obtained by PLP-MALDI-ToF-MS

The combination of MALDI-ToF-MS and pulsed laser polymerization has been used to study the propagation rate coefficients for the copolymer system styrene-methyl methacrylate. For the first time, complete information regarding mode of termination, reactivity of photoinitiator-derived radicals, copolymer molecular mass, chemical composition, and copolymerization rates is obtained interrelated. The polymerizations were carried out in bulk with varying styrene concentrations at a temperature of 15.2 degrees C by an excimer pulsed laser with varying frequencies. Both chemical composition distributions and molecular weight distributions were determined by MALDI-ToF-MS. The data were fitted to the implicit penultimate unit model and have resulted in new point estimates of the monomer and radical reactivity ratios for the copolymer system styrene-methyl methacrylate: r(St) = 0.517, r(MMA) = 0.420, s(St) = 0.296, s(MMA) = 0.262. Comparison between Monte Carlo simulations and the obtained results further confirmed the very successful combination of pulsed laser copolymerization experiments with MALDI-ToF-MS. The obtained results are believed to be the most accurate and complete set of copolymerization parameters to date.     

甲基丙烯酸甲酯和二乙烯苯对苯乙烯共聚合的影响

以甲基丙烯酸甲酯(MMA)、苯乙烯(St)和二乙烯苯(DVB)三元共聚体系为研究对象,采用气相色谱法研究了体系中MMA和DVB浓度对聚苯乙烯型树脂交联的影响。结果表明:MMA加速St和DVB的聚合速率,其中对St的加速作用又明显大于对DVB的。随MMA含量的增加,聚苯乙烯型树脂交联不均匀的情况得以明显改善,而增加体系中DVB的含量,DVB与St、MMA反应速率的差异变大,树脂交联不均匀的情况变严重。     

可聚合的光引发转移终止剂合成接枝共聚物

采用一种可聚合的光引发转移终止剂 ,2 N ,N 二乙基二硫代氨基甲酰氧基乙酸 β 甲基丙烯酰氧基乙酯 (MAEDCA) ,通过两种途径制备了含有聚甲基丙烯酸甲酯 (PMMA)和聚苯乙烯 (PSt)链段的接枝共聚物 .其一是将MAEDCA作为引发剂 ,在紫外光照射下引发MMA聚合 ,得到大分子单体 ,通过大分子单体与St的共聚合得到 .考察了所用大分子单体的分子量和浓度对共聚合的影响 .其二是将MAEDCA作为单体与MMA共聚得到侧链上含有N ,N 二乙基二硫代氨基甲酰氧基 (DC)基团的无规共聚物 ,P(MMA co MAEDCA) .在紫外光照射下 ,P(MMA co MAEDCA)作为大分子引发剂引发St聚合 ,得到P(MMA co MAEDCA) g PSt的共聚物 ,研究了接枝共聚合过程的活性自由基聚合特征     

悬浮-乳液复合聚合聚苯乙烯-聚甲基丙烯酸甲酯复合粒子的颗粒特性和成粒机理

采用在苯乙烯 (St)悬浮聚合过程中滴加甲基丙烯酸甲酯 (MMA)乳液聚合组分的悬浮 乳液复合聚合方法 ,制备大粒径聚苯乙烯 聚甲基丙烯酸甲酯 (PS PMMA)复合粒子 .研究聚合物粒径分布和颗粒形态的变化发现 ,在St悬浮反应中期滴加MMA乳液聚合组分后 ,聚合体系逐渐由悬浮粒子与乳胶粒子并存向形成单峰分布复合粒子转变 ,最终形成核 壳结构完整的大粒径PS PMMA复合粒子 ;在St悬浮反应初期滴加MMA乳液聚合组分 ,St与MMA一起分散成更小液滴 ,反应后期凝并成非核 壳结构复合粒子 ;在St悬浮反应后期滴加MMA乳液聚合组分 ,PMMA乳胶粒子与PS悬浮粒子基本独立存在 .根据以上结果 ,提出了St MMA悬浮 乳液复合聚合的成粒机理 .     

Kinetic and ESR studies on radical polymerization of methyl methacrylate in the presence of fullerene

The effect of fullerene (C₆₀) on the radical polymerization of methyl methacrylate (MMA) in benzene was studied kinetically and by means of ESR, where dimethyl 2,2′-azobis(isobutyrate) (MAIB) was used as initiator. The polymerization rate (R_p) and the molecular weight of resulting poly(MMA) decreased with increasing C₆₀ concentration ((0–2.11) × 10⁻⁴ mol/L). The molecular weight of polymer tended to increase with time at higher C₆₀ concentrations. R_p at 50°C in the presence of C₆₀ (7.0 × 10⁻⁵ mol/L) was expressed by R_p = k[MAIB]^0.5[MMA]^1.25. The overall activation energy of polymerization at 7.0 × 10⁻⁵ mol/L of C₆₀ concentration was calculated to be 23.2 kcal/mol. Persistent fullerene radicals were observed by ESR in the polymerization system. The concentration of fullerene radicals was found to increase linearly with time and then be saturated. The rate of fullerene radical formation increased with MAIB concentration. Thermal polymerization of styrene (St) in the presence of resulting poly(MMA) seemed to yield a starlike copolymer carrying poly(MMA) and poly(St) arms. The results (r₁ = 0.53, r₂ = 0.56) of copolymerization of MMA and St with MAIB at 60°C in the presence of C₆₀ (7.15 × 10⁻⁵ mol/L) were similar to those (r₁ = 0.46, r₂ = 0.52) in the absence of C₆₀. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2905–2912, 1998     

Long-lived polymer radicals. IV. Reactions of poly(N-methylacrylamide) and poly(N-methylmethacrylamide) radicals with binary mixtures of vinyl monomers

N-methylacrylamide (NMAAm) and N-methylmethacrylamide (NMMAm) were polymerized to give polymer microspheres containing living propagating radicals. The microsphere polymer radicals were allowed to react with some binary mixtures of vinyl monomers including alternating copolymerization combinations. The reaction processes were investigated by ESR spectroscopy. In the poly(NMMAm) radical/methyl methacrylate (MMA)/styrene (St) system, the propagating radical from MMA was mainly observed at the higher MMA concentration, while polySt radical prevailed at the lower MMA concentration. In the poly(NMMAm) radical/α-methylstyrene (α-MeSt)/diethyl fumarate system, the α-MeSt radical was exclusively observed, while the maleic anhydride (MAn) radical was predominantly observed in the α-MeSt/MAn system. In the MAn/diphenylethylene system, the propagating radicals from both monomers were observed at comparable concentrations. The poly(NMAAm) microsphere radical behaved differently in the reaction with the MMA/St mixture. The poly(NMAAm) microsphere was found to incorporate preferentially St, leading to formation of the St radical. The St preference was enhanced in the St/cyclohexyl methacrylate (CHMA) system. These results were in agreement with those of block copolymerization via the reaction of poly(NMAAm) radical with the MMA/St or CHMA/St mixture, where the compositions of the resulting polymers were analyzed by pyrolysis gas chromatography.     

Synthesis and characterization of linear ABC triblock copolymer of ethylene oxide,methyl methacrylate,and styrene

A well‐defined linear ABC triblock copolymer of ethylene oxide (EO), methyl methacrylate (MMA), and styrene (St) was prepared by sequential living anionic and photo‐induced charge transfer polymerization (CTP) using p‐aminophenol as parent compound. In the first step, the diblock copolymer of PEO‐b‐PMMA with a protected aniline end group at PEO end was prepared by initiating of phenoxo‐anion the polymerization of EO and MMA successively, then the diblock copolymer of PEO‐b‐PMMA via deprotection of aniline at PEO end constituted a binary initiation system with benzophenone (BP) by charge transfer complex mechanism to initiate the polymerization of St under UV‐irradiation. The GPC and NMR measurements support that in copolymerization, either in the first or second step, neither homopolymer nor side reactions, such as chain transfer or chain termination, was found. The effect of the concentration of PEO_a‐b‐PMMA and St, and the polarity of solvent on the polymerization rate (R_p) of CTP is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 825–833, 1999     

耐热性星形甲基丙烯酸甲酯共聚物的合成

195 6年 ,Swarzc等 [1,2 ] 报道了一种没有链转移和链终止的阴离子聚合技术 ,提出了“活性”聚合的概念 . 1 995年王锦山等 [3]发现和提出原子转移自由基聚合 ( ATRP)以来 ,活性自由基聚合就成了高分子合成领域的研究热点 ,并合成出各类指定结构的聚合物 [4～ 12 ] .具有环状结构的 N -环己基马来酰亚胺 ( NCMI)被广泛地用于与甲基丙烯酸甲酯 ( MMA)自由基共聚合制备耐热性有机透明材料 [13,14 ] ,但NCMI的引入将降低聚合物的加工流动性 ,若能利用多官能团引发剂如四溴甲基苯实现含 NCMI单体结构的可控 ATRP共聚合 ,合成出星形耐…     

一种大分子引发剂的引发作用研究

将溶液聚合合成的α-甲基苯乙烯(AMS)和甲基丙烯酸缩水甘油酯(GMA)的低相对分子质量共聚物(计为PAG)作为大分子引发剂,分别研究了PAG引发单体甲基丙烯酸甲酯(MMA)和苯乙烯(St)的本体聚合反应,采用GPC和FTIR等手段对聚合产物进行了表征.研究结果表明,在加热到一定温度时,PAG具有引发作用,可以引发MMA和St进行本体聚合反应;聚合产物具有再引发功能,且其分子量与聚合物产率和聚合反应时间之间均有较好的线性关系.     

Kinetics and mechanism of emulsifier-free emulsion copolymerization: Styrene-methyl methacrylate-acrylic acid system

The emulsifier-free emulsion copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of functional monomer acrylic acid (AA) was carried out in batch process. The kinetics was investigated in detail using model function, Integrated Gamma Function. The morphology and size of particles were monitored continuously by TEM all along the polymerization. It was found that the nucleation, polymerization rate increase with increasing concentration of the functional monomer AA, initiator ammonium persulfate (APS), and polymerization temperature T, and APS plays a predominant role in the particle nucleation process. The particle nucleation stage ceased at about 10% conversion and the steady stage can be extended to about 70% conversion. The particle nucleation is likely to yield primary particle via the mechanism of homogeneous coagulative nucleation and coagulation of the primary particle to yield uniform particles. The particle growth in the postnucleation stage is via a shell growth mechanism. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2649–2656, 1999