4-乙烯基吡啶-氯化锌络合物与电子给体单体光照下共聚合研究

受电子单体4-乙烯基吡啶-氯化锌络合物(4-VP)_2ZnCl_2(M_1)可以和电子给体单体如苯乙烯(M_2)在365nm光照下共聚合。聚合是二者形成的基态电荷转移复合物(CTC)吸收光后产生自由基引发的。测得竞聚率为r_1=2.04,r_2=0.23。对溶剂极性的影响和(4-VP)_2Znal_2与其它电子给体单体光照下共聚合也作了研究。     

Termination Rates in Free Radical Copolymerizations

The rates of free radical copolymerizations at given rates of initiation can be analyzed ideally in terms of monomer feed concentrations and reactivity ratios, propagation rate constants for homopolymerizations of the particular monomers, and an overall rate constant for termination during copolymerization. This model, which is due to Atherton and North, can account for the effects of initiator concentration and viscosity of the polymerization medium on copolymerization rates.

This article reports an empirical formulation for the overall termination rate constant in terms of monomer concentrations and reactivity ratios and a cross-termination factor. The new model accounts for experimental data in the styrene-methyl methacrylate system in which polarity differences between unlike radicals may result in enhanced termination rates. It also predicts observed copolymerization rates of methyl methacrylate-vinyl acetate and styrene-α-methylstyrene mixtures in which polarity effects are absent. The cross-termination factor may be approximated from reactivity ratio data for predictive purposes.     

全氟甲基乙烯基醚和其它含氟单体乳液共聚合的竞聚率测定

分别通过气相色谱法测定了全氟甲基乙烯基醚 (PMVE)与偏氟乙烯 (VDF)以及PMVE与四氟乙烯(TFE)二元乳液共聚反应中的气相单体组成和共聚物组成 ,然后用非线性回归法 (RREVM )计算得TFE PMVE及VDF PMVE乳液共聚合反应的表观竞聚率分别为γTFE =3 89和γPMVE =0 0 5以及γVDF =1 0 6和γPMVE =0 11.结合已经测定的TFE VDF二元乳液共聚的表观竞聚率 ,计算了由VDF TFE PMVE三元乳液共聚合反应合成的共聚物组成 ,后者与由1 9F NMR实测的共聚物组成吻合     

丙烯酸甲酯/4-丙烯酰胺基-2,2,6,6-四甲基哌啶光共聚合体系的竞聚率和序列分布研究

以丙烯酸甲酯(MA,M1)和4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP,M2)溶液光共聚合体系为研究对象,采用1H-NMR手段测定了MA/AATP共聚物的组成,用Mayo-Lewis积分法和扩展Kelen-Tüdos方法计算的竞聚率分别为0.88相似文献   

有电荷转移络合物参与的共聚体系竞聚率

从有电荷转移络合物参与的共聚体系增长基元反应出,提出一种有ＣＴＣ参与的共聚体系竞聚率的求法,从中得到４个竞聚率,自由单体和ＣＴＣ的相对活性等信息。     

Alternating copolymerization of polar vinyl monomers in the presence of zinc chloride. I. Propagation and initiation of the copolymerization of acrylonitrile with styrene copolymer

Copolymerization of acrylonitrile with styrene spontaneously occurred on addition of zinc chloride without addition of any other radical initiator. The composition of the copolymer approached that of strictly alternating copolymer as zinc chloride added to the copolymerization system increased. The significance of the apparent monomer reactivity ratios of this copolymerization system was studied from a kinetic point of view, and it was shown that the monomer sequence distribution is indicated by the apparent monomer reactivity ratios. Further, equations which represent the relation between the apparent monomer reactivity ratios and Q,e values at a given salt concentration were derived. These equations reasonably accounted for the decrease of the apparent monomer reactivity ratios of the copolymerization of acrylonitrile with styrene in the presence of zinc chloride and the behavior of the other acrylonitrile copolymerization systems in the presence of zinc chloride. The initiation step of the spontaneous radical copolymerization of acrylonitrile with styrene in the presence of zinc chloride was explained by a cross-initiation mechanism.     

EFFECTS OF SOLVENT POLARITY ON FREE RADICAL COPOLY MERIZATION OF 5-HEXENOIC ACID AND ACRYLONITRILE

The effects of solvent polarity on free radical copolymerization of 5-hexenoie acid and acrylonitrile at 60℃ were studied. It was observed thatas the polarity of solvents enhanced, both the copolymcrization rate and the reactivity ratios r_1, r_2 increased, while the alternating tendency of monomer units in copolymer chain decreased. It is believed that the solvent polarity raises the reactivities of acrylonitrile monomer and its growing chain radical, but causes no distinct variation in those of 5-hexenoic acid.     

Free‐radical copolymerization of ethyl α‐hydroxymethylacrylate with methyl methacrylate by reversible addition–fragmentation chain transfer

The controlled free‐radical homopolymerization of ethyl α‐hydroxymethylacrylate and copolymerization with methyl methacrylate were performed in chlorobenzene at 70 °C by the reversible addition–fragmentation chain transfer polymerization technique with 2,2′‐azobisisobutyronitrile as the initiator. 2‐Phenylprop‐2‐yl dithiobenzoate and 2‐cyanoprop‐2‐yl dithiobenzoate were used as chain‐transfer agents in the homopolymerization, whereas only the former was used in the copolymerization. All reactions presented pseudolinear kinetics. The effect of the monomer feed ratio on the copolymerization kinetics was examined. The conversion level decreased when the proportion of ethyl α‐hydroxymethylacrylate in the monomer feed was larger. Kinetic studies indicated that the radical polymerizations proceeded with apparent living character according to experiments, demonstrating an increase in the molar mass with the monomer conversion and a relatively narrow molar mass distribution. All copolymers were statistical in chain structure, as confirmed by determinations of the monomer reactivity ratios. The monomer reactivity ratios were determined, and the Mayo–Lewis terminal model provided excellent predictions for the variations of the intermolecular structure over the entire conversion range. Additionally, the chemical modification of poly(ethyl α‐hydroxymethylacrylate) was carried out to introduce glucose pendant groups into the structure. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5618–5629, 2006     

Statistical copolymers of styrene and 2-vinylpyridine with trimethylsilyl methacrylate and trimethylsilyloxyethyl methacrylate

Statistical copolymers of styrene with trimethylsilyl methacrylate, STMS, and trimethylsilyloxyethyl methacrylate, STME, and of 2-vinylpyridine with trimethylsilyloxyethyl methacrylate, VTME were prepared by free radical copolymerization in benzene with 2,2′-azobisisobutyronitrile, AIBN. The reactivity ratios of the different monomers were estimated using the Finemann-Ross, the inverted Finemann-Ross, and the Kelen-Tüdos or the extended Kelen-Tüdos graphical methods. Structural parameters of the copolymers were obtained by calculating the diad sequence fractions, which were derived using the monomer reactivity ratios. The results were compared with those obtained from the copolymerization of styrene and 2-vinylpyridine with methacrylic acid and 2-hydroxyethyl methacrylate.     

Copolymerization of ethylene with a homologous series of vinyl esters

The effect of the alkyl group on the relative reactivity of a homologous series of vinyl esters (2) has been studied with ethylene (1) as reference monomer, tert-butyl alcohol as solvent, at 62°C and 35 kg/cm². The experimental method was based on frequent measurement of the monomer feed composition throughout the copolymerization reaction by means of quantitative gas-chromatographic analysis. Highly accurate monomer reactivity ratios were estimated in a statistically justified manner by a nonlinear least-squares method applied to the integrated copolymer equation. The reactivity of the vinyl ester monomers towards an ethylene radical increased with decreasing electron-with-drawing ability of the ester group. All vinyl ester radicals considered turned out to have the same preference for their own monomer over ethylene (constant r₂ = 1.50). Reactivity ratios are discussed in terms of the Q–e scheme and the Taft relation. It appeared that chiefly polar factors contribute to the observed relative reactivity, while probably resonance stabilization only plays a minor part. Steric hindrance seems to impair monomer reactivity, only from vinyl pivalate on. Relative reactivities of the vinyl esters are compared with literature values, where other reference monomers have been used.     

TiCl_4/MgCl_2催化丙烯/1-辛烯共聚合研究

本文用TiCl_4/MgCl_2-Al(i-Bu)_3催化剂进行丙烯/1-辛烯共聚合,研究发现引入少量共聚单体1-辛烯时,能提高丙烯的聚合活性。30℃时,测得共聚合竟聚率为r_丙=5.63,r_辛=0.32。共聚物的结晶度和己烷不溶物含量随其1-辛烯含量的增加而迅速下降。X射线衍射及~(13)C-NMR测定结果表明,共聚物的己烷可溶部分为非结晶的无规共聚物,己烷不溶部分是具有镶嵌着半个1-辛烯单体单元的长嵌段聚丙烯链结构的结晶性共聚物。     

HEMA—NVP—St三元共聚体系中单体的表观竞聚率

本文采用计算机数字积分和单纯形调优法根据Alfrey-Goldfinger共聚方程微分式,从HEMA-NVP—St三元共聚高转化率体系的转化率一组成数据,直接求算了各单体的表观竞聚率,用求得的表观竞聚率计算的转化率一组成曲线,与实验值符合很好。讨论了单体部分互溶对表观竞聚率的影响。发现在此三元共聚体系中,引入少量的均化剂,可以明显改善St与其它单体的互溶程度,使相应的表观竞聚率显著降低。     

氯乙烯/N-取代马来酰亚胺共聚竞聚率及共聚物组成

研究了氯乙烯(VC)与多种N-取代马来酰亚胺的溶液共聚合,求得各对单体的竞聚率.结果表明,各种马来酰亚胺的竞聚率都远高于VC的竞聚率,即N-取代马来酰亚胺单体的活性均比VC单体活性高.计算得到N-取代马来酰亚胺Q和e值.由于苯环的共轭效应,N-苯基及N-取代苯基马来酰亚胺具有较大的Q值.各对单体的e值差别较大,表明有形成交替共聚物的倾向.此外,还考察了聚合过程中共聚物组成的变化,用递推法预测了这类体系共聚物瞬时和累积组成随转化率的变化.     

二乙基二烯丙基氯化铵均聚及其与丙烯酰胺或丙烯酸共聚动力学研究

采用膨胀计法研究了以过硫酸铵为引发剂,二乙基二烯丙基氯化铵(DEDAAC)在水溶液中的均聚及其与丙烯酰胺(AM)和丙烯酸(AA)共聚动力学,测定了相应的聚合表观活化能;采用元素分析法测定了DEDAAC分别与AM和AA在低转化率下共聚物的组成,并采用氯离子选择性电极法测定了DEDAAC-AM共聚物中的氯离子含量,按Kelen-Tudos方法求得了相应的竞聚率.结果表明,DEDAAC均聚速率方程为RP=k[M]0.99[I]0.76,表观活化能Ea=77.00kJ/mol,说明链终止为单基终止和双基终止并存,引发过程与单体浓度无关;DEDAAC与AM在摩尔比为4∶1时,共聚动力学方程为RP=[M]2.53[I]0.90,表观活化能Ea=67.06kJ/mol,单体竞聚率为rDE=0.31±0.02、rAM=5.27±0.53;DEDAAC与AA在摩尔比为4∶1时,共聚动力学方程为RP=k[M]2.94[I]0.83,表观活化能Ea=70.07kJ/mol,竞聚率为rDE=0.28±0.03、rAA=5.15±0.28;DEDAAC与AM和AA等共聚为非理想共聚,得到的产物均为无规共聚物.     

“Living”/controlled radical copolymerization of N-phenylmaleimide and styrene using Fréchet-type dendritic initiators

Polyarylether dendrons as macroinitiators for the "living"/controlled free radical copoly-merization of N-phenylmaleimide (PhMI) and styrene (St) have been demonstrated. The copoly-merization was carried out in bulk or anisole with CuBr/bipy catalyst at 100-130℃. It is found that the resulting copolymers possess predetermined molecular weights and narrower polydispersities (1.18 < Mw/Mn<1.32). The effects of reaction temperature and monomer feed on the copolymeri-zation kinetics were investigated in detail. By using the Fineman-Ross method, the apparent monomer reactivity ratios for the atom transfer radical copolymerization of PhMI and St were determined to be rphM1 = 0.0207, and rst = 0.0484, respectively.     

对氯甲基苯乙烯与丙烯腈、甲基丙烯酸酯类的自由基共聚研究

<正> 对氯甲基苯乙烯(p-CMS)是合成功能高分子的一个非常有用的起始单体,利用它的均聚以及与其它烯类单体的共聚反应,可制得含活性基团的高分子材料。但以往对该单体的聚合及共聚研究,较多的是以邻、间、对位氯甲基取代苯乙烯的混合物作为研究对象。本文采用纯对氯甲基苯乙烯,在开展对其基本性质、均聚反应机理研究的同     

Studies on propagating species in cationic polymerization of styrene derivatives by acetyl perchlorate or iodine. III. Effect of salt on cationic copolymerization of styrene derivatives with vinyl ethers by acetyl perchlorate

A common-ion salt, tetra-n-butylammonium perchlorate, was found to affect the monomer reactivity ratios in the cationic copolymerization by acetyl perchlorate of styrene with p-methylstyrene and of 2-chloroethyl vinyl ether with p-methylstyrene, but not those for the copolymerization of 2-chloroethyl vinyl ether with isobutyl vinyl ether. In the copolymerization of p-methylstyrene with styrene or with 2-chloroethyl vinyl ether, the addition of the common-ion salt in a polar solvent shifted the monomer reactivity ratios to those in a less polar solvent. The molecular weight distribution analysis of the copolymer suggested that the addition of the common-ion salt depresses the dissociation of propagating species. Therefore, it was concluded that a propagating species with a different degree of dissociation shows a different relative reactivity towards two monomers. The nature of propagating species was also discussed on the basis of the common-ion effect on the monomer reactivity ratios in various solvents.     

丙烯酰胺与N,N′-亚甲基双丙烯酰胺的共聚反应研究

本文利用凝胶模量测定法、气相色谱法和紫外光谱法对丙烯酰胺与N,N’-亚甲基双丙烯酰胺水溶液共聚反应进行了研究,证实了N,N’-亚甲基双丙烯酰胺的反应活性明显大于丙烯酰胺的反应活性。用气相色谱法测得单体的竞聚率分别为r_(AM)=0.117,,r_(Bis)=5.756;用紫外光谱法研究了聚合反应中氧化还原引发剂浓度和反应温度对聚合反应速率的影响,得出共聚反应速率方程中,氧化剂的方次为0.66,还原剂浓度的方次为0.55,并求出共聚反应表现活化能为37.1KJ/mol。     

Kinetics and mechanism of the polymerization of styrene–acrylonitrile in the presence of polybutadiene

The mechanism of free radical grafting of styrene–acrylonitrile with polybutadiene was studied. By assuming a copolymerization mechanism an equation that related the amount of homopolymer formed and its molecular weight to a reactivity ratio and the charged ratio of monomer to polydiene was derived. Polymerizations that contained a variety of ratios of monomer to polybutadiene, two different catalysts, and variable amounts of a mercaptan modifier were studied. The weight fraction of homopolymer and its molecular weight were determined by high-speed GPC. The results were analyzed by the new equation and all showed a constant value of the reactivity ratio, which strongly suggests that the mechanism of the grafting reaction is copolymerization. Evidence that suggests that none of the grafting is a result of a hydrogen abstraction mechanism is also presented.     

New Methacrylate Copolymers Based on the Benzofurane Ring: Synthesis,Characterization, Monomer Reactivity Ratios and Biological Activity

The free radical copolymerization of (5-bromo-1-Benzofuran-2-yl)(phenyl)-O-methacrylketoxime (BPMKO) with 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate(AOEMA) has been carried out in 1, 4-dioxane at 65°C ± 1 and was analyzed by Fourier transform infrared, ¹H-NMR, ¹³C-NMR and gel permeation chromatography. Elemental analysis was used to determine the molar fractions of BPMKO and AOEMA in the copolymers. The monomer–reactivity ratios were calculated according to the general copolymerization equation using Kelen-Tüdõs and Finemann-Ross linearization methods. The reactivity ratios indicated a tendency toward random copolymerization. The polydispersity indices of the polymers were determined by gel permeation chromatography and suggested a strong tendency for chain termination by disproportionation. The thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass-transition temperature of the copolymers increased with increasing BPMKO content in the copolymers. All the products showed moderate activity against different strains of bacteria and fungi.