甲基丙烯酸甲酯-苯乙烯自由基共聚合微型化研究

采用甲基丙烯酸甲酯-苯乙烯自由基共聚合微型化实验,研究了微型化实验条件下,聚合反应工艺条件对共聚产物性能及转化率的影响,说明了高分子微型化实验的可行性。同时,通过微型实验与常规实验相比,进一步阐述微型高分子化学实验不仅装置精巧、新颖,还有利于减少火灾、爆炸等事故的发生几率,而且原料用量及废液量大幅减少,具有节约和环保的双重意义。微型化学实验由于简化了实验装置和实验操作,将其用在教学或科研上,比起常规实验更加简单易行、安全可靠。     

CuX／bpy催化体系中甲基丙烯酸甲酯的原子转移自由基聚合

讨论了以α－溴代丙酸乙酯（ＥＰＮ－Ｂｒ）为引发剂、卤化亚铜（ＣｕＸ）／联二吡啶（ｂｐｙ）为催化剂，８０℃下，甲基丙烯酸甲酯（ＭＭＡ）地不同溶剂中的原子转移自由基聚合（ＡＴＲＰ）反应。通过对催化剂ＣｕＢｒ或ＣｕＣｌ及几种溶剂的考察，发现在８０℃下ＥＰＮ－Ｂｒ／ＣｕＢｒ／ｂｐｙ能有效控制丙烯酸甲酯（ＭＡ）的本体ＡＴＲＰ反应，但并不能很好地控制ＭＭＡ在ＥＡｃ中的聚合反应为一可控聚合过程，引发效率为０．８     

富马酸亚铁催化甲基丙烯酸甲酯活性自由基聚合的研究

以畜马酸亚铁为催化剂,以2-溴代异丁酸乙酯为引发剂,在90℃下进行甲基丙烯酸甲酯的原子转移自由基本体聚合及溶液聚合.聚合物的数均相对分子质量随单体转化率的增加而线性增加,与时间呈良好线性关系,本体聚合时分子量分布(PDI)在1.5～1.7之间,溶液聚合时PDI＜1.5.通过聚合物扩链反应和端基分析,表明富马酸亚铁催化原子转移自由基聚合反应具有活性(可控)聚合的特征.     

富马酸亚铁催化甲基丙烯酸甲酯活性自由基聚合的研究

以富马酸亚铁为催化剂,以2-溴代异丁酸乙酯为引发剂,在90℃下进行甲基丙烯酸甲酯的原子转移自由基本体聚合及溶液聚合.聚合物的数均相对分子质量随单体转化率的增加而线性增加,与时间呈良好线性关系,本体聚合时分子量分布 (PDI) 在1.5～1.7之间,溶液聚合时PDI＜1.5.通过聚合物扩链反应和端基分析,表明富马酸亚铁催化原子转移自由基聚合反应具有活性(可控)聚合的特征.     

AIBN/SmCl3/乳酸体系催化甲基丙烯酸甲酯的反向原子转移自由基聚合

利用稀土金属化合物三氯化钐(SmCl3)和二氯化钐(SmCl2)之间的单电子转移反应,以AIBN/SmCl3/乳酸作为反向原子转移自由基聚合(ReverseATRP)的催化体系,成功地实现了甲基丙烯酸甲酯(MMA)的反向ATRP,并考察了温度、溶剂和组分比对聚合反应的影响.MMA在该体系中的聚合反应是一级反应,所得PMMA的分子量与单体转化率成正比,聚合物的分子量分布较窄(Mw/Mn<1.5),具有活性聚合的特征.     

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。     

新型引发体系引发MMA"活性"自由基聚合

传统的原子转移自由基聚合(ATRP)引发体系是由卤化物(引发剂)、低价过渡金属和合适的配体组成的络合物(催化剂)[1,2],即RX/Mnt/LX,三部分组成的.但由于卤化物的毒性和低价过渡金属易被空气中的氧气氧化,因此Matyjaszewski等[3,4]和Teyssié等[5]提出了新的引发体系反向ATRP.反向ATRP用传统引发剂(如AIBN)代替卤化物,用高价过渡金属络合物代替原来的催化体系,即AIBN/Mn+1t/LX,就避免了上述两个缺点.反向ATRP的引发反应机理表述如下:　　目前已见诸报道的关于反向ATRP的文献甚少[3～5],所使用的引发剂均为AIBN.Wang和Matyja…     

稳定自由基存在下苯乙烯聚合的加速剂

研究了稳定自由基存在下苯乙烯的活性聚合,发现在β－酮酸酯－乙酰乙酸乙酯,乙二酸二乙酯,1,3－二酮－乙酰丙酮的少量存在下,苯乙烯聚合速率显著增加,分子量可控,分子量在布较窄。而乙酰丙酮较大量存在下,聚苯乙烯分散性稍微变宽。     

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     

甲基丙烯酸甲酯自由基聚合歧化终止机理

首先用过氧化二苯甲酰(BPO)引发甲基丙烯酸甲酯(MMA)自由基聚合合成聚甲基丙烯酸甲酯(PMMA),然后用偶氮二异丁腈(AIBN)为引发剂,研究PMMA中由歧化终止生成的末端双键与苯乙烯(St)的共聚合反应行为。采用体积排除色谱(SEC)、核磁共振波谱(NMR)对聚合物进行了分析表征。结果表明：与单体MMA相似,PMMA在化学位移δ=6.20和5.47处有对应于聚合物末端双键氢的NMR信号。远程异核和近程异核相关NMR,¹³C-NMR和DEPT-135 NMR分析和自由基共聚合实验确证：MMA自由基聚合的双基歧化终止为单一的链自由基末端β位甲基氢自由基转移机理,生成1,1-二取代甲基丙烯酸酯型双键。除双基歧化终止反应外,体系还明显地存在苯甲酰初级自由基和苯初级自由基与链自由基间的初级终止反应。     

Radical Copolymerization of Methyl Methacrylate with Styrene in Several Solvents

Radical copolymerization of styrene (M₁) with methyl methacrylate has been carried out in several solvents. The monomer reactivity ratio (r) was affected by the solvent. The values of log 1/r, Q₂, and e₂ were found to increase with the decreases of the V _C[dbnd]O and v _n[dbnd]c stretcning frequencies determined in the corresponding solvents.     

Radical Copolymerization of Methyl Methacrylate and Styrene in the Presence of Metallocenes

The effect of ferrocene and zirconocene dichloride on the rate and constants of copolymerization of methyl methacrylate with styrene was studied. The results obtained suggest that the metallocenes in the elementary steps of the reaction.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 297–300.Original Russian Text Copyright © 2005 by Yumagulova, Kolesov, Monakov.     

Radical Copolymerization of Acrylic Monomers. II Effect of Solvent on Radical Copolymerization of Methyl Methacrylate and Styrene

The influence of various solvents on the copolymerization behavior of methyl methacrylate with styrene has been investigated. In these systems there is a significant solvent effect on both r_S and r_M which may be attributed to changes in the dielectric constant of the solvents used. The calculated relative reactivity of the polystyryl radical towards the methyl methacrylate monomer increases with increasing solvent polarity, whereas the reactivity of poly(methyl methacrylate) radical towards styrene monomer decreases. The results obtained are discussed taking into account the behavior of both monomers in homopolymerization with the same experimental conditions as in copolymerization.     

Photochemical Copolymerization of Styrene with Methyl Methacrylate

The photochemical copolymerization of styrene with methyl methacrylate were investigated under various conditions. The reactivity ratio and the ? values were evaluated.     

氢氧根对苯乙烯和甲基丙烯酸甲酯ATRP悬浮共聚的影响

在85℃下,以α-溴异丁酰溴为引发剂、氯化亚铜为催化剂、2,2′-联吡啶(bpy)为配体,研究了氢氧化钠(NaOH)含量对苯乙烯和甲基丙烯酸甲酯的原子转移自由基悬浮共聚合的影响。1H-NMR分析和共聚竞聚率(rSt=0.83,rMMA=0.82)表明St/MMA原子转移悬浮共聚容易形成恒比共聚。ATRP的悬浮聚合表现出较好的可控/活性特征。在试验水相中氢氧根浓度为0至3%的范围内,单体转化率、ln[M]0/[M]和表观反应速率常数kappp都随着氢氧根浓度增大而增大。氢氧根并不影响聚合反应的一级动力学特征,但具有加速St/MMA原子转移悬浮共聚反应的作用。探讨了氢氧根在St/MMA原子转移悬浮共聚反应中的作用机理。     

甲基丙烯酸丁酯和苯乙烯的原子转移自由基共聚

研究了甲基丙烯酸丁酯和苯乙烯两种不同极性单体的原子转移自由基嵌段共聚和无规共聚，得到了实测分子量与理论分子量相近、分子量分布较窄的嵌段共聚物和无规共聚物。聚合过程中分子量和单体转化率成比例增加，多分散性指数变化不大。用＾１Ｈ ＮＭＲ法测定共聚组成，Ｋdisplay status     

甲基丙烯酸丁酯和苯乙烯的原子转移自由基嵌段共聚

活性聚合以其无链转移、无链终止和引发速度远大于增长速率的特点,应用于合成单分散聚合物、预定序列结构的嵌段共聚物等．常用的活性聚合方法如阴离子聚合、阳离子聚合及基团转移聚合对反应条件要求苛刻,不能用于丙烯酸酯类极性单体和苯乙烯类非极性单体的嵌段共聚．与...     

Copolymerization of Styrene and Methyl Methacrylate with Lithium as Initiator

Copolymers of styrene and methyl methacrylate prepared with lithium dispersion as initiator do not contain random sequences of both monomers. Fractionation of the copolymers with acetonitrile and the NMR spectra of the insoluble fractions show that these are block copolymers which consist of a polystyrene portion and a poly(methyl methacrylate) portion. When the copolymerization is stopped at low conversion the copolymer has a high styrene content, which sometimes exceeds the value expected for radical copolymerization. This fact would indicate that styrene is preferentially polymerized at the early stages of chain propagation. When the copolymerization is carried to high conversion some crosslinked polymer is formed which contains more styrene than the soluble part of the same experiment. When a piece of metallic lithium is used as initiator, it is found that the crosslinked polymer is formed on the surface of the metal. The addition of lithium phenoxide or β-naphthoxide to the system eliminates the formation of crosslinked polymer. A possible mechanism is proposed.     

Radical Copolymerization of Fluoroalkyl Methacrylates with Methyl Methacrylate

Lauryl peroxide initiated radical copolymerization of 1,1,3-trihydroperfluoropropyl methacrylate and 1,1,5-trihydroperfluoroamyl methacrylate with methyl methacrylate was studied. The kinetic parameters of copolymerization for these systems were determined at low degrees of conversion. Optically transparent copolymers with glass transition points within 50–80°C were synthesized.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 5, 2005, pp. 818–821.Original Russian Text Copyright © 2005 by Man’ko, Mel’nichenko, Bovkunenko, Shendrik, Fedoseeva, Goncharov.