丙烯酸酯和甲基丙烯酸酯基团转移共聚研究

研究了三种丙烯酸酯分别和四种甲基丙烯酸酯的基团转移共聚，用１Ｈ ＮＭＲ法测定共聚物组成，扩展的Ｋｅｌｅｎ Ｔｕｄｏｓ法测定竞聚率，结果为γＭＡ＝９２３、γＭＭＡ＝００６；γＥＡ＝１４１５、γＭＭＡ＝００１；γＢＡ＝７５１、γＭＭＡ＝００２；γＭＡ＝１４４１、γＥＭＡ＝００１；γＭＡ＝１３９６、γＢＭＡ＝０２３；γＭＡ＝８６６、γｉ ＢＭＡ＝００８，表明基团转移聚合同阴离子聚合有明显的相似之处．     

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（ＢＭＡ）和苯乙烯（Ｓ）这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,Ｋｅｌｅｎ Ｔｕｄｏｓ法计算竞聚率．得到ｒＳｔ＝０９１,ｒＢＭＡ＝０３２．     

甲基丙烯酸二甲氨基乙酯溴代烷季铵盐与苯乙烯共聚合的研究

以甲基丙烯酸二甲氨基乙酯溴代乙烷（ Ｍ Ａ Ｅ Ｂ） 或丁烷（ Ｍ Ａ Ｂ Ｂ） 季胺盐与苯乙烯（ Ｓｔ）为单体,采用溶液自由基共聚合方法,合成了一类新型阳离子两亲共聚物．详细地研究了聚合条件及共聚物的溶解性．共聚物“亲油”和“亲水”单元的无规结构被 Ｉ Ｒ、１ Ｈ Ｎ Ｍ Ｒ 及１３ Ｃ Ｎ Ｍ Ｒ所证实．最后,用线性化（ Ｙ Ｂ Ｒ） 法分别求得 Ｍ Ａ Ｅ Ｂ／ Ｓｔ 和 Ｍ Ａ Ｂ Ｂ／ Ｓｔ 的单体竞聚率,ｒ Ｍ Ａ Ｂ Ｂ ＝０４４ ,ｒ Ｓｔ ＝ ０１５ ,ｒ Ｍ Ａ Ｅ Ｂ＝ ０６６ ,ｒ Ｓｔ＝ ０３６ ．     

丙烯酸-β-羟乙酯和甲基丙烯酸正丁酯共聚合参数的测定与研究

用＾１Ｈ－ＮＭＲ分析法测定了丙烯酸－β－羟乙酯（Ｍ１）和甲基丙烯酸正丁酯（Ｍ２）的共聚物组成,用Ｍａｙｏ－Ｌｅｗｉｓ模型的误差变量法计算出不同温度下该体系的溶液聚合的竞聚率,分别为ｒ１＝０．６３,ｒ２＝１．１７（６０℃）;ｒ１＝０．６１,ｒ２＝１．０１（８０℃）;ｒ１＝０．６１,ｒ２＝０．９７（１００℃）;ｒ１＝０．７０,ｒ２＝１．０３（１２０℃）;ｒ１＝０．６８,ｒ２＝０．８８（１４０℃）和ｒ１＝０．６６,ｒ２＝０．８６（１６０℃）。根据Ａｒｒｈｅｎｉｕｓ方程计算获得了体系均聚、共聚反应频率因子之比Ａｉｉ／Ａｉｊ和活化能之差Ｅｉｉ－Ｅｉｊ,并讨论了溶剂、氢键对共聚合单体活性的影响。     

甲基丙烯酸甲酯与1—（2—叔丁基过氧异丙基）—3—异丙烯基苯的共？…

讨论了甲基丙烯酸甲酯与１－（２－叔丁基过氧异丙基）－３－异丙烯基苯的共聚行为。通过自由基共聚得到了带过氧侧基的聚合物。通过红外光谱，紫外光谱和凝胶色谱对共聚物进行了表征。用碘量法测定了共聚物中活性氧的含量，并由此测定了两者的竞聚率，ｒＤ１２０＝０．６９±０．０８，ｒＭＭＡ＝０．６３±０．０８。     

甲基丙烯酸甲酯与1-(2-叔丁基过氧异丙基)-3-异丙烯基苯的共聚研究

讨论了甲基丙烯酸甲酯与１－（２－叔丁基过氧异丙基）－３－异丙烯基苯的共聚行为。通过自由基共聚得到了带过氧侧基的聚合物。通过红外光谱，紫外光谱和凝胶色谱对共聚物进行了表征。用碘量法测定了共聚物中活性氧的含量，并由此测定了两者的竞聚率，ｒＤ１２０＝０．６９±０．０８，ｒＭＭＡ＝０．６３±０．０８。     

二烯丙基二甲基氯化铵—丙烯酰胺反相乳液聚合的动力学特征研究

采用油酸失水山梨醇酯（ＳＰＡＮ）－壬基酚聚氧化乙烯醚（ＯＰ）复合乳化剂与Ｋ２Ｓ２Ｏ８－Ｎａ２ＳＯ３氧化还原引发剂，进行二烯丙基二甲基氯化铵－丙烯酰胺反相乳液共聚合，测得单体的竞聚率为γＤＡＤＭＡＣ＝０．１４±０．１１，γＡＭ＝５．０５±０．６６；在单体浓度为２５─４５％，引发剂浓度０．０６—０．１％，乳化剂浓度为５—９％，聚合温度３０３Ｋ条件下，得到了共聚反应动力学方程：Ｒｐ＝ｋ［Ｍ］０．６８［Ｉ］１．３１［Ｅ］０．７３，文中对上述结果做了解释．     

丙烯腈和(甲基)丙烯酸酯基团转移共聚合的竞聚率

研究了丙烯腈（ＡＮ）和甲基丙烯酸甲酯（ＭＭＡ）、乙酯（ＥＭＡ）、丁酯（ＢＭＡ）、丙烯酸丁酯（ＢＡ）和顺丁烯二酸二丁酯（ＤＢＭ）等５种酯类单体的基团转移无规共聚．用Ｋｅｌｅｎ Ｔｕｄｕｓ法测定了二元共聚体系的竞聚率，分别为ｒＡＮ＝１０２２、ｒＭＭＡ＝０７７、ｒＡＮ＝５６８、ｒＥＭＡ＝０１６、ｒＡＮ＝８５９、ｒＢＭＡ＝００９、ｒＡＮ＝４０８、ｒＢＡ＝００６；ｒＡＮ＝１３８，ｒＤＢＭ＝００６．发现竞聚率，单体组分对聚合速率的影响等都和阴离子共聚类似．     

单茂钛催化剂的丙烯无规聚合反应及其动力学研究

比较了不同钛化合物／甲基铝氧烷（ＭＡＯ）催化体系的丙烯无规聚合，催化活性次序为ＣｐＴｉ（ＯＲ）３＞ＣｐＴｉ（ＯＰｈ）３＞ＣｐＴｉＣｌ３＞Ｃｐ２ＴｉＣｌ２＞Ｔｉ（ＯＢｕ）４＞ＴｉＣｌ４＞Ｔｉ（ＯＢｕ）２Ｃｌ２，所得聚丙烯用沸庚烷抽提８ｈ，溶解９５％以上，可溶部分经１３Ｃ ＮＭＲ、ＷＡＤＸ、ＦＴＩＲ等分析证明为无规聚丙烯（ａＰＰ），是没有结晶性的弹性体．ＧＰＣ测出其分子量Ｍｗ＝８．０～１０．０×１０４，Ｍｗ／Ｍｎ≈２．０．探索了催化体系ＣｐＴｉ（Ｏ ｎ Ｐｒ）３／ＭＡＯ中钛的浓度、［Ａｌ］／［Ｔｉ］摩尔比，丙烯聚合压力，聚合温度和时间对丙烯聚合反应的影响．研究了该催化体系丙烯聚合反应动力学规律，表观聚合反应速率对催化剂浓度和单体压力（浓度）都呈一级反应关系，表观聚合速率常数ＫＰ＝２９２×１０５ｍｏｌ／Ｌ·ｈ（４０℃）．活化能ΔＥ＝－７．８８×１０３Ｊ·ｍｏｌ－１，碰撞因子Ａ＝１．４１×１０－４ｍｏｌ／Ｌ·ｈ．     

螺旋藻中钙、锌、铁的测定

用日立Ｚ－８２３０原子吸收分光光度计测定了螺旋藻粉、螺旋藻提取液及螺旋藻功能饮料中Ｃａ、Ｚｎ、Ｆｅ的含量,结果为螺旋藻粉Ｃａ（８８１５５±５６５）×１０－６、Ｚｎ（４２８４±２２７）×１０－６、Ｆｅ（４２５７３±１６２４）×１０－６;螺旋藻提取液Ｃａ２２１０±１５３、Ｚｎ３９０±０５６、Ｆｅ９７０±０８８ｍｇ／Ｌ;螺旋藻功能饮料Ｃａ９７５±１０３、Ｚｎ１１５±０２５、Ｆｅ２０５±０３２ｍｇ／Ｌ。     

甲基丙烯酸三丁基锡酯与丙烯酸酯的共聚合

采用自由基引发剂对甲基丙烯酸三丁基锡酯和丙烯酸酯进行共聚合 ,其竞聚率用YBR法解出共聚方程的微分式而求得。甲基丙烯酸三丁基锡酯 (M1 )和丙烯酸甲酯 (M2 )、丙烯酸乙酯 (M2 )、丙烯酸丁酯 (M2 )共聚反应的竞聚率分别为r1 =1 .0 1± 0 .0 6,　r2 =0 .2 9± 0 .0 3;　r1 =1 .0 7± 0 .0 5 ,r2 =0 .38± 0 .0 3;　r1 =1 .1 1± 0 .0 5 ,　r2 =0 .45± 0 .0 3;　而所得到的甲基丙烯酸三丁基锡酯的Q、e值是它对各个单体的所有Q、e值的平均值 ,其Q =0 .5 7,e=- 0 .39     

Electrospinning of the hydrophilic poly (2-hydroxyethyl methacrylate) and its copolymers with 2-ethoxyethyl methacrylate

The goal was to electrospin 2-hydroxyethyl methacrylate — based biocompatible polymers and prepare submicron fibres (nanofibers) for biomedicinal applications. Syntheses of poly(2-hydroxyethyl methacrylate) (HEMA) and its copolymer with 2-ethoxyethyl methacrylate (EOEMA), and their characterization by viscometry and molecular weight are described. Their relation to electrospinning is discussed. Electrospinning of HEMA homopolymer from water-ethanol is successful for molecular weights 6.31 × 10⁵ and 1.80 × 10⁶ g/mol. Electrospinning of HEMA/EOEMA copolymers is feasible from ethanol.      

甲基丙烯酸酯的基团转移嵌段共聚研究

甲基丙烯酸酯的基团转移嵌段共聚研究戴李宗邹友思陈良坦潘容华（厦门大学化学系厦门３６１００５）关键词基团转移聚合，甲基丙烯酸酯，嵌段共聚物，结构表征基团转移聚合［１］（ＧｒｏｕｐＴｒａｎｓｆｅｒＰｏｌｙｍｅｒｉｚａｔｉｏｎ，ＧＴＰ）具有活性聚合的特点...     

甲基丙烯酸磺酸基己酯钠盐的共聚合、聚合及其均聚物的抗凝血性能

研究了甲基丙烯酸6-磺酸基己酯钠盐与甲基丙烯酸甲酯、甲基丙烯酸β-羟乙酯及甲基丙烯酸正己酯的共聚合,并测定了它在水及二甲亚砜中的聚合速度关系式。聚甲基丙烯酸6-磺酸基己酯钠盐的抗凝血性能在一定分子量范围内相差不多。     

An alternating copolymer of maleimide and atropic acid with narrow molecular weight distribution prepared by radical mechanism

Three basic conditions for preparation of alternating copolymer with narrow molecular weight distribution were derived from the element kinetic equations of binary radical copolymerization. Using maleimide (MI) and atropie acid (ATA) as model monomer pairs and dioxane as the solvent the alternating copolymer with molecular weight distribution in the range of 1.09--1.20 was prepared successfully by charger transfer complex (CTC) mechanism in the presence of benzoyl peroxide at 85℃. The monomer reactivity ratioes r_1(MI)=0.05±0.01 and r_2(ATA)=0.03±0.02 were measured. The alternating eopolymerization was carried out through formation of a contact-type CTG and then alternating addition of MI and ATA monomers. The molecular weight of the copolymers is nearly independent of the feed ratio in a large range and the polymerization rate dropped with an increase in ATA in feed ratio.     

甲基丙烯酸2-N,N-二甲氨基乙酯与甲基丙烯酸甲酯的氧化共聚合的机理研究

研究了CuCl/五甲基二亚乙基三胺(PMDETA)催化的甲基丙烯酸2-N,N-二甲氨基乙酯(DMAEMA)与甲基丙烯酸甲酯(MMA)在氧气存在下的氧化共聚合,通过改变单体配比、催化剂浓度和反应温度对实验条件进行研究.结果显示,在本实验中的单体配比([DMAEMA]∶[MMA]=10∶0～5∶5)、催化剂浓度([CuCl/PMDETA3]=3.1×10-5 mol/L～6×10-3 mol/L)和反应温度(30～80℃)下,聚合均可以顺利发生,而且聚合过程中单体转化率和所得聚合物的分子量都随着反应进行而增加,且分子量呈现宽分布.1H-NMR结果显示所得聚合物中含有DMAEMA和MMA的单体单元.DSC结果显示所得聚合物是一个部分相容体系.利用此方法所得的PDMAEMA进行MMA的原子转移自由基聚合(ATRP)扩链过程则证实,所得聚合物具有C—Cl末端官能团.由此可以认为,在以上过程中,O2先将CuCl氧化成[Cu(Ⅱ)Cl]+,[Cu(Ⅱ)Cl]+再将二甲胺基氧化成N—CH2.自由基,N—CH2.自由基与[Cu(Ⅱ)Cl]+构成反向ATRP体系,从而得到以C—Cl为末端的聚合物.     

Nitroxide‐mediated radical copolymerization of methyl methacrylate controlled with a minimal amount of 9‐(4‐vinylbenzyl)‐9H‐carbazole

The controlled nitroxide‐mediated homopolymerization of 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK) and the copolymerization of methyl methacrylate (MMA) with varying amounts of VBK were accomplished by using 10 mol % {tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino} nitroxide relative to 2‐({tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino}oxy)‐2‐methylpropionic acid (BlocBuilder?) in dimethylformamide at temperatures from 80 to 125 °C. As little as 1 mol % of VBK in the feed was required to obtain a controlled copolymerization of an MMA/VBK mixture, resulting in a linear increase in molecular weight versus conversion with a narrow molecular weight distribution (M_w /M_n ≈ 1.3). Preferential incorporation of VBK into the copolymer was indicated by the MMA/VBK reactivity ratios determined: r_VBK = 2.7 ± 1.5 and r_MMA = 0.24 ± 0.14. The copolymers were found significantly “living” by performing subsequent chain extensions with a fresh batch of VBK and by ³¹P NMR spectroscopy analysis. VBK was found to be an effective controlling comonomer for NMP of MMA, and such low levels of VBK comonomer ensured transparency in the final copolymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

SYNTHESIS OF POLY(METHYL METHACRYLATE)-graft-POLYSTYRENE BY ATOM TRANSFER RADICAL POLYMERIZATION

The radical copolymerization of methyl methacrylate and 2-hydroxyethyl methacrylate was carried out via atomtransfer radical polymerization (ATRP) initiated by ethyl 2-bromoisobutyrate and catalyzed by CuBr/2,2'-bipyridinecomplex. This polymerization proceeds in a living fashion with controlled molecular weight and low polydispersity. Theobtained copolymer was esterified with 2-bromoisobutylryl bromide yielding a macroinitiator, poly(methyl methacrylate-co-2-hydroxyethyl methacrylate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate), and its structure was characterized by ~1H-NMR. This macroinitiator was used for ATRP of styrene to synthesize poly(methyl methacrylate)-graft-polystyrene. Themolecular weight of graft copolymer increased with the monomer conversion, and the polydispersity remained relatively low.The individual grafted polystyrene chains were cleaved from the macroinitiator backbone by hydrolysis and the hydrolyzed product was characterized by ~1H-NMR and GPC.     

Studies on the copolymerisation of N-isopropyl-acrylamide with glycidyl methacrylate

The paper describes the homopolymerisation and copolymerisation of N-isopropyl acrylamide (NIPAM) with glycidyl methacrylate (GMA) in solution at 60°C using azobisisobutyronitrile (AIBN) as an initiator and dioxan as solvent. Copolymers were synthesized by varying the mol fraction of GMA in the initial feed from 0.025-0.125. All the polymerization reactions were terminated at low % conversion (10-15%) and the copolymer composition was determined by measuring the epoxy content. Percent epoxy content was determined by titration method using pyridine-HCl mixture. The reactivity ratios determined using Fineman-Ross method were found to be 0.94±0.05 (r₁, NIPAM) and 1.05±0.08 (r₂, GMA). All the polymers have high molecular weights with wide molecular weight distribution as determined by gel permeation chromatography (GPC) i.e. M_n in the range of 3.7 x 10⁴ - 7.8 x 10⁴ and M_w in the range of 1.2 x 10⁵ - 4.1 x 10⁵ with a polydispersity index in the range of 2.3-5.3. Lower critical solution temperature (LCST) of NIPAM homopolymer and copolymers was determined by recording DSC scans of polymers in aqueous solution. Incorporation of GMA in the poly(NIPAM) backbone resulted in a decrease in the LCST.