Synthesis of Dendritic-Linear Block Copolymers by Atom Transfer Radical Polymerization

The dendritic polyarylether 2-bromoisobutyrate as the macromolecular initiator for the controlled free radical polymerization of styrene was investigated. The polymerization was carried out with CuBr/2,2 ' -bipyridine catalyst at 110 degreesC. It is found that the hybrid dendritic-linear block copolymers possess well-defined molecular weights and low polydispersities.

SYNTHESIS OF BLOCK COPOLYMER FROM 5,6 -BENZO-2-METHYLENE-1,3-DIOXEPANE AND METHYL ACRYLATE VIA ATOM TRANSFER RADICAL POLYMERIZATION

Poly(methyl acrylate)-b-poly(5,6-benzo-2-methylene-1,3-dioxepane) (PMA-b-PBMDO) was synthesized by two-step atom transfer radical polymerization (ATRP). Firstly, ATRP of methyl acrylate (MA) was realized using ethyl alpha-bromobutyrate (EBrB) as initiator in the presence of CuBr/2,2'-bipyridine. After isolation, poly(methyl acrylate) with terminal bromine (PMA-Br) was synthesized. Secondly, the resulting PMA-Br was used as a macromolecular initiator in the ATRP of BMDO. The structure of block copolymer was characterized by H-1-NMR spectroscopy. Molecular weight and molecular weight distribution were determined on a gel permeation chromatograph (GPC).

SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION(ATRP)

Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene) oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator. Then the PS-CH2CH2OCOCCl3 (PS-Cl-3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl-3) was used as the macroinitiator in the polymerization of(meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl-3 and the P(S-b-MMA) were identified by FTIR and H-1-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

A NOVEL PHOTO-INITIATING SYSTEM FOR ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE

A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(NN-diethyldithiocarbamate) [Fe(DC)(3)], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)(3) as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)(2) as catalyst under UV light irradiation via a conventional ATRP process.

Synthesis of α-Bromine-Terminated Polystyrene Macroinitiator and Its Initiation of MMA Polymerization by ATRP

In the present paper the synthesis of block copolymers via the transformation from living anionic polymerization (LAP) to atom transfer radical polymerization (ATRP) was described. α-Bromine-terminated polystyrenes(PStBr) in the LAP step was prepared by using n-BuLi as initiator, tetrahydrofuran (THF) as the activator, α-methylstyrene (α-MeSt) as the capping group and liquid bromine (Br_2) as the bromating agent. The effects of reaction conditions such as the amounts of α-MeSt, THF, and Br_2 as well as molecular weight of polystyrene on the bromating efficiency (BE) and coupling extent (CE) were examined. The present results show that the yield of PStBr obtained was more than 93. 8% and the coupling reaction was substantially absent. PStBr was further used as the macroinitiator in the polymerization of methyl-methacrylate (MMA) in the presence of copper (I ) halogen and 2, 2' -bipyridine (bpy) complexes. It was found that the molecular weight of the resulted PSt-b-PMMA increased linearly with the increase of the conversion of MMA and the polydispersity was 1. 2-1.6. The structures of PStBr and P(St-b-MMA) were characterized by ~1H NMR spectra.

Atom transfer radical polymerization and copolymerization of isoprene catalyzed by copper bromide/2,2＇-bipyridine

ATRP, as one of the most successful controlled/‘‘living＇＇ radical polymerization techniques, has been applied to a large variety of monomers including styrenes,（meth）acrylates,（meth）acrylamides,acrylonitrile, and vinyl acetate. However, ATRP of isoprene still remains a challenge due to poor solubility of copper catalysts in isoprene and low chain propagation rate constant of the monomer. In this work,Cu Br/2,2＇-bipyridine was found to effectively mediate ATRP of isoprene at 100 °C, 130 °C, and 150 °C with ethyl 2-bromopropionate as an initiator. The polymerizations proceeded smoothly and reached 48.1%,53.3%, and 71.0% conversions, respectively, in 72 h, producing polyisoprenes with molecular weights close to theoretical values and relatively narrow distributions. A block copolymer of polystyrene-bpolyisoprene was prepared using Cu Br/2,2＇＇-bipyridine as a catalyst and polystyrene as a macroinitiator.The-1H NMR and-（13）C NMR analysis of polyisoprene indicated that the polymer had 88.8% 1,4-addition structure and 63.9% of the polymer backbone units were in trans-configuration.

Synthesis of Well-Defined Dendritic-Linear Diblock and Triblock Copolymers by Controlled Free Radical Polymerization

The design and synthesis of novel dendritic-linear block copolymers were described. The copolymers were synthesized by atom transfer radical polymerization (ATRP) using dendritic polyarylether 2-bromoisobutyrate macroinitiator. ATRP carried out in bulk with CuBr/bipy catalyst at 120癈, yielded well-defined block copolymers with polydispersities less than 1.36.

Synthesis and characterization of H-type amphiphilic liquid crystalline block copolymers by ATRP

H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the ATRP ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.

An Observation on the Microphase Separation of Poly(methyl methacrylate)-block-Polystyrene Copolymer

The phase behavior of a well-defined poly(methyl methacrylate)- b- polystyrene block copolymer was studied by transmission electron microscope. The results show that a microphase transition may have occurred in the copolymer film. A kind of lamellae and an ordered bicontinuous double-diamond morphology are observed clearly. The lamellar morphology reveals a larger period of about 400 nm.

Synthesis,Structure and Properties of a Novel Copolymer with Photochromic and Photoluminescence Functions

Photochromic and photoluminescence materials show bright colors under different excitation conditions,and thus,these functional materials have been applied in many fields.Based on the photochromic and photoluminescence theories,a block copolymer,which could be directly processed into nanofibers by electrospinning,was successfully prepared through atom transfer radical polymerization(ATRP).To synthesize the block copolymer,a vinyl monomer containing a spiropyran unit was employed to prepare the photochromic chain segment,and a polymethyl methacrylate(PMMA)chain segment was introduced to improve the processability of the block copolymer.Acting as the photoluminescence unit,the rare earth complex was linked to the side chain through coordination bonding between the rare earth ions and the ester groups of PMMA.When the photochromic and photoluminescence block copolymer was exposed to different wavelengths of ultraviolet(UV)light and visible(Vis)light,it could show white,red,green,yellow,and blue-purple.These results provide the potential of the as-prepared photochromic and photoluminescence block copolymer for application in fibers and fabrics.

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

Polyarylether dendrons as macroinitiators for the 'living'/controlled free radical copolymerization of N-phenylmaleimide (PhMI) and styrene (St) have been demonstrated. The copolymerization 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 copolymerization 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 rPhMI = 0.0207, and rSt = 0.0484, respectively.

窄分布两亲性嵌段共聚物的合成及其胶束化行为研究

利用原子转移自由基聚合合成了具有两亲性的嵌段聚合物聚苯乙烯 -b-聚丙烯酸 ( PS-b-PAA) ,用FTIR,1 H NMR,SEC对其进行了表征 ,并利用荧光探针技术研究了其在水溶液中的胶束化行为 .进一步的研究表明 。

ABA型两亲嵌段共聚物的合成及表征

以α ,α′ 二溴代二甲苯为引发剂 ,CuBr/2 ,2′ 联吡啶为催化体系 ,制备了双溴端基的分子量分布窄的聚苯乙烯 (MWD =1 18) .再以此作为大分子引发剂 ,实现了甲基丙烯酸对硝基苯酯的原子转移自由基聚合 ,制得了分子量可控且分子量分布窄的ABA型嵌段共聚物 ,再经水解、酸化 ,得到了聚甲基丙烯酸 b 聚苯乙烯 b

新型线状-树枝状两亲嵌段共聚物的合成

<正>结构规整的两亲嵌段共聚物的不寻常化学性质，已引起人们的广泛关注~[1,2]，树枝体（dendrimer）是一类架构密集、结构对称和具有多功能的新型特殊大分子。

窄分子量分布聚丙烯酸-g-聚甲基丙烯酸酯接枝共聚物的合成

利用合成的一种新型原子转移自由基聚合大分子引发剂和从主干接枝的方法制备了窄分布的两亲性接枝共聚物聚丙烯酸-g-聚甲基丙烯酸酯,并对其结构进行表征.产物主链和侧链的分子量可分别通过调整单体与引发剂的投料比和反应时间进行控制,结构规整,侧链单体适用范围广.该合成方法不仅推动了接枝共聚物合成研究的进展,其产物更为两亲性接枝共聚物自组装行为的研究提供了很好的研究对象.

含羧基的含氟嵌段共聚物的合成及表面性能研究

利用原子转移自由基聚合反应以及随后的大分子链中叔丁酯基团的水解反应 ,合成了一系列具有不同含氟量和羧基含量的二嵌段共聚物 ,并分别通过GPC ,1 HNMR和FT IR对共聚物的组成和结构进行了表征 .进一步考察了这些含羧基或羧酸钠基团的含氟嵌段共聚物在吡咯烷酮或水中的溶解性能、临界胶束浓度、表面活性、达到饱和吸附时每个分子在表面所占据的面积 ,以及成膜后的临界表面张力等性能 .实验结果表明 ,此含氟嵌段共聚物能显著降低吡咯烷酮和水的表面张力 。

酶促缩聚和原子转移自由基聚合法合成AB型两亲性嵌段共聚物

Novozym e-435催化10-羟基癸酸进行自缩聚反应得到线性聚酯,端基分别是羟基(—OH)和羧基(—COOH),在三乙胺催化下,分别用α-溴代丙酰溴和三甲基氯硅烷(TMSCL)进行端基官能化生成一个单官能度的大分子引发剂,在CuC l/2,2′-联吡啶(bpy)催化体系中,引发甲基丙烯酸环氧丙酯(GMA)的原子转移自由基反应(ATRP),得到聚(10-羟基癸酸酯)/聚甲基丙烯酸环氧丙酯(PHDA-b-PGMA)AB型两亲性嵌段共聚物,其结构及分子量(分布)通过核磁共振和凝胶渗透色谱(GPC)确证.此AB型两亲性嵌段共聚物在水溶液中能自组装形成纳米粒子,用原子力显微镜(AFM)观察粒子的形状和大小.

酶促开环聚合和原子转移自由基聚合制备新型H型嵌段共聚物

在生物酶催化剂Novozyme-435的作用下,乙二醇引发己内酯(ε-CL)酶促开环聚合,再用三乙胺作催化剂,将PCL端羟基与2,2-二氯代乙酰氯反应,生成四官能度大分子引发剂,引发甲基丙烯酸环氧丙酯(GMA)的原子转移自由基聚合(ATRP),合成了H型三嵌段共聚物(PGMA)2-b-PCL-b-(PGMA)2.嵌段共聚物的结构通过核磁共振和凝胶渗透色谱(GPC)得到了确证,其多分散性为1.32,分子量为32000.通过差热扫描量热法对嵌段共聚物的热性能进行了研究.

PBMA-b-PDMS-b-PBMA嵌段聚合物的合成与表征

以羟基封端的聚二甲基硅氧烷和α-溴代异丁酰溴为原料,制备了双官能度Br-PDMS-Br,并以此为大分子引发剂,CuCl和2,2’-联吡啶为催化剂,通过原子转移自由基聚合制备了聚甲基丙烯酸丁酯-聚二甲基硅氧烷-聚甲基丙烯酸丁酯(PBMA-b-PDMS-b-PBMA)三嵌段聚合物。利用傅里叶变换红外光谱仪(FT-IR)、核磁(1 H NMR)、凝胶渗透色谱分析仪(GPC)、热失重分析仪(TGA)、接触角测试仪、扫描电子显微镜(SEM)对三嵌段聚合物的结构及聚合反应进行了表征与测试。结果表明三嵌段聚合物具有较好的热稳定性、疏水性和微相分离。