原子转移自由基聚合在分子结构设计中的应用进展

原子转移自由基聚合(ATRP)是一种新型"活性"/可控聚合技术,可有效地实现对聚合物分子结构的设计,精准地控制聚合物分子结构。本文在介绍了官能团反应法、偶联反应法以及自由基聚合法制备ATRP大分子引发剂的基础上,进一步介绍了通过控制大分子引发剂"活性"点位置进行聚合物结构设计。同时还着重综述了大分子引发剂在嵌段聚合物、梳状聚合物、分子刷聚合物、树状及超支化聚合物和星形聚合物分子设计中的应用。     

非线形嵌段共聚物的合成

主要介绍了非线形嵌段共聚物，如星型嵌段共聚物、杂臂星型共聚物、梳型聚合物等的合成方法，包括多官能团引发剂法、大分子引发剂法等。各种活性聚合方法，如阳离子开环聚合、原子转移自由基聚合(ATRP)和氮氧稳定自由基聚合等都可以用于合成非线形嵌段共聚物。     

原子转移自由基聚合(ATRP)在二氧化硅表面接枝中的应用

ATRP方法是在二氧化硅(SiO2)表面接枝聚合物的一种有效方法.通过硅烷偶联剂把ATRP引发剂键接到SiO2表面,然后进行表面ATRP聚合,可以在SiO2表面接枝各种均聚物、嵌段共聚物、超支化聚合物.聚合可以在有机溶剂或水中进行.把ATRP方法同其它聚合方法如氮氧稳定自由基聚合或开环聚合相结合,可以在SiO2表面接枝复杂结构的聚合物如V型嵌段共聚物、梳型共聚物等.SiO2表面ATRP聚合可以通过外加引发剂或外加二价铜来实现聚合可控.     

树状化-线形两亲嵌段聚合物的合成及自组装研究

合成了缩酮保护的一代甲基丙烯酸羟乙酯单体DHEMA(G1),通过顺序ATRP聚合方法,制备得到大分子引发剂PDHEMA(G1)-Br,再引发苯乙烯单体得到一代嵌段聚合物PDHEMA(G1)-b-PS.以PDHEMA(G1)-b-PS为反应前体,通过重复的缩酮保护和脱保护反应,进一步得到了二代和三代的树状化-线形两亲嵌段...     

ATRP技术制备末端和中间功能化的温度敏感性聚N,N-二乙基丙烯酰胺

合成了2种含有二硫吡啶结构的原子转移自由基聚合(ATRP)引发剂,ATRP引发剂结构采用核磁共振氢谱(1H-NMR)表征.结果显示,二硫吡啶结构被成功引入引发剂结构末端或链中间.利用2种ATRP引发剂分别制备了链末端功能化和链中间功能化的聚N,N-二乙基丙烯酰胺(pDEAAm).采用1H-NMR和凝胶渗透色谱(GPC)对聚合物结构和分子量进行了表征.1H-NMR结果显示,二硫吡啶基团被引入聚合物链末端或中间.GPC结果表明,末端功能化和中间功能化的聚N,N-二乙基丙烯酰胺(pDEAAm)分子量分布指数分别为1.21和1.23,实现了分子量的可控聚合.并且,具有2个引发位点的引发剂引发单体得到聚合物的分子量较大.采用紫外-可见分光光度法研究了聚合物在溶液中的温度响应性.紫外-可见分光光度法结果说明,pDEAAm溶液在28°C发生相分离,在溶液中表现出温度响应性,且最低临界溶解温度(LCST)为28°C.在末端功能化和中间功能化温敏型pDEAAm可用于嵌段共聚物的合成以及与生物大分子的定位结合.特别对于中间功能化的pDEAAm,有望用于星型聚合物和多臂聚合物的设计和制备.     

ATRP大分子引发剂的合成及应用

原子转移自由基聚合(ATRP)是一种新型的可控/活性聚合技术,现已广泛应用于聚合物分子结构设计、无机材料表面修饰、蛋白质检测以及生物大分子的分离和杀菌防污等.在此类反应过程中涉及的三大要素:单体、引发体系(引发剂、催化剂、配位剂)及反应介质,其中核心要素为ATRP引发剂,其结构与性质是ATRP反应成败的决定因素之一.本文在综述了小分子引发剂的种类与性质及ATRP的反应机理的基础上,着重综述了近年来官能团反应法、偶联反应法及自由基聚合法制备ATRP大分子引发剂的最新进展.同时还综述了大分子引发剂通过ATRP反应在聚合物结构设计中的应用,以及对无机材料和生物材料的表面修饰的最新进展,最后对ATRP引发体系的未来发展与应用进行了展望.     

星型POSS/PMMA复合材料的ATRP合成及其热性能研究

以γ-氯丙基三乙氧基硅烷为原料合成八官能团γ-氯丙基多面体低聚倍半硅氧烷(POSS),以该POSS为引发剂,通过原子转移自由基聚合(ATRP)合成具有星型结构的POSS/PMMA复合材料.通过傅立叶红外(FTIR)、核磁共振(NMR)、凝胶渗透色谱(GPC)和X-射线衍射(XRD)等手段对POSS和POSS/PMMA的化学组成和结构进行了表征,结果表明已经合成八官能团γ-氯丙基POSS,POSS/PMMA复合材料具有分子设计的预定结构,且复合材料的分子结构得到了较好的控制.通过ATRP法实现了POSS在聚合物中的单分散.此外,TGA的研究表明,POSS的引入提高了聚合物的热稳定性.     

亚表面引发原子转移自由基聚合制备牢固的嵌入式聚合物刷

本文展示了一种新的材料表面改性方法:原子转移自由基聚合(sSI-ATRP)的亚表面修饰,即通过ATRP反应在聚合物材料界面嵌入聚合物刷,构筑稳定的、厚的聚合物亚表面层.首先,将ATRP引发剂分子通过共价键引入到丙烯酸树脂、聚氨酯、聚酯、环氧树脂等聚合物材料中,然后该基底材料在含有催化剂的单体溶液中引发表面原子转移自由基聚合.表面接枝的亲水聚合物刷使材料的表面变得亲水并发生溶胀,使得单体溶液可以进一步接触到材料内部的引发剂而引发新的ATRP反应,该过程不断重复,最后在基材表面上形成几十微米厚的聚合物刷改性的亚表面层.与传统的表面接枝的聚合物刷相比,这种嵌入式的聚合物刷赋予材料表面改性层更好的机械性能,可承受高载摩擦和更好的抗海生物附着特性,且在改性亚表面层破坏后,不需要引发剂修饰组装而再次重复引发聚合改性.     

原子转移自由基法合成八臂星型聚苯乙烯

设计合成了星型聚合物引发剂四(2,2-二氯乙酸)季戊四醇酯(TDCAP), 并通过原子转移自由基聚合合成了八臂星型聚苯乙烯. 用FTIR, 1H NMR和GPC等手段对引发剂和星型高分子的结构进行了表征.     

原子转移自由基聚合及其催化引发体系研究进展

原子转移自由基聚合(ATRP)作为一种有效的"活性"/可控聚合可对聚合物进行分子设计,制备结构和相对分子质量可控的各类聚合物,具有潜在而广泛的研究价值。本文综述了ATRP的研究进展,特别是对传统ATRP催化引发体系、RATRP催化引发体系、AGET ATRP催化引发体系、SR&NI ATRP催化引发体系、ICAR ATRP催化引发体系、ARGET ATRP催化引发体系、杂化或双金属催化体系等的催化引发机理进行了详细的介绍。并综述了ATRP聚合中各种实施方法如本体聚合法、溶液聚合法、悬浮聚合法、乳液聚合法等的研究现状。     

Synthesis of miktoarm star and miktoarm star block copolymers via a combination of atom transfer radical polymerization and stable free‐radical polymerization

A trifunctional initiator, 2‐phenyl‐2‐[(2,2,6,6‐tetramethyl)‐1‐piperidinyloxy] ethyl 2,2‐bis[methyl(2‐bromopropionato)] propionate, was synthesized and used for the synthesis of miktoarm star AB₂ and miktoarm star block AB₂C₂ copolymers via a combination of stable free‐radical polymerization (SFRP) and atom transfer radical polymerization (ATRP) in a two‐step or three‐step reaction sequence, respectively. In the first step, a polystyrene (PSt) macroinitiator with dual ω‐bromo functionality was obtained by SFRP of styrene (St) in bulk at 125 °C. Next, this PSt precursor was used as a macroinitiator for ATRP of tert‐butyl acrylate (tBA) in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 80 °C, affording miktoarm star (PSt)(PtBA)₂ [where PtBA is poly(tert‐butyl acrylate)]. In the third step, the obtained St(tBA)₂ macroinitiator with two terminal bromine groups was further polymerized with methyl methacrylate by ATRP, and this resulted in (PSt)(PtBA)₂(PMMA)₂‐type miktoarm star block copolymer [where PMMA is poly(methyl methacrylate)] with a controlled molecular weight and a moderate polydispersity (weight‐average molecular weight/number‐average molecular weight < 1.38). All polymers were characterized by gel permeation chromatography and ¹H NMR. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2542–2548, 2003     

Photoresponsive poly(methyl methacrylate)2–(polystyrene)2 miktoarm star copolymer containing an azobenzene moiety at the core

We prepared a novel miktoarm star copolymer with an azobenzene unit at the core via combination of atom transfer radical polymerization (ATRP) and nitroxide‐mediated free radical polymerization (NMP) routes. For this purpose, first, mikto‐functional initiator, 3 , with tertiary bromide (for ATRP) and 2,2,6,6‐tetramethylpiperidin‐1‐yloxy (TEMPO) (for NMP) functionalities and an azobenzene moiety at the core was synthesized. The initiator 3 thus obtained was used in the subsequent living radical polymerization routes such as ATRP of MMA and NMP of St, respectively, to give A₂B₂ type miktoarm star copolymer, (PMMA)₂‐(PSt)₂ with an azobenzene unit at the core with controlled molecular weight and low polydispersity (M_w/M_n < 1.15). The photoresponsive properties of 3 and (PMMA)₂‐(PSt)₂ miktoarm star copolymer were investigated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1396–1403, 2006     

Synthesis,characterization, and fluorescence of pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer with pentaerythritol core

Novel and well‐defined pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymers were successfully achieved by combination of esterification, atom transfer radical polymerization (ATRP), divergent reaction, ring‐opening polymerization (ROP), and coupling reaction on the basis of pentaerythritol. The reaction of pentaerythritol with 2‐bromopropionyl bromide permitted ATRP of styrene (St) to form four‐arm star‐shaped polymer (PSt‐Br)₄. The molecular weights of these polymers could be adjusted by the variation of monomer conversion. Eight‐hydroxyl star‐shaped polymer (PSt‐(OH)₂)₄ was produced by the divergent reaction of (PSt‐Br)₄ with diethanolamine. (PSt‐(OH)₂)₄ was used as the initiator for ROP of ε‐caprolactone (CL) to produce eight‐arm star‐shaped dendrimer‐like copolymer (PSt‐b‐(PCL)₂)₄. The molecular weights of (PSt‐b‐(PCL)₂)₄ increased linearly with the increase of monomer. After the coupling reaction of hydroxyl‐terminated (PSt‐b‐(PCL)₂)₄ with 1‐pyrenebutyric acid, pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer (PSt‐b‐(PCL‐pyrene)₂)₄ was obtained. The eight‐arm star‐shaped dendrimer‐like copolymers presented unique thermal properties and crystalline morphologies, which were different from those of linear poly(ε‐caprolactone) (PCL). Fluorescence analysis indicated that (PSt‐b‐(PCL‐pyrene)₂)₄ presented slightly stronger fluorescence intensity than 1‐pyrenebutyric acid when the pyrene concentration of them was the same. The obtained pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer has potential applications in biological fluorescent probe, photodynamic therapy, and optoelectronic devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2788–2798, 2008     

Synthesis of block and star copolymers by photoinduced radical coupling process

The general design for the synthesis of AB diblock, and A₂B and AB₂ star copolymers based on the statistical coupling of poly(styrene) (PSt) and poly (methyl methacrylate) (PMMA) macromolecules containing photoreactive benzophenone is presented. For this purpose, mono- and bifunctional initiators for Atom Transfer Radical Polymerization (ATRP) bearing benzophenone group were synthesized and characterized. End- and mid-chain benzophenone functional PSt and PMMA with low molecular weights were obtained by ATRP using these initiators in the presence of CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) catalytic complex. Poly(styrene-block-methyl methacrylate) (PSt-b-PMMA) copolymers were prepared by photolysis of the solutions containing end functional PSt and PMMA in THF at λ = 350 nm for 60 min in the presence of a hydrogen donor such as N-methyldiethanolamine (NMDEA). The proposed mechanism assumes hydrogen abstraction of photoexcited benzophenone moiety by NMDEA. Ketyl radicals resulting from abstraction reaction undergo radical-radical coupling to form benzpinacol structure at the core. Formation of A₂B and AB₂ type star copolymers upon irradiation of solutions containing appropriate combinations of end- and mid-chain functional polymers was also demonstrated. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2938–2947, 2009     

Block and star block copolymers by mechanism transformation. VI. Synthesis and characterization of A4B4 miktoarm star copolymers consisting of polystyrene and polytetrahydrofuran prepared by cationic ring‐opening polymerization and atom transfer radical polymerization

The synthesis of A₄B₄ miktoarm star copolymers, where A is polytetrahydrofuran (PTHF) and B is polystyrene (PSt), was accomplished with orthogonal initiators and consecutive cationic ring‐opening polymerization (CROP) and atom transfer radical polymerization (ATRP). The compound formed in situ from the reaction of 3‐{2,2‐bis[2‐bromo‐2‐(chlorocarbonyl) ethoxy] methyl‐3‐(2‐chlorocarbonyl) ethoxy} propoxyl‐2‐bromopropanoyl chloride [C(CH₂OCH₂CHBrCOCl)₄] with silver perchlorate was used to initiate the CROP of tetrahydrofuran. The obtained polymer contained four secondary bromine groups at the α position to the original initiator sites and was used to initiate the ATRP of styrene with a CuBr/2,2′‐bipyridine catalyst to form a C(PTHF)₄(PSt)₄ miktoarm star copolymer. The miktoarm copolymer was characterized by gel permeation chromatography and ¹H NMR. The macroinitiator C(PTHF)₄Br₄ was hydrolyzed to afford PTHF arms. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2134–2142, 2001     

Three‐arm star block copolymers of aromatic polyether and polystyrene from chain‐growth condensation polymerization,atom transfer radical polymerization,and click reaction

Well‐defined (AB)₃ type star block copolymer consisting of aromatic polyether arms as the A segment and polystyrene (PSt) arms as the B segment was prepared using atom transfer radical polymerization (ATRP), chain‐growth condensation polymerization (CGCP), and click reaction. ATRP of styrene was carried out in the presence of 2,4,6‐tris(bromomethyl)mesitylene as a trifunctional initiator, and then the terminal bromines of the polymer were transformed to azide groups with NaN₃. The azide groups were converted to 4‐fluorobenzophenone moieties as CGCP initiator units by click reaction. However, when CGCP was attempted, a small amount of unreacted initiator units remained. Therefore, the azide‐terminated PSt was then used for click reaction with alkyne‐terminated aromatic polyether, obtained by CGCP with an initiator bearing an acetylene unit. Excess alkyne‐terminated aromatic polyether was removed from the crude product by means of preparative high performance liquid chromatography (HPLC) to yield the (AB)₃ type star block copolymer (M_n = 9910, M_w/M_n = 1.10). This star block copolymer, which contains aromatic polyether segments with low solubility in the shell unit, exhibited lower solubility than A₂B or AB₂ type miktoarm star copolymers. In addition, the obtained star block copolymer self‐assembled to form spherical aggregates in solution and plate‐like structures in film. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Novel miktofunctional initiator for the preparation of an ABC‐type miktoarm star polymer via a combination of controlled polymerization techniques

An ABC‐type miktoarm star polymer was prepared with a core‐out method via a combination of ring‐opening polymerization (ROP), stable free‐radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). First, ROP of ϵ‐caprolactone was carried out with a miktofunctional initiator, 2‐(2‐bromo‐2‐methyl‐propionyloxymethyl)‐3‐hydroxy‐2‐methyl‐propionic acid 2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yl oxy)‐ethyl ester, at 110 °C. Second, previously obtained poly(ϵ‐caprolactone) (PCL) was used as a macroinitiator for SFRP of styrene at 125 °C. As a third step, this PCL–polystyrene (PSt) precursor with a bromine functionality in the core was used as a macroinitiator for ATRP of tert‐butyl acrylate in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 100 °C. This produced an ABC‐type miktoarm star polymer [PCL–PSt–poly(tert‐butyl acrylate)] with a controlled molecular weight and a moderate polydispersity (weight‐average molecular weight/number‐average molecular weight < 1.37). The obtained polymers were characterized with gel permeation chromatography and ¹H NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4228–4236, 2004     

Preparation of ABC miktoarm star terpolymer containing poly(ethylene glycol), polystyrene,and poly(tert‐butylacrylate) arms by combining diels–alder reaction,atom transfer radical,and stable free radical polymerization routes

The ABC type miktoarm star terpolymer was prepared utilizing “core‐in” and “core‐out” methods via combination of Diels–Alder reaction (DA), stable free radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). First, in DA reaction, poly(ethylene glycol)‐maleimide (PEG‐maleimide) precursor was reacted with succinic acid anthracen‐9‐ylmethyl ester 3‐(2‐bromo‐2‐methyl‐propionyloxy)‐2‐methyl‐2‐[2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yloxy)‐ethoxy‐carbonyl]‐propyl ester, 8 , to give DA adduct, 9 , which has appropriate functional groups for SFRP and ATRP. Second, a previously obtained 9 was used as a macroinitiator for SFRP of styrene at 125 °C. As a third step, this PEG‐polystyrene (PEG‐PSt) precursor with a bromine functionality in the core was employed as a macroinitiator for ATRP of tert‐butylacrylate (tBA) in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 80 °C to give ABC type miktoarm star terpolymer (PEG‐PSt‐PtBA) with controlled molecular weight and low polydispersity (M_w/M_n < 1.27). The obtained polymers were characterized by gel permeation chromatography and ¹H NMR. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 499–509, 2006     

Facile synthesis of dendrimer-like star-branched poly(isopropylacrylamide) via combination of click chemistry and atom transfer radical polymerization

We report a facile synthesis method of dendrimer-like star-branched poly(N-isopropylacrylamide) (PNIPAM) via the combination of click chemistry and atom transfer radical polymerization (ATRP) by employing the arm-first approach. First, the α-azido-ω-chloro-heterodifunctionalized building block, N ₃-PNIPAM-Cl (G0-Cl), was synthesized via ATRP by 3-azidopropyl 2-chloropropionate as the initiator. Taking advantage of click chemistry, the first generation (G1) of dendrimer-like star-branched PNIPAM, G1-(Cl)₃, was facilely prepared via the click coupling reaction between G0-Cl and tripropargylamine. For the construction of second generation (G2) dendrimer-like star-branched PNIPAM, G2-(Cl)₆, terminal chloride moieties of G1-(Cl)₃ were first converted to azide, and then reacted with excess tripropargylamine to give G1-(alkynyl)₆; G2-(Cl)₆ was subsequently prepared via click reaction between G1-(alkynyl)₆ and G0-Cl. Gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry were employed to confirm the successful construction of dendrimer-like star-branched polymers. The unique thermal phase transition behavior of this dendrimer-like star-branched polymer in aqueous solutions was further investigated by turbidimetry and micro-differential scanning calorimetry (Micro-DSC).     

Facile synthesis of AB2‐type miktoarm star polymers through the combination of atom transfer radical polymerization and ring‐opening polymerization

A novel miktofunctional initiator ( 1 ), 2‐hydroxyethyl 3‐[(2‐bromopropanoyl)oxy]‐2‐{[(2‐bromopropanoyl)oxy]methyl}‐2‐methyl‐propanoate, possessing one initiating site for ring‐opening polymerization (ROP) and two initiating sites for atom transfer radical polymerization (ATRP), was synthesized in a three‐step reaction sequence. This initiator was first used in the ROP of ?‐caprolactone, and this led to a corresponding polymer with secondary bromide end groups. The obtained poly(?‐caprolactone) (PCL) was then used as a macroinitiator for the ATRP of tert‐butyl acrylate or methyl methacrylate, and this resulted in AB₂‐type PCL–[poly(tert‐butyl acrylate)]₂ or PCL–[poly(methyl methacrylate)]₂ miktoarm star polymers with controlled molecular weights and low polydispersities (weight‐average molecular weight/number‐average molecular weight < 1.23) via the ROP–ATRP sequence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2313–2320, 2004