RAFT聚合法合成聚丙烯酰胺基偶氮苯的研究

以二硫代苯甲酸苄酯(BDTB)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,丙烯酰胺基偶氮苯(AAAB)为单体,DMF为溶剂,利用可逆加成-断裂链转移(RAFT)聚合法合成了聚丙烯酰胺基偶氮苯(PAAAB),并考察了聚合温度和链转移剂浓度对聚合反应的影响。通过FT-IR、1 H-NMR、GPC等对链转移剂和聚合物结构进行了表征。结果表明:聚合反应动力学曲线呈良好的线性关系,分子量分布窄;随着[BDTB]/[AIBN]比例的增大,聚合速率和分子量下降,分子量分布变窄。     

RAFT聚合法合成PDMAEMA-b-PAAAB嵌段共聚物的研究

以甲基丙烯酸二甲氨基乙酯(DMAEMA)为单体、二硫代苯甲酸异丙苯酯(CDB)为链转移剂、偶氮二异丁腈(AIBN)为引发剂,利用RAFT聚合法合成了聚甲基丙烯酸二甲氨基乙酯(PDMAEMA)。以所得PDMAEMA为大分子链转移剂,丙烯酰胺基偶氮苯(AAAB)为单体,AIBN为引发剂,采用RAFT聚合法合成了PDMAEMA-b-PAAAB共聚物,并考察了AAAB的RAFT聚合反应动力学,利用FT-IR、1 H-NMR、GPC和TG对聚合物的结构和热性能进行了表征。结果表明,PDMAEMA的分子量随聚合反应时间的增加而增加,且分子量分布较窄;PDMAEMA-b-PAAAB嵌段共聚物的分子量随着AAAB单体转化率的升高而线性增加,且分子量分布较窄(PDI1.3),聚合反应动力学曲线呈良好的线性关系,且具有较好的热稳定性。     

聚[2-(4-苯基偶氮苯氧基)乙基丙烯酸酯]的合成及光响应性能研究

从4-羟基偶氮苯出发,依次与2-氯乙醇、丙烯酰氯反应,合成了2-(4-苯基偶氮苯氧基)乙基丙烯酸酯(PAPEA)。接着以PAPEA为单体,二硫代苯甲酸异丁腈酯(CPDB)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,利用可逆加成-断裂链转移(RAFT)聚合法合成了聚[2-(4-苯基偶氮苯氧基)乙基丙烯酸酯](PPAPEA)均聚物,同时考察了反应时间、引发剂和链转移剂浓度等因素对聚合反应的影响。利用FT-IR、1H-NMR和GPC等对单体和聚合物的结构进行了表征,并利用UV对聚合物的光响应性能进行了测试。结果表明,PAPEA的聚合反应动力学曲线呈良好的线性关系,分子量分布较窄(小于1.3);均聚物在紫外光照下的异构化速率随分子量的增大而减缓,而其在自然光下的回复速率变化不大。     

RAFT活性聚合法制备光响应型偶氮苯聚合物

以6-(4'-甲氧基-4-氧基偶氮苯)甲基丙烯酸乙酯(Azo MA)为单体,三硫代碳酸酯(DMP)为RAFT试剂,偶氮二异丁腈(AIBN)为引发剂,采用可逆加成-裂解链转移聚合法制备了偶氮苯聚合物(PAzo MA),其结构和性能经1H NMR,FT-IR,GPC和UV-Vis表征。结果表明:PAzo MA结构规整,分子量分布较窄(1.25),在光照下可发生构型反转。     

含氟丙烯酸酯与苯乙烯共聚物的RAFT合成及表征

通过可逆加成-断链链转移(RAFT)溶液聚合,以三硫代碳酸酯为RAFT试剂,偶氮二异丁腈(AIBN)为引发剂,1,4-二氧六环为溶剂,制备甲基丙烯酸(2,2,2-三氟)乙酯(TFEMA)和苯乙烯(St)共聚物.详细研究了不同引发剂的用量、RAFT试剂与引发剂摩尔比以及聚合温度等实验条件对聚合反应过程的影响.通过GPC、FTIR测试共聚物的分子量、分子量分布和分子结构,并用静态接触角仪和AFM分别表征聚合物膜的接触角、表面能及膜的表面形貌.     

聚丙烯酸-b-聚丙烯酸甲酯的制备及其在丙烯酸丁酯乳液聚合中的应用

采用三硫代碳酸S-1-十二烷基-S'-(a,a'-二甲基-a″-乙酸)酯(MTTCD)作为链转移剂,偶氮二异丁腈(AIBN)为引发剂,丙烯酸(AA)为第一单体,通过可逆加成-断裂链转移(RAFT)自由基聚合合成大分子链转移剂PAA-MTTCD,以丙烯酸甲酯(MA)为第二单体,合成5种不同嵌段比的两亲性嵌段共聚物聚丙烯酸-b-聚丙烯酸甲酯(PAA-b-PMA)。采用FT IR和1H NMR确定了PAA-MTTCD和PAA-b-PMA的结构,用GPC测定了PAA-MTTCD和PAA-b-PMA的分子量及分子量分布。分析了聚合反应动力学,发现该聚合具有活性可控聚合的特征,聚合动力学呈一级线性关系。测定了PAA-b-PMA的乳化性能,并将其作为乳化剂用于丙烯酸丁酯(BA)的乳液聚合中,同时考察了不同嵌段长度共聚物对乳液聚合的影响。结果表明,具有21个AA单元和18个MA单元的两亲性嵌段共聚物具有较好的乳化性能,其作为乳化剂时乳液聚合效果相对最好。     

聚丙烯酸-b-聚丙烯酸甲酯的制备及其在乳液聚合中的应用

采用三硫代碳酸S-1-十二烷基-S'-(a,a'-二甲基-a"-乙酸)酯(MTTCD)作为链转移剂,偶氮二异丁腈(AIBN)为引发剂,丙烯酸(AA)为第一单体,通过可逆加成-断裂链转移(RAFT)自由基聚合合成大分子链转移剂PAA-MTTCD,以丙烯酸甲酯(MA)为第二单体,合成5种不同嵌段比的两亲性嵌段共聚物聚丙烯酸-b-聚丙烯酸甲酯(PAA-b-PMA).采用FT IR和1H NMR确定了PAA-MTTCD和PAA-b-PMA的结构,用GPC测定了PAA-MTTCD和PAA-b-PMA的分子量及分子量分布.分析了聚合反应动力学,发现该聚合具有活性可控聚合的特征,聚合动力学呈一级线性关系.测定了PAA-b-PMA的乳化性能,并将其作为乳化剂用于丙烯酸丁酯(BA)的乳液聚合中,同时考察了不同嵌段长度共聚物对乳液聚合的影响.结果表明,具有21个AA单元和18个MA单元的两亲性嵌段共聚物具有较好的乳化性能,其作为乳化剂时乳液聚合效果相对最好.     

RAFT链转移剂存在下凹凸棒土表面甲基丙烯酸甲酯接枝聚合

将γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)接枝到凹凸棒土(AT)表面,制得表面带有可聚合碳碳双键的改性粒子AT-MPS;以二硫代苯甲酸氰基异丙酯(CPDB)为链转移剂,采用可逆加成断裂链转移(RAFT)聚合技术,在AT表面进行甲基丙烯酸甲酯(MMA)接枝聚合.通过红外(FTIR)、热失重(TGA)等方法进行了表征,考察了引发剂以及RAFT链转移剂用量对聚合反应动力学和AT表面接枝聚合接枝率的影响.结果表明,PMMA通过RAFT聚合成功接枝在AT表面;基于RAFT过程的接枝聚合比传统自由基接枝聚合具有更长的反应时间和较高的接枝率.本体系相对适宜条件:温度为70℃,[MMA]/[CPDB]/[AIBN]为400/1/0.5.此条件下聚合反应具有很好的可控性,溶液中的聚合物分子量分布指数为1.2~1.3,AT表面PMMA接枝率为16.33%.引发剂和RAFT链转移剂用量过大均会造成接枝率降低.     

氮氧自由基调控下苯乙烯的活性自由基聚合

本文用亚磷酸三-(2,2,6,6-四甲基哌啶氮氧自由基)酯(PT3)作为稳定自由基,偶氮二异丁腈(AIBN)和四乙基秋兰姆(TETD)分别作为起始自由基引发剂引发苯乙烯在125℃聚合。实验结果表明：在两种自由基引发剂存在下,Pb都可以有效地控制苯乙烯的聚合,分子量随转化率线性增长,分子量分布控制在1．15-1．6。对AIBN和TETD聚合过程比较可以发现：TETD引发下的聚合速度快于AIBN的聚合速度,就分子量分布和分子量的控制而言,两者具有相拟的能力。用得到的大分子聚合物为引发剂戚功进行的扩链实验也证明在三臂聚合物中心的烷氧胺可以继续引发苯乙烯聚合。     

分散聚合法制备窄分子量分布的聚苯乙烯微球

以无水乙醇为反应介质,以聚乙烯吡咯烷酮(PVP)为分散剂,偶氮二异丁腈(AIBN)为引发剂,采用分散聚合法制备分子量分布较窄的聚苯乙烯(PS)微球。研究了反应温度及反应时间、引发剂浓度和单体浓度对苯乙烯转化率和PS分子量分布的影响,采用SEM、GPC、FT-IR和TG对产物的形貌、分子结构和性能等进行了表征。结果表明:单体浓度为20%,引发剂用量为单体总量的0.7%,75℃下反应13h后,聚合反应的单体转化率可达87.8%,所制得的PS球形度较好,重均分子量为16.6万,分子量分布1.21,且具有优异的热稳定性。     

甲基丙烯酸N,N-二甲氨基乙酯/丙烯酸N,N-二甲氨基乙酯的可逆加成断裂链转移聚合研究

合成了二硫代苯甲酸2- (乙氧基羰基)异丙酯(ECPDB)、二硫代苯甲酸异丙苯酯(CDB)、二硫代苯甲酸1 苯基乙酯(PEDB) 3种二硫代苯甲酸酯链转移剂.以这3种转移剂为基础,用凝胶渗透色谱和核磁共振测试了甲基丙烯酸N ,N 二甲氨基乙酯(DMAEMA)和丙烯酸N ,N 二甲氨基乙酯(DMAEA)两种碱性单体的可逆加成断裂链转移(RAFT)聚合的聚合物分子量、分子量分布和结构.发现有的聚合体系聚合物分子量分布较窄,但实验数均分子量与理论数均分子量相差较大;有的体系则转化率很低,聚合物分子量很小.这些可能是由聚合体系中单体活性和链转移剂链转移能力之间的匹配不太协调,使可逆加成断裂链转移快速平衡反应发生偏移或破坏造成的.因此,可通过更换单体或链转移剂来调节这种匹配,从而使可逆加成断裂链转移快速平衡保持稳定,达到聚合更可控,实验分子量与理论分子量更接近,分子量分布更窄的目的.     

PS-b-P4VP两嵌段共聚物的合成及其自组装的研究

双硫酯 (PhC(S)SCH2 Ph)作为链转移剂 ,AIBN作为引发剂 ,用可逆的加成 断裂链转移 (RAFT)活性自由基聚合方法 ,合成了PS大分子链转移剂 .然后在AIBN引发下 ,利用制得的大分子链转移剂 ,以DMF为溶剂 ,80℃下采用RAFT方法 ,合成了PS b P4VP两嵌段共聚物 ,通过核磁共振谱及动力学的研究证明了其活性聚合的特征 .结果表明聚合反应在 2 4h内转化率可达 95 % .并用透射电子显微镜 (TEM )和扫描电子显微镜(SEM)研究了PS b P4VP两嵌段共聚物在选择性溶剂硝基苯 四氢呋喃中的自组装行为 ,研究结果表明改变聚合物的浓度以及选择性溶剂 ,可观察到自组装行为的变化 .     

Reversible addition–fragmentation transfer polymerization of p‐nitrophenyl acrylate and synthesis of diblock copolymers poly(p‐nitrophenyl acrylate)‐b‐polystyrene

Poly(p‐nitrophenyl acrylate)s (PNPAs) with different molecular mass and narrow polydispersity were successfully synthesized for the first time by reversible addition–fragmentation transfer (RAFT) polymerization with azobisisobutyronitrile (AIBN) as an initiator and [1‐(ethoxy carbonyl) prop‐1‐yl dithiobenzoate] as the chain‐transfer agent. Although the molecular mass of PNPAs can be controlled by the molar ratio of NPA to RAFT agent and the conversion, a trace of homo‐PNPA was found, especially at the early stage of polymerization. The dithiobenzoyl‐terminated PNPA obtained was used as a macro chain‐transfer agent in the successive RAFT block copolymerization of styrene (St) with AIBN as the initiator. After purification by two washings with cyclohexane and nitromethane to remove homo‐PSt and homo‐PNPA, the pure diblock copolymers, PNPA‐b‐PSt's, with narrow molecular weight distribution were obtained. The structural analysis of polymerization products by ¹H NMR and GPC verified the formation of diblock copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4862–4872, 2004     

通过RAFT法制备聚合物/膨润土杂化材料

通过可逆加成-断裂链转移(RAFT)自由基聚合方法合成了聚合物/膨润土(蒙脱石)杂化材料. 以乙基黄原酸基膨润土为链转移剂, AIBN为引发剂, 在环己酮溶液中, 通过甲基丙烯酸甲酯的RAFT自由基聚合, 得到了一系列的聚合物/膨润土杂化材料. 并用FT-IR, NMR, SPM, TG, GPC等分别对产物的微观结构、热性能、有机物含量以及分子量和分子量分布进行了表征和测试.     

RAFT聚合合成高分子量嵌段聚合物

以合成高分子量聚合物为目标,以苯基二硫代乙酸-1-苯基乙酯(PEPDTA)作为RAFT试剂,研究引发剂的种类(偶氮二异丁腈(AIBN)、1-1′-偶氮环己腈(ACC))、用量及聚合温度对苯乙烯/丙烯酸丁酯RAFT共聚合过程和聚合物结构的影响.结果发现,由于体系中RAFT浓度很低,相应的引发剂浓度要比传统自由基聚合低得多,只有采用较高的聚合温度和低分解速率常数的引发剂(ACC),才能制得无活性聚合物分率低(<0.1)、分子量高的聚合物,并进一步得到杂质含量少、分子量分布窄的嵌段聚合物.     

AMPHIPHILIC STAR-BLOCK COPOLYMERS BY IODIDE-MEDIATED RADICAL POLYMERIZATION

Amphiphilic star-block copolymers composed of polystyrene and poly(acrylic acid)were synthesized by iodide- mediated radical polymerization.Firstly,free radical polymerization of styrene was carried out with AIBN as initiator and 1,1,1-trimethyolpropane tri(2-iodoisobutyrate)as chain transfer agent,giving iodine atom ended star-shaped polystyrene with three arm chains,R(polystyrene)_3.Secondly,tert-butyl acrylate was polymerization using polystyrene obtained as macro-chain transfer agent,and star-block copolymer,R(polystyrene-b-poly(tert-butyl acrylate))_3 with controlled molecular weight was obtained.Finally,amphiphilic star-block copolymer,R(polystyrene-b-poly(acrylic acid))_3 was obtained by hydrolysis of R(polystyrene-b-poly(tert-butyl acrylate))_3 under acidic condition.     

Controlled Radical Polymerization of 2,3‐Epithiopropyl Methacrylate

We report first results on the controlled radical polymerization of 2,3‐epithiopropyl methacrylate (ETMA) also known as thiiran‐2‐ylmethyl methacrylate. Reversible addition‐fragmentation chain transfer (RAFT) of ETMA was carried out in bulk and in solution, using AIBN as initiator and the chain transfer agents: cyanopropyl dithiobenzoate (CPDB) and cumyl dithiobenzoate (CDB). A linear increase of the number‐average molecular weight and decrease of the polydispersity with monomer conversion were observed using CPDB as transfer agent, indicating a controlled process. Atom transfer radical polymerization (ATRP) of ETMA was performed under different reaction conditions using copper bromide complexed by tertiary amine ligands and ethyl 2‐bromoisobutyrate (EBiB) or 2‐bromopropionitrile (BPN) as initiator. All experiments lead to a crosslinked polymer. Preliminary studies in the absence of initiator showed that the CuBr/ligand complex alone initiates the ring‐opening polymerization of thiirane leading to a poly(propylene sulfide) with pendant methacrylate groups.

     

Reversible addition–fragmentation chain transfer/miniemulsion polymerization of butyl methacrylate in the presence of β‐cyclodextrin

In the presence of β‐cyclodextrin (β‐CD), reversible addition–fragmentation chain transfer (RAFT) polymerization has been successfully applied to control the molecular weight and polydispersity [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] in the miniemulsion polymerization of butyl methacrylate, with 2‐cyanoprop‐2‐yl dithiobenzoate as a chain‐transfer agent (or RAFT agent) and 2,2′‐azoisobutyronitrile (AIBN) as an initiator. β‐CD acted as both a stabilizer and a solubilizer, assisting the transportation of the water‐insoluble, low‐molecular‐weight RAFT agent into the polymerization loca (i.e., droplets or latex particles) and thereby ensuring that the RAFT agent was homogeneous in the polymerization loca. The polymers produced in the system of β‐CD exhibited narrower polydispersity (1.2 < M_w/M_n < 1.3) than those without β‐CD. Moreover, the number‐average molecular weight in the former case could be controlled by a definite amount of the RAFT agent. Significantly, β‐CD was proved to have a favorable effect on the stability of polymer latex, and no coagulum was observed. The effects of the concentrations of the RAFT agent and AIBN on the conversion, the molecular weight and its distribution, and the particle size of latices were investigated in detail. Furthermore, the influences of the variations of the surfactant (sodium dodecyl sulfate) and costabilizer (hexadecane) on the RAFT/miniemulsion polymerization were also studied. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2931–2940, 2005     

Kinetic modeling of two-step RAFT process for the production of novel fluorosilicone triblock copolymers

Well-defined poly(dimethylsiloxane)-b-poly(2,2,3,3,4,4,4-heptafluorobutylmethacryl-ate-b-poly(styrene) (PDMS-b-PHFBMA-b-PS) triblock copolymers were prepared by two-step reversible addition-fragmentation chain transfer (RAFT) polymerization. A comprehensive mathematical model for the two-step RAFT polymerization in a batch reactor was presented using the method of moments. The model described molecular weight, monomer conversion and polydispersity index as a function of polymerization time. Good agreements in the polymerization kinetics were achieved for fitting the kinetic profiles with the suggested model. In addition, the model was used to predict the effects of initiator concentration, chain transfer agent concentration and monomer concentration on the two-step RAFT polymerization kinetics. The simulated results showed that for the two-step RAFT polymerizations, the effects initiator concentration, chain transfer agent concentration and monomer concentration are identical and the influence degrees are different yet.     

Reversible addition–fragmentation chain transfer polymerization of glycidyl methacrylate with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate as a chain‐transfer agent

A reversible addition–fragmentation chain transfer (RAFT) agent, 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN), was synthesized and applied to the RAFT polymerization of glycidyl methacrylate (GMA). The polymerization was conducted both in bulk and in a solvent with 2,2′‐azobisisobutyronitrile (AIBN) as the initiator at various temperatures. The results for both types of polymerizations showed that GMA could be polymerized in a controlled way by RAFT polymerization with CPDN as a RAFT agent; the polymerization rate was first‐order with respect to the monomer concentration, and the molecular weight increased linearly with the monomer conversion up to 96.7% at 60 °C, up to 98.9% at 80 °C in bulk, and up to 64.3% at 60 °C in a benzene solution. The polymerization rate of GMA in bulk was obviously faster than that in a benzene solution. The molecular weights obtained from gel permeation chromatography were close to the theoretical values, and the polydispersities of the polymer were relatively low up to high conversions in all cases. It was confirmed by a chain‐extension reaction that the AIBN‐initiated polymerizations of GMA with CPDN as a RAFT agent were well controlled and were consistent with the RAFT mechanism. The epoxy group remained intact in the polymers after the RAFT polymerization of GMA, as indicated by the ¹H NMR spectrum. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2558–2565, 2004