线形聚(D,L-乳酸)和星形聚(D,L-乳酸)的合成研究

在辛酸亚锡Sn(Oct)₂催化下，分别用丙炔醇和季戊四醇引发D,L-丙交酯(DLLA)的开环聚合(ROP),合成了具有末端炔基的线形聚(D,L-乳酸)(PDLLA)和四臂星形聚(D,L-乳酸)(S-(PDLLA)₄),通过核磁共振氢谱(¹H NMR)和凝胶渗透色谱(GPC)对聚合物的结构和相对分子质量进行了表征。合成产物可用于后续制备基于聚乳酸的两亲性嵌段共聚物，为生物可降解性高分子材料的开发应用提供实验依据。     

草酸催化ε-己内酯开环聚合反应的研究

以含有双羧基的有机质子酸草酸作为ε-己内酯单体(ε-CL)开环聚合的催化剂,以体系存在的水分作为引发剂,使ε-己内酯单体开环聚合形成生物可降解的材料聚己内酯(PCL),研究催化剂浓度、在50℃和室温(20~25℃)下反应96 h己内酯开环聚合状态。结果表明,0.5%浓度的草酸能有效催化ε-CL单体的开环聚合形成PCL,50℃热聚合的PCL晶体结构更加完善,热稳定性良好。     

草酸催化ε-己内酯开环聚合反应的研究

以含有双羧基的有机质子酸草酸作为ε-己内酯单体(ε-CL)开环聚合的催化剂,以体系存在的水分作为引发剂,使ε-己内酯单体开环聚合形成生物可降解的材料聚己内酯(PCL),研究催化剂浓度、在50℃和室温(20²5℃)下反应96 h己内酯开环聚合状态。结果表明,0.5%浓度的草酸能有效催化ε-CL单体的开环聚合形成PCL,50℃热聚合的PCL晶体结构更加完善,热稳定性良好。     

乙酰丙酮钛催化本体开环聚合制备聚己内酯

聚己内酯(PCL)是一种环境友好、生物相容性和生物可降解性良好的高分子材料,在生物医学、涂料和包装等领域中得到广泛应用。以价格低廉的乙酰丙酮和四氯化钛为原料,采用简单易制的方法制得乙酰丙酮钛;然后以此作为ε-己内酯(ε-CL)单体的催化剂,采用本体开环聚合法制备了高转化率和高Mη(黏均相对分子质量)的PCL。研究结果表明:当n(ε-CL)∶n(催化剂)=150∶1、聚合时间为210 min和聚合温度为110℃时,所得PCL的转化率(99.5%)和M_η(2.662×10~4)相对最大。     

聚己内酯的制备及改性研究进展

综述了PCL(聚己内酯)合成的研究进展,介绍了引发ε-CL(ε-己内酯)开环聚合的几种引发体系(如活泼氢引发体系、稀土金属引发体系、碱金属引发体系和酶催化引发体系等)和辅助手段,并探讨了PCL的多种改性方法(PCL与淀粉共混改性、PCL与壳聚糖共聚改性、PCL与聚乳酸共混或共聚改性、PCL与聚醚共混或共聚改性、PCL与其他高分子材料共混或共聚改性)。最后对PCL的改性研究方向进行了展望。     

多臂聚乳酸的制备及其性能

以L-丙交酯为原料,以辛酸亚锡为催化剂,分别以1,6-己二醇、三羟甲基丙烷、季戊四醇(PET)、双季戊四醇为支化剂,采用熔融开环法合成了含有不同臂数的聚乳酸。用粘度计、差示扫描量热仪、热台偏光显微镜、X射线衍射等手段对分子量相似但臂数不同的星形聚乳酸进行了表征。结果表明,多臂聚乳酸的特性粘度、玻璃化转变温度、熔点、结晶度以及结晶速率随着臂数的增加而减小;冷结晶温度随着臂数的增加而增大。     

多臂聚乳酸的制备及其性能

以L-丙交酯为原料,以辛酸亚锡为催化剂,分别以1,6-己二醇、三羟甲基丙烷、季戊四醇(PET)、双季戊四醇为支化剂,采用熔融开环法合成了含有不同臂数的聚乳酸。用粘度计、差示扫描量热仪、热台偏光显微镜、X射线衍射等手段对分子量相似但臂数不同的星形聚乳酸进行了表征。结果表明,多臂聚乳酸的特性粘度、玻璃化转变温度、熔点、结晶度以及结晶速率随着臂数的增加而减小;冷结晶温度随着臂数的增加而增大。     

多功能PCL@CD纤维的制备与性能研究

以柠檬酸(CA)和乙二胺(EDA)为原料,采用一步微波法制备了强荧光碳点(CD).首次采用低毒性植酸(PA)催化ε-己内酯(ε-CL)开环聚合成功制备出生物可降解性聚己内酯碳点杂化材料(PCL@CD),并以不同质量比例的PCL@CD和纯PCL通过静电纺丝获得荧光可降解多功能纤维(SF).通过对SF进行形态和性能表征,结...     

阳离子型催化剂催化ε-己内酯开环聚合反应的研究进展

聚己内酯(PCL)是一种无毒、可生物降解的多功能高分子材料,广泛应用于生活用品和医药化工等行业。目前PCL主要通过催化ε-己内酯开环聚合获得,阳离子催化剂由于具有催化活性高、无毒等特点,在PCL的合成中已得到广泛应用,成为ε-己内酯开环常用的催化剂之一。介绍了PCL的理化性质和合成方法,详细阐述了各类型阳离子催化剂催化ε-己内酯开环聚合的反应机理。着重介绍了近几年阳离子型催化剂在己内酯聚合中的应用发展,并展望了阳离子催化在PCL开环聚合反应中的发展方向。     

ε-己内酯均聚物及共聚物的合成与表征

分别以D,L-乳酸和L-乳酸为原料制得D,L-丙交酯(D,L-LA)和L-丙交酯(L-LA);以辛酸亚锡为内酯开环聚合引发剂,用ε-己内酯(ε-CL)开环均聚合制备聚ε-己内酯,考察了引发剂用量、聚合时间和温度等对聚合产物特性黏数的影响。由ε-CL与D,L-LA和L-LA共聚合制得聚(ε-己内酯-D,L-丙交酯)和聚(ε-己内酯-L-丙交酯),并用傅里叶变换红外光谱、核磁共振氢谱、差示扫描量热法、X射线衍射等对聚合物的结构进行表征;力学性能测试结果表明,聚(ε-己内酯-L-丙交酯)具有很好的弹性和较高的断裂伸长率。     

Synthesis of amphiphilic heteroarm star‐shaped polymer via free radical polymerization using polyfunctional chain transfer agent and its self‐assembly behavior

Amphiphilic heteroarm star‐shaped polymers have important theoretical and practical significance. In this work, amphiphilic heteroarm star‐shaped polymer was synthesized by the use of polyfunctional chain transfer agent via sequential free radical polymerization in two steps. First, conventional free radical polymerization of methyl methacrylate (MMA) initiated by 2,2′‐azobis (isobutyronitrile) (AIBN) was carried out in the presence of polyfunctional chain transfer agent, pentaerythritol‐tertrakis (3‐mercaptopropinate) (PETMP). At appropriate monomer conversion, about two‐arm s‐PMMA having two residual thiol groups at the chain center was obtained. Second, the s‐PMMA obtained above was used as macro‐chain‐transfer agent for free radical polymerization of acrylic acid (AA). The heteroarm star‐shaped polymer with the hydrophobic PMMA segment and the hydrophilic PAA segment was obtained. The successful synthesis of heteroarm star‐shaped polymers, (PMMA)₂(AA)₂, was confirmed by ¹H‐NMR and its self‐assembly behavior in different solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of well-defined bisbenzoin end-functionalized poly(ε-caprolactone) macrophotoinitiator by combination of ROP and click chemistry and its use in the synthesis of star copolymers by photoinduced free radical promoted cationic polymerization

A new well-defined bisbenzoin group end-functionalized poly(ε-caprolactone) macrophotoinitiator (PCL-(PI)₂) was synthesized by combination of ring opening polymerization (ROP) and click chemistry. The ROP of ε-CL monomer in bulk at 110 °C, by means of a hydroxyl functional initiator namely, 3-cyclohexene-1-methanol in conjunction with stannous-2-ethylhexanoate, (Sn(Oct)₂), yielded a well-defined PCL with a cyclohexene end-chain group (PCL-CH). The bromination and subsequent azidation of the cyclohexene end-chain group gave bisazido functionalized poly(ε-caprolactone) (PCL-(N₃)₂). Separately, an acetylene functionalized benzoin photoinitiator (PI-alkyne) was synthesized by using benzoin and propargyl bromide. Then the click reaction between PCL-(N₃)₂ and PI-alkyne was performed by Cu(I) catalysis. The spectroscopic studies revealed that poly(ε-caprolactone) with bisbenzoin photoactive functional group at the chain end (PCL-(PI)₂) with controlled chain length and low-polydispersity was obtained. This PCL-(PI)₂ macrophotoinitiator was used as a precursor in photoinduced free radical promoted cationic polymerization to synthesize an AB₂-type miktoarm star copolymer consisting of poly(ε-caprolactone) (PCL, as A block) and poly(cyclohexene oxide) (PCHO, as B block), namely PCL(PCHO)₂.     

两个ATRP大分子引发剂的合成与表征

以十二醇为引发剂,通过开环聚合反应合成单端羟基的聚己内酯(PCL),将PCL进一步与α-溴丙酰溴反应,合成了原子转移自由基聚合(ATRP)的大分子引发剂-α-溴代丙酸聚己内酯。通过α-溴丙酰溴与聚乙二醇(PEG)的反应合成了另一种ATRP大分子引发剂-α-溴代丙酸聚乙二醇酯。用1H NMR和IR证实了这两种大分子引发剂的结构。     

Photoinduced living cationic polymerization of tetrahydrofuran. II: Synthesis of four‐armed star‐shaped poly(tetrahydrofuran)

A four‐armed star‐shaped poly(tetrahydrofuran) (THF) having a pentaerythritol unit at the center of the molecule was synthesized from photoinduced cationic copolymerization of THF and pentaeryithritol tetrakis(3,4‐epoxybutanoate) (PETE) in the presence of diphenyliodonium hexafluorophosphate. It was found that the molecular weight of the resulting polymer increases with increasing percent conversion and the rate of cationic polymerization of THF is remarkably increased by the addition of PETE when the concentration of PETE is kept much lower than that of THF. A similar enhancement effect was also observed in the photoinduced cationic polymerization of THF in the presence of epichlorohydrin (ECH). The enhancement effect of ECH and PETE was ascribed to the increased concentration of the cationic propagating species due to a rapid protonation process. The living nature was explained in terms of the stabilization of the cationic growing chain end by ion pair formation. Accordingly, the arm length of the polymer was determined by the molar ratio of THF and PETE. However, the polymer of well‐defined structure was only obtainable in the early stage of the reaction because chain transfer to the polymer process plays an important role when the concentration of the polymer becomes high. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2637–2644, 1999     

P2VP-b-PS-b-PI三嵌段共聚物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯(DDMAT)为链转移剂,通过可逆加成-断裂链转移自由基聚合(RAFT)方法制备了窄分布的聚2-乙烯基吡啶。再以该聚合物为大分子链转移剂,引发苯乙烯的RAFT聚合,得到聚2-乙烯基吡啶-b-聚苯乙烯(P2VP-b-PS)的两嵌段共聚物。以P2VP-b-PS为RAFT试剂,合成聚2-乙烯基吡啶-b-聚苯乙烯-b-聚异戊二烯(P2VP-b-PS-b-PI)的三嵌段共聚物。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,采用原子力显微镜(AFM)观察三嵌段共聚物薄膜的微相分离结构。结果表明,所得三嵌段共聚物P2VP72-b-PS136-b-PI300分子量分布较窄(PDI=1.69),合成过程具有活性/可控聚合特征,聚合物薄膜经溶剂退火处理后出现了明显的微观相分离结构。     

原位合成引发剂引发原子转移自由基及衰减链转移同步聚合

在甲基丙烯酸甲酯(MMA)单体中,以偶氮二异丁腈(AIBN)与I2反应原位合成α-碘代异丁腈(IIBN),进一步作为原子转移自由基聚合引发剂分别与CuCl、FeCl2.4H2O等催化剂,MA5-DETA、PMDETA等络合剂相匹配引发MMA的ATRP,同时又作为衰减链转移聚合(DT)的可逆链转移剂同步进行DT聚合。实验结果表明:所得聚合物分子量可控,分子量分布(PDI)很窄(1.05～1.25),引发剂效率较高。动力学的研究结果显示:分子量随转化率而增长;由Ln[M]0/[M]t对时间作图,呈现良好的线形关系,表明聚合过程中增长自由基浓度是一个恒定值,证明由IIBN引发的聚合是典型的活性自由基聚合;这种方法克服了极不稳定的在α-位带有吸电子基团的碘化物的购运和储存的困难。不失是一种简单,快捷,方便的方法。     

甲基丙烯酸二甲氨基乙酯的ATRP聚合

2-溴代异丁酸-Ⅳ-丁二酰亚胺酯（NHS—BIBA酯）由2-溴代异丁酸和,v-羟基丁二酰亚胺通过酯化反应制得。以它为引发剂,2,2＇-联吡啶（bpy）／CuBr为催化体系、水为溶剂,采用原子转移自由基聚合（ATRP）合成了带有功能基团的聚甲基丙烯酸二甲氨基乙酯（PDMAEMA）高分子。研究了引发剂、温度、反应时间、pH值和浓度对聚合产率的影响,利用凝胶渗透色谱（GPC）和核磁共振（1HNMR）测定了聚合物的分子量、多分散指数（PDI）和链结构。由GPC可知在最高产率下,Mn和Mw／Mn分别为8674和1．59,结果表明,NHS-BIBA酯引发的PDMAEMA实际数均分子量高于理论分子量,并具有低分散度,链结构上氢原子出峰符合特有的化学位移。     

异端基遥爪聚乙二醇的合成研究进展

异端基遥爪聚乙二醇的传统合成方法是端基改性法,它是以同端基遥爪聚乙二醇为原料,对其端基进行改性,得到异端基遥爪聚乙二醇;而直接合成法是用含有不同双官能团的引发剂来引发环氧乙烷的阴离子开环聚合,获得异端基遥爪聚乙二醇,同时两活性端基还可以进一步改性,衍生出更多种类的异端基遥爪聚乙二醇。对异端基遥爪聚乙二醇的直接合成法、端基改性法和通用性合成方法的研究进展进行了综述。     

Synthesis of azobenzene-functionalized star polymers via RAFT and their photoresponsive properties

Azobenzene-functionalized star polymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. First, azobenzene-functionalized linear macro chain transfer agents (Macro-CTA) were synthesized by RAFT polymerization of 6-[4-(4′-Methoxyphenylazo)phenoxy]hexylmethacrylate (MAz6Mc) using 2-(2′-cyanopropyl)dithiobenzoate (CPDB) as RAFT agent in presence of AIBN as initiator in anisole. Subsequently, star azopolymers were synthesized by polymerization of a difunctional azomonomer, BMA2Az, with resultant Macro-CTA in presence of AIBN as initiator in anisole. Star azopolymers were characterized by GPC and spectroscopic methods. Thermal properties of star azopolymers were determined by DSC and TMA. Molecular weight versus conversion and molecular weight versus polymerization time attest to living polymerization characteristics. Photoisomerization behaviors of star azopolymers were studied by irradiation of both UV and visible light. Surface relief gratings were inscribed on star azopolymer films upon exposure to an interference pattern of (RCP + RCP) Ar⁺ laser. A diffraction efficiency of 20% was obtained by exposure of Star-8 K(2.6 K) polymer film to an (RCP + RCP) Ar⁺ laser for about 30 min. Surface relief grating structures were investigated by AFM and polarized optical microscopy.     

Tailor‐Made Functional Polymethacrylates with Dual Characteristics of Self‐Healing and Shape‐Memory Based on Dynamic Covalent Chemistry

New shape memory polymers with self‐healing behavior are obtained by thermoreversible Diels–Alder (DA) cross‐linking of a furfuryl group‐containing star‐block copolymer with 1,1′‐(methylenedi‐4,1‐phenylene)bismaleimide. The star‐block copolymer consisting of a 3‐arm polycaprolactone (PCL) core and a polyfurfuryl methacrylate shell is synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. For this, a 3‐arm macro‐RAFT agent based on PCL is converted with an appropriate amount of furfuryl methacrylate in the presence of a radical initiator. Films of the DA network are partly insoluble at ambient temperatures. After annealing at 120 °C the films become completely soluble because of the progressing retro‐DA reaction. Evaporation of the solvent and subsequent annealing at 60 °C restores the original insoluble state of the material. By means of a scratch test and tensile tests on cut and subsequently mended samples it is shown that the retro‐DA reaction facilitates self‐healing. Additionally, the films show pronounced shape memory effects with reasonable shape recovery and fixity ratios, which are attributed to the melting and crystallization of the PCL phase.