卟啉四臂星型聚乳酸的制备与表征

利用本体聚合方法,采用辛酸亚锡为催化剂,四氨基苯基卟啉为引发剂,引发丙交酯开环聚合,制备四臂星型聚乳酸功能高分子材料.采用1 H-NMR,FTIR,GPC等对星型聚合物的分子结构、分子量及其分布等进行了研究.利用溶液浇铸成膜方法,制备了聚乳酸薄膜材料;并利用XRD方法,研究了聚乳酸薄膜的结构.研究表明,利用四氨基苯基卟啉为引发剂,合成了以卟啉为核的四臂星型聚合物,其溶液浇铸薄膜具有正交晶系α晶型结构,而线型聚乳酸呈非晶态结构.利用紫外可见吸收光谱研究了星型聚乳酸的光谱性质,结果表明合成聚合物具有锡卟啉的光学特性.     

以聚乳酸为侧链的光学活性聚苯乙炔的合成与表征

通过4-溴苯甲醇和三甲基硅基乙炔的Sonagashira偶联反应与三甲基硅基的脱除反应,合成4-乙炔基苯甲醇.以4-乙炔基苯甲醇为引发剂,以有机氮杂环化合物DBU为催化剂,常温常压下进行丙交酯的活性开环聚合反应,采用1H-NMR和GPC对产物结构、分子量与分子量分布进行表征分析,结果表明,合成以了苯乙炔为端基的聚乳酸大...     

聚乳酸接枝丙烯酰胺制备抗菌材料

采用自由基接枝聚合法,以过氧化苯甲酰为引发剂,制备聚乳酸接枝丙烯酰胺共聚物;对接枝共聚物进行氯化,制备表面含卤胺基团的抗菌聚乳酸高分子材料.考察了丙烯酰胺含量、引发剂浓度、聚合温度、聚合时间等对接枝率的影响.采用核磁共振氢谱、红外光谱等对接枝聚合物的分子结构进行了表征;利用溶液浇铸法,制备抗菌聚乳酸薄膜,并对薄膜的抗菌性能等进行了研究.结果表明:实验获得的卤胺接枝聚乳酸对大肠杆菌抗菌性能明显.     

两亲性六臂星型端氨基PEG-PLGA的合成、表征及胶束化行为

采用本体开环聚合法,以乙交酯(GA)和DL-丙交酯(DLA)为原料,肌醇为引发剂,合成了一系列不同分子量的六臂星型聚乳酸聚乙醇酸(PLGA)(6-s-PLGA50,6-s-PLGA100,6-s-PLGA200,其中50,100,200为原料与引发剂的摩尔比),采用羧基化反应对其端基进行羧化处理.以聚乙二醇4000(PEG4000)为原料用对甲苯磺酰化法得到sTO-PEG-OTs,再进行氨解得到双端氨基PEG(H2N-PEG-NH2).末端羧基6-s-PLGAx通过N-环己基碳二亚胺(DCC)缩合反应与双端氨基PEG连接得到两亲性星型六臂结构的聚合物(6-s-PLGAx-PEG-NH2).分别用核磁共振氢谱法(1H NMR)、凝胶排阻色谱法(GPC)及差示热量热分析法(DSC)等手段对6-s-PLGAx和6-s-PLGAx-PEG-NH2进行了表征.以6-s-PLGA100-PEG-NH2聚合物为例,自组装得到空白的纳米粒子,并用透射电子显微镜法(TEM)和动态光散射法(DLS)考察了粒子的表面形态以及粒径分布特征,用1H NMR分析了胶束的"核-壳"结构.用噻唑蓝四氮唑溴化物(MTT)比色法探讨了该两亲性材料的体外细胞毒性.研究结果表明,合成了不同分子量的两亲性六臂星型端氨基PEG-PLGA,该两亲性聚合物可自组装形成纳米胶束,粒径范围在40～60 nm,与PLGA相比体外细胞毒性无显著性差异.     

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。     

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.     

开环聚合-固相缩聚法制备立体嵌段聚乳酸

首先,采用乳酸为引发剂,辛酸亚锡为催化剂,引发丙交酯开环聚合制得具有缩聚活性的L-聚乳酸和D-聚乳酸;然后,将两者熔融共混后进行固相缩聚,合成了一系列立体嵌段聚乳酸。采用核磁共振(NMR)、凝胶渗透色谱(GPC)及差示扫描量热仪(DSC)分析了产物的链结构、重均分子量、热性能,并探讨了均相晶体和立体复合晶体共存情况下的固相缩聚机理。结果表明,固相缩聚产物分子量增长的适宜反应条件为:反应时间30h,较低的催化剂含量,L-聚乳酸质量分数为80%。L-聚乳酸和D-聚乳酸共混物较低的初始立体复合晶体结晶度有利于后续固相缩聚过程中产物分子量的增长;固相缩聚不仅发生在异链之间,而且也发生在同链之间。     

蓖麻油与乳酸的共聚物合成与表征

用熔融聚合法合成了一种蓖麻油和乳酸的共聚物.以丁二酸酐作为共聚体系的引发剂和封端剂,制得端羧基共聚物P(LA-CO)-COOH.研究了反应条件对共聚物分子量的影响,通过核磁共振表征了共聚物的结构.DSC和TG研究表明,蓖麻油链段的引入破坏了聚乳酸的结晶性,提高了共聚物的热稳定性.     

聚合条件对N-羧基-L-丙氨酸-环内酸酐开环聚合产物分子量的影响

用光气法制备了N-羧基-L-丙氨酸-环内酸酐(L-Alanine NCA).系统研究了L-Alanine NCA开环聚合反应过程中引发剂、溶剂、温度对聚合物分子量的影响.用硝基苯作溶剂,三乙胺作引发剂,所得聚合物特性粘度[η]=1.18.实验中发现,L-Alanine NCA可以顺利地进行热聚合反应。反应具有速率快,转化率高,分子量大的特点。甲苯溶剂中反应5小时所得聚合物[η]=2.35,高于采用引发剂的聚合体系产物的相应值。     

乙烯-醋酸乙烯酯-α-烯烃三元共聚物

以乙烯、醋酸乙烯酯和α-烯烃为原料,以偶氮二异丁腈为引发剂,通过高压本体聚合制备三元聚合物.考察了聚合条件对共聚物数均分子量和醋酸乙酯(VA)质量分数的影响.结果表明:在引发剂用量为1.1g,反应压力为6 MPa,反应温度95℃,醋酸乙烯酯和α-烯烃的质量比为2:1的条件下能得到数均分子量为8 600和VA质量分数为0.35的产物.实验证明该产物性能优良,可作为蜡的添加剂.     

Effect of Star-shaped chain architectures on the polylactide stereocomplex crystallization behaviors

Linear and star-shaped polylactides (PLA) with similar molecular weights of each arm are synthesized via ring-opening polymerization of LA with 3-butyn-l-ol and pentaerythritol as initiators,respectively.By solution blending of equivalent mass of poly(L-lactic acid)s (PLLAs) and poly(D-lactic acid)s (PDLAs),perfect PLA stereocomplexes (scPLAs) are prepared and confirmed by WAXD and FTIR analysis.Effect of chain architectures on stereocomplex crystallization is investigated by studying the non-isothermal and isothermal crystallization of linear and star-shaped polylactide stereocomplexes.In dynamic DSC and POM test,star-shaped PLLA (4sPLLA)/PDLA and PLLA/star-shaped PDLA (4sPDLA) stereocomplexes reach rapid crystallization and higher crystallinity due to larger spherulite density of star-shaped chain and excellent chain mobility of linear chain.In isothermal crystallization test,much faster crystallization and less crystallization half-time is obtained with the increase of star-shaped chain.Meanwhile,4sPLLA/PDLA and PLLA/4sPDLA are found to have the highest crystallinity,suggesting limitation of too much star-shaped chain for 4sPLLA/4sPDLA and restriction of linear chain in nucleation capacity for PLLA/PDLA.The results reveal that star-shaped chain has an important influence on the crystallization of scPLAs.     

Properties and Polymerization of Biodegradable Thermoplastic Poly(Ester-urethane)

Abstract

Aliphatic polyesters, such as poly(lactic acids), need high molecular weight for acceptable mechanical properties. This can be achieved through ring-opening polymerization of lactides. The lactide route is, however, relatively complicated, and alternative polymerization routes are of interest. In this paper we report the properties of a polymer made by a two-step process: first a condensation polymerization of lactic acid and then an increase of the molecular weight with diisocyanate. The end product is then a thermoplastic poly(ester-urethane). The hydroxylterminated prepolymer was made with condensation polymerization of L–lactic acid and a small amount of 1,4-butanediol. The polymerization was performed in the melt under nitrogen and reduced pressure. The preparation of poly(ester-urethane) was done in the melt using aliphatic diisocyanates as the chain extenders reacting with the end groups of the prepolymer. The polymer samples were carefully characterized, including preliminary degradation studies. The results indicate that this route to convert lactic acid into thermoplastic biodegradable polymer has high potential. Lactic acid is converted into a mechanically attractive polymer with high yield, which could make the polymer suitable for high volume applications. The mechanical properties of the poly(ester-urethane) are comparable with those of poly(lactides). Capillary rheometer measurements indicate that the polymer is processible both by injection molding and extrusion.     

Photo-grafting Poly(acrylic acid) onto Poly(lactic acid) Chains in Solution

Poly(lactic acid)(PLA)is one of the most important bio-plastics,and chemical modification of the already-polymerized poly(lactic acid)chains may enable optimization of its material properties and expand its application areas.In this study,we demonstrated that poly(lactic acid)can be readily dissolved in acrylic acid at room temperature,and acrylic acid can be graft-polymerized onto poly(lactic acid)chains in solution with the help of photoinitiator benzophenone under 254 nm ultraviolet(UV)irradiation.Similar photo-grafting polymerization of acrylic acid(PAA)has only been studied before in the surface modification of polymer films.The graft ratio could be controlled by various reaction parameters,including irradiation time,benzophenone content,and monomer/polymer ratios.This photo-grafting reaction resulted in high graft ratio(graft ratio PAA/PLA up to 180%)without formation of homopolymers of acrylic acid.When the PAA/PLA graft ratio was higher than 100%,the resulting PLA-g-PAA polymer was found dispersible in water.The pros and cons of the photo-grafting reaction were also discussed.     

四臂星形嵌段共聚物s-PDLLA-b-PEG的合成

季戊四醇与D,L-丙交酯开环聚合制得末端为羟基的四臂星形聚乳酸(s-PDLLA);s-PDLLA与羧基封端的聚乙二醇单甲醚(CT-mPEG)完成酯化反应,合成了以季戊四醇为核,以聚乳酸为内部嵌段、聚乙二醇为外部嵌段的四臂星形聚(D,L-乳酸)-聚乙二醇嵌段共聚物(s-PDLLA-b-PEG),其结构经1H NMR,IR和GPC表征。     

Synthesis and self‐assembly of novel amphiphilic copolymers poly(lactic acid)‐block‐poly(ascorbyl acrylate)

In this study, a novel type of amphiphilic block copolymers poly(lactic acid)‐block‐poly(ascorbyl acrylate) (PLA‐block‐PAAA) with biodegradable poly(lactic acid) as hydrophobic block and poly(ascorbyl acrylate) (PAAA) as hydrophilic block was successfully developed by a combination of ring‐opening polymerization and atom transfer radical polymerization, followed by hydrogenation under normal pressure. The chemical structures of the desired copolymers were characterized by ¹H NMR and gel permeation chromatography. The thermal physical properties and crystallinity were investigated by thermogravimetric analysis, differential scanning calorimetry, and wide angle X‐ray diffraction, respectively. Their self‐assembly behavior was monitored by fluorescence‐probe technique and turbidity change using UV–vis spectrometer, and the morphology and size of the nanocarriers via self‐assembly were detected by cryo‐transmission electron microscopy and dynamic light scattering. These polymeric micelles with PAAA shell extending into the aqueous solution have potential abilities to act as promising nanovehicles for targeting drug delivery. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Organic/inorganic hybrid star-shaped block copolymers of poly(l-lactide) and poly(N-isopropylacrylamide) with a polyhedral oligomeric silsesquioxane core: Synthesis and self-assembly

The star-shaped organic/inorganic hybrid poly(l-lactide) (PLLA) based on polyhedral oligomeric silsesquioxane (POSS) was prepared using octa(3-hydroxypropyl) polyhedral oligomeric silsesquioxane as initiator via ring-opening polymerization (ROP) of l-lactide (LLA). The molecular weight of POSS-containing star-shaped hybrid PLLA (POSSPLLA) can be well controlled by the feed ratio of LLA to initiator. The POSSPLLA was further functionalized into the macromolecular reversible addition-fragmentation transfer (RAFT) agent for the polymerization of N-isopropylacrylamide (NIPAM), leading to the POSS-containing star-shaped organic/inorganic hybrid amphiphilic block copolymers, poly(l-lactide)–block–poly(N-isopropylacrylamide) (POSS(PLLA–b–PNIPAM)). The self-assembly behavior of POSS(PLLA–b–PNIPAM) block copolymers in aqueous solution was investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). DLS showed the PNIPAM block in the aggregates is temperature-responsive and its phase-transition is reversible. TEM proved that the star-shaped POSS(PLLA–b–PNIPAM) amphiphilic block copolymers can self-assemble into the vesicles in aqueous solution. The vesicular wall and coronas are composed of the hydrophobic POSS core and PLLA, and hydrophilic PNIPAM blocks, respectively. Therefore, POSSPLLA and POSS(PLLA–b–PNIPAM) block copolymers, as a class of novel organic–inorganic hybrid materials with the advantageous properties, can be potentially used in biological and medical fields.     

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.     

Stereoblock poly(lactic acid): synthesis via solid-state polycondensation of a stereocomplexed mixture of poly(L-lactic acid) and poly(D-lactic acid)

Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time.     

New Attempt at the Stereoselective Polymerization of Lactide by Using Crystallization during Polymerization

Summary: The stereoselective polymerization of partial rac‐lactide was attempted by using crystallization during polymerization. Polymerizations were carried out with trifluoromethanesulfonic acid in a mixed solvent of toluene and octane. The molar content of L ‐lactate in the feed was 95%. Polymerization proceeded with the elimination of D ‐lactate by means of crystallization. Poly(L ‐lactic acid) (PLLA) crystals were first precipitated and then plate‐like poly(lactic acid) (PLA) crystals were finally obtained, of which the composition of L ‐lactate was 97.6% and the was 1.68 × 10⁴.

The polymerization time dependence of the microstructure of poly(lactic acid), i.e., the percentage of mm triads (mm%), prepared from partial rac‐lactide in toluene‐70.     

Effect of vermiculite dispersion in poly(lactic acid) preparation and its biodegradability

In the present work, the research on the preparation, crystallization behavior and biodegradability of poly(lactic acid)-vermiculite nano-composites was carried out. Surfactant modified vermiculite was used accompanied with the poly(lactic acid) to prepare the nano-composites via in situ intercalative polymerization. The purpose was to evaluate the impact of the vermiculite and its different content on the morphology and properties of nano-composites. The crystal structure and morphology of poly(lactic acid) before and after nano-composites preparation were examined by wide-angle X-ray diffraction, polar optical microscopy and differential scanning calorimetry. The as-prepared nano-composites exhibited remarkable improvement of multiple materials properties due to the decrease in crystallinity. The enhanced biodegradability of nanocomposites was also presented along with the increase of vermiculite content.