可生物降解聚酯P(DHCA-co-LA)的合成与表征

由3,4-二羟基肉桂酸(DHCA)与D,L-乳酸(LA)经熔融缩聚法得到了新型可生物降解聚酯P(DHCA-co-LA),采用傅立叶变换红外(FTIR),核磁共振(1H-NMR)和凝胶渗透色谱(GPC)对该共聚物的组成与相对分子量进行表征,结果表明其结构明确.改变DHCA与LA单体的配比,得到的P(DHCA-co-LA)的分子量和分子量分布在同一数量级.通过差示扫描量热仪(DSC)、紫外(UV)和荧光光谱研究了共聚物的热性能、紫外与荧光性能,结果表明,P(DHCA-co-LA)有明显的玻璃化转变温度(Tg),随LA的投料比从0增加至50 mol%时,其Tg从132.26℃下降至99.12℃;当LA的投料比为20 mol%时,所得到的聚酯型共聚物溶液呈现最强的荧光强度;在紫外光照下,共聚物可进行环加成反应,但交联度总体较低;紫外光照65 min后,在荧光显微镜下观察到交联颗粒形态稳定、有较强的荧光.X-射线衍射(XRD)测定结果显示,由结晶性DHCA和LA共聚形成的P(DHCA-co-LA)为无定形聚合物,有利于生物降解.共聚物在土壤中的降解实验表明,其降解速度随体系中LA含量的增加而减缓.     

新型PDHCA-b-PEG聚酯的合成与性能

以3,4-二羟基肉桂酸(DHCA)和聚乙二醇(PEG)为主要原料进行熔融缩聚,制得了分子链中具有类嵌段结构的新型聚酯(PDHCA-b-PEG)共聚物.用核磁共振(1H-NMR)、傅里叶红外(FT-IR)光谱和凝胶渗透色谱(GPC)对PDHCA-b-PEG的结构与数均分子量进行了表征,结果表明所合成的共聚物结构明确.通过差示扫描量热(DSC)、荧光光谱和X-射线衍射(XRD)研究了共聚物的热性能、荧光性能与结晶性能,结果表明:PDHCA-b-PEG具有明显的玻璃化转变温度(L),当PEG的投料量(PEG与DHCA的质量比)为15%时,共聚物的TG为73℃,达到最低值;当PEG的投料量为5%时,所得共聚物溶液发出最强的荧光强度;PDHCA-b-PEG为无定形结构聚合物,易于生物降解.体外细菌培养结果显示,PDHCA-b-PEG对白色葡萄球菌具有一定的抑制作用.     

梳状P(MMA-co-MAh)-g-PEGME共聚物的合成及结构与性能

用自制的甲基丙烯酸甲酯和马来酸酐的共聚物P(MMA-co-MAh)为反应物,聚乙二醇单甲醚(PEGME)为接枝单体,合成了梳状P(MMA-co-MAh)共聚物多缩乙二醇酯(P(MMA-co-MAh)-g-MPEG).采用傅立叶红外光谱(FTIR)、核磁共振(NMR)13C谱、1H谱以及H,C-COSP谱对所合成的梳状共聚物结构进行表征;热失重分析(TGA)和示差扫描量热法(DSC)对所合成的共聚物的物理性能进行了分析.FTIR及NMR结果表明,聚乙二醇单甲醚通过酯化反应接枝到P(MMA-co-MAh)共聚物上,形成以MMA/MAh共聚物为主链,聚乙二醇单甲醚为侧链的梳状共聚物,其在马来酸酐上的接枝率大约为20%;热性能分析结果表明,合成的梳状共聚物热分解温度与共聚物P(MMA-co-MAh)的分解温度相差不大,接枝后的梳状共聚物也具有高的热稳定性,起始热分解温度在325.9℃左右,且该梳状共聚物具有两个玻璃化转变温度,一个是由于侧链的玻璃化转变引起的,温度为32℃左右;一个是主链的玻璃化转变引起的,温度为120℃左右.在主链玻璃化转变温度以下,侧链是可以移动的,有利于电活性物质和离子等在聚合物基体中的扩散和迁移.     

通过原子转移自由基聚合合成可光交联的聚苯乙烯接枝共聚物

聚苯乙烯(PS)在氯化锌(ZnCl_2)做催化剂下,通过氯甲基甲基醚氯甲基化反应,合成了氯甲基化聚苯乙烯(CMPS).在氯化亚铜/联二吡啶(CuCl/bpy)催化下,以CMPS为大分子引发剂引发甲基丙烯酸甲酯(MMA)、甲基丙烯酸酯化查尔酮(MSPK)进行原子转移自由基聚合,成功合成了侧链含有查尔酮结构的光敏聚苯乙烯接枝共聚物(PSMM),所得聚合物结构经过红外光谱(FT-IR)、核磁共振氢谱(~1H NMR)得到确认,通过热重分析(TG)、示差扫描量热法(DSC)测试了该聚合物的热学性能.结果表明,该接枝共聚物具有较好的热学性能及良好的光敏性.     

含活性侧基马来酰亚胺/苯乙烯共聚物的合成与性能研究

合成了含活性侧基的苯乙烯/N-对羟苯基马来酰亚胺共聚物(SHMI),使某些具有特定功能的有机小分子接枝到聚合物主链上.用FTIR,NMR及GPC研究了其化学结构,并用DSC和TGA研究了其热转变和热降解性能.结果表明,SHMI是交替共聚物,其玻璃化转变温度(Tg)高达526K,于661K开始降解,降解动力学遵循Arrhenius方程,有良好的溶解成膜性能.     

含mPEG侧链的水溶性梳状聚合物的合成及其侧链受限结晶行为研究

采用大单体与小单体共聚的技术,通过自由基引发溶液聚合,合成了一系列水溶性梳状聚合物———聚丙烯酸接枝聚乙二醇单甲醚(PAA-g-mPEG).制备过程分两步进行,首先合成大单体聚乙二醇单甲醚丙烯酸酯,然后将大单体与丙烯酸单体共聚,合成了梳状聚合物.通过控制反应条件,获得了一系列主链和支链组成比不同的接枝共聚物.用傅立叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征了共聚物的结构,并对其侧链的结晶行为进行了研究.采用差热扫描量热法(DSC)表征并分析了不同侧链长度的mPEG的热性能及其结晶情况.利用相差显微镜和原子力显微镜(AFM)观察薄膜的结晶形貌,表明梳状聚合物的侧链mPEG在受限条件下的薄膜结晶形貌为高度支化的晶体,初步分析了mPEG链长及其在共聚物中的重量百分含量对晶体形貌的影响.     

聚对二氧环己酮/聚乙二醇多嵌段共聚物的合成与表征

首先合成双端羟基的聚对二氧环己酮预聚物(PPDO)和双端羧基的聚乙二醇预聚物(PEG),然后以丁二酸酐/二环己基碳二亚胺(DCC)将PPDO与PEG偶联共聚,得到PPDO/PEG多嵌段共聚物.通过1H-NMR和GPC表征了聚合物的结构和分子量.采用差示扫描量热法(DSC)和热重分析(TGA)研究了共聚物的结晶性能和热稳定性.用透析法制备了共聚物纳米粒子,并用动态光散射(DLS)表征了共聚物纳米粒子的粒径及分散度,结果表明,随着共聚物亲水链段PEG含量的增加,其纳米粒子更易形成,粒子粒径随共聚物分子量增大而增大.     

PLA,PPC和PHBV共混物的热性能、力学性能和生物降解性能研究

将聚乳酸(PLA)、聚碳酸酯(PPC)及β-羟基丁酸酯与β-羟基戊酸酯共聚物(PHBV)以溶液浇注法制备了各种不同比例的共混膜(60/20/20,40/20/40,40/40/20,20/60/20,20/40/40,20/20/60)。采用示差扫描量热分析(DSC)和热重分析(TG)研究了共混物的热性能,采用万能材料试验机研究了共混物的力学性能,通过土壤悬浊拟环境降解实验和扫描电子显微镜(SEM)研究了共混材料的环境生物降解性能。结果显示,该三元共混体系是部分相容的体系,PLA增加了材料的强度,PPC增加了材料的断裂伸长,PHBV则提高了材料的环境生物降解速率,三者优势互补,是一种有应用前景的生物降解共混体系。     

引入δ-内酯疏水取代烷基结构实现聚对二氧环己酮的性能调控

可反复化学循环、可生物降解的聚对二氧环己酮(PPDO),存在水解降解快等问题,不利于其储存和使用.基于此,本文通过将不同正烷基取代的δ-内酯(RVL)分别与对二氧环己酮(PDO)在磷酸二苯酯催化下本体共聚,高效地合成了3种结构和组分可控的PPDO基共聚物(PDRVL).通过热重分析(TGA)、差示扫描量热分析(DSC)...     

可光、化学降解聚苯乙烯的合成与性能研究

通过1,3-二碘甲基-2-硝基苯与双(2-甲基丙酸)三硫代碳酸酯的高效聚酯化反应合成了主链中含有邻硝基苄酯和三硫代碳酸酯基团的聚合物,以其作为大分子链转移剂,进行苯乙烯的可逆加成断裂链转移(RAFT)聚合,获得了多嵌段聚苯乙烯.大分子链转移剂和多嵌段聚苯乙烯的结构及分子量通过核磁氢谱(1H-NMR)和凝胶渗透色谱(GPC)进行了表征.考察了多嵌段聚苯乙烯溶液和固态的降解性能及热性能.实验结果表明,多嵌段聚苯乙烯不仅在紫外辐照条件下可发生光降解,而且也可通过胺解和水解反应进行降解.热重分析(TGA)和示差扫描量热(DSC)结果显示,邻硝基苄酯基团和三硫代碳酸酯基团的引入,对于多嵌段聚苯乙烯玻璃化转变温度和热稳定性并没有明显的影响.     

聚乳酸接枝葡聚糖共聚物的合成及其体外降解行为的研究

研究了聚乳酸接枝葡聚糖梳型共聚物的合成 ,以及共聚物的结构特征、亲水性能及降解行为的表征 .结果表明由于亲水性葡萄糖单元组分的引入以及共聚物的梳型结构特征 ,聚乳酸接枝葡聚糖共聚物的亲水性明显优于相应的线型聚乳酸 ,而且降解速度也明显加快 .由于这类梳型结构的聚多糖 聚酯共聚物综合了聚多糖细胞亲和性好和聚酯生物降解速率可调节性的特点 ,因此有望成为一类优良的细胞支架材料 .     

Biodegradable polycarbonates containing side carboxyl groups—synthesis,properties, and degradation study

The main objective of the presented research was to synthesise biodegradable aliphatic polycarbonates containing reactive carboxyl pendant groups and to examine the influence of the copolymer chain microstructure and composition on the process of their hydrolytic degradation and cytocompatibility. The work describes copolymerization of cyclic trimethylene carbonate derivative containing benzyl‐ester pendant group (benzyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate) with trimethylene carbonate. The copolymerization was conducted with the use of zinc (II) and lanthanum (III) acetylacetonates as ring‐opening polymerization coordination initiators. Detailed NMR analysis allowed to define the microstructure of the obtained copolymers, which depended on the composition and type of used initiator. The final tapered chain microstructure of the obtained copolymers was related to huge differences in comonomers reactivity and evidenced low level of transesterification of the main copolymer backbone. Chosen copolymers, with unprotected carbonyl groups, were subjected to in vitro degradation test and cytocompatibility studies. It was found that high concentration of carboxyl groups resulted in copolymers which formed hydrogels and were very prone to hydrolytic degradation; they were also cytotoxic toward osteoblast‐like MG 63 cells. Copolymers with lower content of carboxyl groups were found less susceptible to degradation and cytocompatible with studied cells. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2756–2769     

聚烯丙基氯化铵模板对AM/AA共聚物结构的影响

采用IR,1H-NMR和13C-NMR研究了聚烯丙基氯化铵(PAAC)模板对丙烯酰胺(AM)/丙烯酸(AA)共聚产物结构的影响,发现这种模板对共聚物P(AM/AA)序列结构和分子量有重要影响.由于共聚合体系中AA单体在PAAC模板聚合物上预组装,使得模板体系共聚物比无模板体系共聚物的AA和AM序列长度显著增加.这种类似多嵌段结构得到pKa′测定的进一步验证.另外模板分子量大小,模板和AA单体摩尔比,AM和AA摩尔比对共聚物结构的影响也进行了研究.应当指出这种模板聚合产物分离模板后仍有少量不能分离掉的PAAC聚合物存在.     

具有电活性苯胺四聚体接枝聚谷氨酸的合成与表征

以N-羟基琥珀酰亚胺(NHS)活化聚L-谷氨酸的羧基并与苯胺四聚体的氨基缩合,得到了以可生物降解的聚谷氨酸为主链,具有电活性的苯胺四聚体为侧链的新型接枝聚合物.用1H-NMR、质谱分析、光谱分析的方法确定了化合物的结构.侧链羧基的存在使聚合物可以溶解于碱性的缓冲溶液中.对聚合物的电化学性质进行了紫外及循环伏安的表征,研究结果表明,接枝后的聚合物具有与苯胺低聚体相似的可逆的氧化还原过程并可被质子酸掺杂,表现出良好的电化学活性.同时,以定量紫外吸收及元素分析的方法分别测定了聚合物的接枝率.实验中通过控制反应的投料比可以使苯胺四聚体的接枝率达到40%以上,并对聚合物的自掺杂现象进行了讨论.     

Synthesis of spherical particles by self-assembly of poly[2-(perfluorooctyl)ethyl acrylate-co-acrylic acid] in supercritical carbon dioxide

Spherical particles were prepared from poly[2-(perfluorooctyl)ethyl acrylateco-acrylic acid] random copolymers (P(POA-co-AA)) by self-assembly in supercritical carbon dioxide (scCO2). The P(POA-co-AA) copolymers with 9:1, 8:2, 7:3, and 6:4 molar ratios of the POA/AA unit completely dissolved in scCO2, however, the solubility was dependent on the POA/AA ratio. The copolymer with the higher AA content had a lower solubility. The scanning electron microscopy (SEM) observations revealed that the spherical particles were obtained in a heterogeneous state at pressures lower than the cloud point pressure. Dynamic light scattering and 1H NMR studies demonstrated that the copolymers formed random copolymer micelles consisting of the shells of the CO2-philic POA units and the cores of the CO2-phobic AA units and main chains. It was found that the formation of spherical particles could be optimized by the manipulation of the CO2 pressure and temperature for the different compositions of the copolymers.     

Synthesis and enzymatic degradation of 2‐methylene‐1,3‐dioxepane and methyl acrylate copolymers

Copolymers of 2‐methylene‐1,3‐dioxepane (MDO) and methyl acrylate (MA) containing ester units both in the backbone and as pendant groups were synthesized by free‐radical copolymerization. The influence of reaction conditions such as the polymerization time, temperature, initiator concentration, and comonomer feed ratio on the yield, molecular weight, and copolymer composition was investigated. The structure of the copolymers was confirmed by ¹H NMR, ¹³C NMR, and IR spectroscopy. Differential scanning calorimetry indicated that the copolymers had a random structure. An NMR study showed that hydrogen transfer occurred during the copolymerization. The reactivity ratios of the comonomers were r_MDO = 0.0235 and r_MA = 26.535. The enzymatic degradation of the copolymers obtained was carried out in the presence of proteinase K or a crude enzyme extracted from earthworms. The experimental results showed that the higher ester molar percentage in the backbone caused a faster degradation rate. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2898–2904, 2003     

PREPARATION AND CELL COMPATIBILITY OF FUNCTIONALIZED BIODEGRADABLE POLY(DL-LACTIDE-co-RS-β-MALIC ACID

In order to create a functionalized biodegradable polymer for vascular tissue engineering application,poly(DL- lactide-co-RS-β-malic acid)(PDLLMAc)was synthesized.PDLLMAc was obtained after hydrogenolysis of poly(DL- lactide-co-RS-β-benzyl malolactonate)(PDLLMA),which was from the ring-opening polymerization of DL-lactide(DLLA) and RS-β-benzyl malolactonate(MA)using stannous octoate as catalyst.The copolymers were characterized by ~1H-NMR, FTIR,GPC and DSC.The tensile strength and water uptake of the copolymers were measured.In copolymerization,the proportion of MA in the derived copolymers was lower than that in the feeding dose,a consequence of its lower reactivity. The molecular weight of the copolymers decreased with increasing MA content.The protective benzyl groups were completely removed in hydrogenolysis.The glass transition temperature(T_g)of the protected copolymers decreased with increasing MA content.The mechanical strength test showed that the tensile strength of PDLLMA decreased while elongation increased with MA content increasing,and the tensile strength increased and elongation decreased with increasing malic acid content in PDLLMAc for the formation of hydrogen bonding.The water uptake showed that more hydrophilic malic acid adsorbed more water in PDLLMAc.In order to test the reactivity of functional pendant groups,bioactive RGD peptide was immobilized on the functionalized polymer film surface and smooth muscle cells(SMCs)were cultured on it. The results showed that the functionalized copolymer was biocompatible and could be potentially applied in vascular tissue engineering.     

Photocatalytic degradation of poly(acrylamide-co-acrylic acid)

Poly(acrylamide-co-acrylic acid) copolymers of different compositions were synthesized and characterized. The copolymers were statistical with a relatively high percentage of acrylamide units, as determined by (13)C NMR. Reactivity ratios calculated by the Finemann-Ross and Kelen-Tudos methods showed that the copolymers were random with a reactivity ratio of r AM = 3.76 and r AA = 0.28. The photolytic and photocatalytic degradation of the copolymers and the homopolymers was conducted in the presence of combustion-synthesized nano anatase titania. The degradation of the copolymer in the presence of combustion-synthesized titania was significantly higher than that observed in the presence of commercial titania, Degussa P-25. The degradation was modeled by using continuous distribution kinetics by following the time evolution of molecular weight distribution. The degradation follows a two step mechanism, wherein the rapid first step comprises the scission of weak acrylic acid units along the chain which is followed by the breakage of relatively strong acrylamide units. The rate constants for the weak and strong links follow a linear trend with the percentage of acrylic acid and acrylamide in the copolymer, respectively. This linear variation can be correlated with a similar trend observed for the activation energies obtained for the pyrolytic degradation of the polymers.     

L-丙交酯-β-苹果酸共聚物的体外降解及细胞亲和性研究

研究了具有功能侧基的新型生物降解高分子——— [聚 (L 丙交酯 co β 苹果酸 ) ](PLMA)在pH 7 4的磷酸缓冲溶液中的降解和鼠的 3T3成纤维细胞在共聚物膜表面的贴附及生长 .研究了不同组成的共聚物在降解过程中的失重、表面形貌、组成及分子量变化 ,发现PLMA为本体降解 ,共聚物中苹果酸含量的提高可以加速降解 ,降解过程中聚苹果酸 (PMA)链段附近的酯键先水解断裂 .鼠的 3T3成纤维细胞在聚L 丙交酯 (PLLA)均聚物和苹果酸含量为 4mol% ,8mol%和 13mol%的共聚物膜上培养 5h ,细胞贴附率分别为 4 3%、71%、80 %和 4 3% .3T3成纤维细胞在苹果酸含量为 4mol%和 8mol%的共聚物膜上的生长情况好于在PLLA均聚物和苹果酸含量为 13mol%含量的共聚物膜上的生长 .