Poly(L-lactide)-Poly(ethylene glycol) Multiblock Copolymers: Synthesis and Properties

Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.

Synthesis and Characterization of Poly(L-lactide-co-ε-caprolactone) Copolymers

A series of random and block poly（ L-lactide-co-e-caprolactone ） （ PCLA ） copolymers whh different composition are prepared using stannous octaoate as catalyst.The effects of the amount of initiator on the intrinsic viscosity have been investigated. The structure of the PCLA copolymers is characterized by means of nuclear magnetic resonance（ NMR ）, Fourier transform infrared spectrum （ FTIR ）, differential scanning calorimetry （ DSC ） and X- ray diffraction （ XRD ） methods. It is shown that the synthesis condition and the composition of copolymers obrious influence on the structure of PCLA copolymers. Hydrolytic degradation of the copolymers in a PBS solution of pH 7.4 at 37.0℃ shows that the copolymers of different composhions degrade at different rates.

Preparation and characterization of biodegradable nanoparticles from methoxy poly(ethylene glycol)-poly(D,L-lactide)block copolymers as novel drug carriers

Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critical micelle concentration (CMC) by fluorescence spectroscopy was 0.0056 mg·ml -1 . The physical state of the inner core region of micelles was characterized with 1HNMR. The size of indomethacin (IMC) loaded micelles measured by dynamic light scattering (DLS) showed narrow monodisperse size distribution and the average diameters were less than 50 nm. In addition, the nanoparticles with relatively high drug loading content (DLC) were obtained.

Supercritical Fluid Impregnation of Essential Bark Oil in Copolymers of L-Lactide with 7-Membered Cyclic Compounds

In order to develop a novel controlled-release material, we previously attempted to impregnate poly(L-lactide) (poly(L-LA)), poly(L-LA-ran-CL) (CL: ε-caprolactone) or poly(L-LA-ran-TEMC) (TEMC: tetramethylene carbonate) with low boiling point, organic useful compounds using supercritical carbon dioxide (scCO2) as the solvent. In this work, the factors influencing impregnation of poly (L-LA) random copolymers with useful compounds were investigated under scCO2 using the copolymers previously used. The influence of temperature, pressure, and time on the impregnation contents of the useful compounds on the copolymers was evaluated. The polymer used, which is a base of this material, was poly(L-LA-ran-CL), poly(L-LA-ran-TEMC), or poly(L-LA-ran-DXO) (DXO: 1,5-dioxepan-2-one). Statistical random copolymers of L-LA with CL, TEMC, or DXO were synthesized using Sn(oct)2 as a catalyst at 150°C for 24 h without solvent. Preparation of the controlled-release materials was carried out using essential bark oil from Thujopsis dolabrata var. hondae and synthetic L-LA random copolymers as a base material under scCO2. The impregnation experiment, which investigated the influence of pressure, was conducted in the range of 10 to 20 MPa. The influence of temperature on impregnation was carried out at 40°C to 100°C. Impregnation time was varied from 1 to 5 h. The pressure of essential oil impregnated into poly(L-LA) random copolymers was the highest at 14 MPa. In the influence of temperature on impregnation, the amount of essential oil increased with increasing temperature.

Synthesis and Characterization of Poly(L-lactide-co-glycolide)

Poly （ l- lactide- co-glycolide ） （ PLGA ） with different compositions was prepared using stannous octaoate as catalyst by bulk ring-opening copolymerization of l-lactide and glycolide. The structure and properties of the PLGA copolymers were cbaracterized by means of attenuated total reflectance-Fourier transform infrared （ATR-FTIR）, ^1H NMR, differential scanning calorimeter （ DSC and X-ray diffraction （XRD） methods, The experimented results indicate that the synthetic conditions and the composition of copolymers have art obvious influence on the structure of PLGA copolymers, The degradation rate of eopolymers increased with the increasing of the glycolide component in the copolymers.

Preparation and Swelling Behavior of L-Lactide Interpenetrating Networks

Novel triblock copolymers of poly (L-lactide)-poly (ethylene glycol)-sebacate-poly (ethylene glycol)-poly (L-lactide) were synthesized by Ring-Opening Polymerization of different ratios of L-lactide with other three pre-prepared poly (ethylene glycol)-sebacate-poly (ethylene glycol) polymers, coded A, B and C which had different poly (ethyleneglycol) chain lengths. The copolymers were characterized by FTIR and 1H NMR spectroscopy, which indicated that the reaction of ROP took place and led to producing nine triblock copolymers having new different lactide chain lengths (n = 10, 25 and 50), AL10, AL25, AL50,BL10, BL25, BL50, CL10, CL25, and CL50. Nine polymer networks were also prepared from copolymers with sodium alginate S1 - S9 and finally mixed with a solution of hydroxyl ethyl cellulose to form SH1 - SH9.

Biodegradable Blend Nanoparticles of Amphiphilic Diblock Copolymers Prepared by Nano-Precipitation Method

Nanoparticles of biodegradable methoxy poly(ethylene glycol)-b-polyester amphiphilic diblock copolymers have widely investigated for use as controlled release drug delivery carriers. In this work, blend nanoparticles of methoxy poly(ethylene glycol)-b-poly(D,L-lactide) (MPEG-b-PDLL) and methoxy poly(ethylene glycol)-b-poly(ε-caprolactone) (MPEG- b-PCL) were prepared by nano-precipitation method without any surfactants. 1H-NMR spectra showed significant difference in integral peak areas, suggesting the nanoparticles with different MPEG-b-PDLL/MPEG-b-PCL blend ratios can be prepared. Transmission electron microscope revealed the blend nanoparticles had nearly spherical in shape with smooth surface. Average size of the blend nanoparticles obtained from light-scattering analysis slightly decreased with increase in blend ratio of MPEG-b-PCL. The MPEG-b-PDLL and MPEG-b-PCL were amorphous and semi-crystalline, respectively. Thermal transition properties of the blend nanoparticles were studied with differential scanning calorimetry (DSC). The DSC results showed that glass transition temperatures of the blend nanoparticles decreased and heats of melting steadily increased, while the melting temperature did not change as the MPEG-b-PCL blend ratio increased. This indicates the miscibility of MPEG-b-PDLL and MPEG-b-PCL in the amorphous phase of the blend nanoparticles. Thermogravimetric analysis showed that the blend nanoparticles clearly exhibited two thermal decomposition steps due to MPEG-b-PDLL decomposition followed with MPEG-b-PCL. The blend nanoparticles had two temperatures of maximum decomposition rate (Td, max) accorded to each blend component. The Td, max of MPEG-b- PDLL phase significantly decreased, while Td, max of MPEG-b-PCL phase did not change as the MPEG-b-PCL blend ratio increased. These results suggested that the desired thermal properties of blend nanoparticles can be tailored by varying the blend ratio.

A convenient method to prepare random LA/CL copolymers from poly(L-lactide) and ε-caprolactone

Sequential addition of L-lactide(LA) followed by ε-caprolactone(CL), and simultaneous addition of both monomers, afforded random LA/CL copolymers in the presence of lanthanide aryloxides under mild conditions. Transesterification was proved to play a predominant role in random copolymer formation. Moreover, treatment of poly(L-lactide) with ε-CL led to random copolymer formation, which provides a new strategy not only to prepare random LA/CL copolymers, but also to directly modify PLLA.

STUDIES ON THE DEGRADATION OF POLY(L-LACTIDE-r-TRIMETHENE CARBONATE) COPOLYMERS

Biodegradable poly（L-lactide-r-trimethene carbonate） copolymers （P（LLA-co-TMC）） with different compositions were synthesized. The degradation of the copolymers was carried out in phosphate buffer saline solutions （pH = 7.4） at 37℃. The compositions, structure and properties of the copolymers in degradation were characterized with IH-NMR, DSC, XRD, GPC, and SEM. The weight loss of the P（LLA-co-TMC） 50/50 was much faster than that of P（LLA-co-TMC） 85/15 and PLLA homopolymer. Interestingly, though the molecular weight of the compolymers decreased greatly during degradation, the compositions were rarely varied. After long time degradation, the PLLA segments were induced to crystallize in the P（LLA-co-TMC） 85/15 copolymer. The SEM observation of the surface and cross-section of P（LLA-co- TMC） 85/15 copolymer films found it was similar to the bulk degradation of PLLA homopolymer.

星型PLLA-PEG嵌段共聚物纤维膜的制备及其亲水性能

星型结构相比较于线型结构具有更稳定的形态和更优异的力学性能。选用季戊四醇(PET)为引发剂,辛酸亚锡(Sn(Oct)_(2))为催化剂,通过L-丙交酯(L-LA)的开环聚合(ROP)制备星型端羟基聚(L-丙交酯)(s-PLLA),并与聚乙二醇(PEG,相对分子质量为1000)缩合制备四臂星型聚(L-丙交酯)-聚乙二醇共聚物(s-PLLA-PEG)。采用^(1)H-核磁共振、^(13)C-核磁共振、傅里叶变换红外光谱、超高效聚合物色谱仪对产物进行表征,并用静电纺丝技术制备s-PLLA-PEG纤维膜进行亲水性能测试。结果表明:s-PLLA-PEG共聚物被成功合成;相对于s-PLLA,s-PLLA-PEG的熔体温度和玻璃化转变温度降低,柔韧性得到改善,韧性增强;s-PLLA-PEG纤维膜对水的接触角是84.10°,随着时间的推移,接触角逐渐减小,最终水被纤维膜完全吸收,相比较s-PLLA纤维膜具有更强的亲水性。该研究表明,PEG嵌段的引入可以有效改善s-PLLA纤维膜的亲水性,展现出静电纺s-PLLA-PEG纤维膜在医用敷料领域的应用前景。

交联共聚物的红外光谱定量分析研究

交联共聚物由于具有不溶不熔性,定量分析方法非常有限,红外光谱分析可以用溴化钾压片制样,故不受此限制。文章用红外内标法测定了甲基含氢硅油-丙交酯交联共聚物中两组分的含量。以KSCN为内标物资,以2 100 cm-1处的强吸收峰为KSCN的定量峰。以1 750 cm-1的强羰基吸收峰为丙交酯的定量峰,二者的吸光度比值为I=ALA/AKSCN。丙交酯和内标物质KSCN的质量比即浓度比为C=MLA/MKSCN,以C对I作图,得内标工作曲线。实验结果表明在2/5<MLA/MKSCN<8/5范围内有较好的线性关系。只要加入适量的内标物质,使C值落在直线范围内,即可获得较为准确的分析结果。文章为交联共聚物以及其他共聚物组成的测定提供了一种简便易行的实验方法。

聚丙交酯/聚乙二醇多嵌段共聚物的合成及其性能

A series of multiblock copolymers of PLLA\|PEG(PLE) with high molecular weight were synthesized by coupling PLLA\|PEG\|PLLA triblock copolymers with succinic anhydride in the presence of ( N,N\| dimethylamino) pyridine(DMAP) and dicyclohexylcarbodimide (DCC).The results of the viscometry measurement,GPC and 1H\|NMR,elucidated that multiblock PLE copolymers with high content of short PEG segments( M n=2000) had been successfully obtained.The crystallinity of the copolymers was investigated by X\|ray diffraction.Mechanical testing showed that multiblock copolymers had relatively high tensile strength and large elongation.In a word,the measurements showed that the multiblock PLE copolymers had high content of short PEG segments( M n=2000),high molecular weight( M w～100,000),excellent hydrophilicity and mechanical properties.The results of cells cultured on the multiblock PLE copolymer indicated that it might be suitable to be utilized as cell scaffold for tissue engineering.

葡聚糖-聚乳酸接枝共聚物的合成及其药物载体输送系统

合成葡聚糖-聚乳酸接枝共聚物,并以此为载体,选择盐酸阿霉素为模型药物,利用纳米沉淀法和双乳法构建出了载药纳米粒子,并通过透射电镜(scanning electron microscope,TEM)、动态光散射(dynamic light scattering,DLS)、紫外(UV-vis)对其形貌、粒径及包封率进行了表征,结果表明:不同共聚物/药物比例会影响载药纳米粒子的粒径、粒径分布及包封率.此外,载药纳米粒子的体外释放实验表明:在弱碱条件(pH=7.4)下的释放速度比在弱酸条件(pH=5.0)下的慢,说明释放介质的pH对其释放性能有较大影响,有利于药物在肿瘤细胞中的控释.

乙交酯/丙交酯/己内酯三元共聚物的合成及表征

A series of tri\|component copolyesters composed of glycolide/lactide/caprolactone (PGLC) were obtained by bulk ring\|opening copolymerization of glycolide(GA),L\|lactide (L\|LA) and caprolactone(CL) with Sn(Oct)\-2 as catalyst for the purpose of biomedical applications.Structure of the PGLC copolyester was characterized by means of GPC,\{\}\+1H\|NMR,DSC and X\|ray diffractometry techniques.It was found that the obtained polymer was a pure copolymer that consisting of no other side\|produced polymers and the copolyester was a random copolymer that presented an amorphous structure in a large range of composition.The hydrophilicity and degradation rate of the copolyester were also studied in detail and it was found that the hydrophilicity and hydrolysis rate were improved by increasing the amount of GA.The mechanical properties of the PGLC copolyester were identified by measuring the tensile strength and the elongation at break.The elongation of the copolyester could be improved by introducing CL to the PLGA.That the PGLC copolyester was a potential biomedical material was suggested.

聚乳酸-聚乙二醇嵌段共聚物结晶行为研究

用^1HNMR，SEC，XRD和DSC对聚乳酸（PLLA）-聚乙二醇（PEG）二嵌段共聚物进行了表征．由于共聚物中两种组分比例的不同，表现出某组分单独结晶或两种组分共同结晶．用DSC和POM方法，对两组分含量相当的共聚物进行了熔体结晶行为研究，并采用Avrami方程进行了结晶动力学计算．用Lauritzen—Hoffmann理论对PLLA—PEG结晶机理进行了分析．在70—94℃范围内，得到成核参数K（POM）=5．23×10^5K^2．共聚物的Kg和链折叠自由能σe。都比均聚物的文献报道值高，表明PEG链段的存在影响了PLLA的结晶，使得其成核较均聚物困难．

三臂支化PLLA-PDLA嵌段共聚物的合成及立构复合结晶行为

以三羟甲基乙烷为起始剂,开环聚合L-丙交酯(LLA),合成三臂支化左旋聚乳酸(PLLA)预聚物.采用端基活化技术对预聚物进行端羟基活化,再与D-丙交酯(DLA)进行开环聚合,合成了不同分子量的三臂支化左旋聚乳酸-右旋聚乳酸(PLLA-PDLA)嵌段共聚物.采用核磁共振谱和凝胶渗透色谱等对样品的结构和分子量进行测试,结果表明,合成的嵌段共聚物链结构具有链段立构规整度和高分子量的特点;通过调节DLA单体与PLLA预聚物的投料比,可实现对PLLA-PDLA嵌段共聚物的序列结构调控.差示扫描量热仪和广角X射线衍射结果表明,三臂支化PLLA-PDLA嵌段共聚物的异构体分子间生成立构复合晶体,其熔点高于200℃;共聚物的嵌段序列结构对材料的凝聚态转变行为有很大的影响.

不同旋光度PLGA的制备及其结晶性能研究

以消旋丙交酯、左旋丙交酯和乙交酯为原料,以辛酸亚锡为引发剂,在高真空条件下本体熔融开环聚合,制得一系列不同旋光度的丙交酯乙交酯共聚物(PLGA),其结构经1H NMR,IR,XRD和DSC表征。并采用DSC研究了PLGA的熔体结晶行为,结果表明其结晶性能随其旋光度的减少而显著降低,甚至不结晶。

聚乳酸-壳聚糖接枝共聚物的制备及性能

以L-乳酸(LLA)和壳聚糖(CS)为原料,4-(二甲胺基)吡啶(DMAP)及N,N′-二环己基碳酰亚胺(DCC)为催化剂在室温下,通过直接缩合方法制备了聚乳酸-壳聚糖接枝共聚物(PLLA-CS)。采用IR、1H-NMR及薄板毛细渗透法对其结构进行了表征。探讨了原料配比、催化剂用量、LLA的二氯甲烷溶液浓度、反应时间等对共聚物收率和亲水性的影响。得到最佳工艺条件:-NH2∶LLA为1∶15,DCC∶LLA为1∶1,LLA的二氯甲烷溶液浓度为1.88 mol/L,反应时间为24 h。此方法合成路线短、反应条件温和。聚乳酸-壳聚糖接枝共聚物具有良好的细胞亲和性,有望成为一类优良的组织工程材料。

DL-乳酸-ε-己内酯无规共聚物改性聚DL-乳酸

合成了高分子量DL-乳酸-ε-己内酯无规共聚物(PLCA),其结构经1H NMR表征。通过溶液共混制备了用PLCA改性DL-聚乳酸(PDLLA)的复合材料PDLLA/PLCA(PLC)。研究了PLC的微观形态,力学性能,降解性等。结果表明,PLCA与PDLLA具有良好相容性;与PDLLA比较,PLC的柔韧性得到显著提高,降解速度加快。

微波辅助壳聚糖接枝聚乳酸共聚物的合成及表征

在微波辅助下,以辛酸亚锡为催化剂、壳聚糖(CS)为大分子引发剂引发消旋丙交酯(D,L-LA)本体开环聚合制备了壳聚糖接枝聚乳酸共聚物。通过正交试验确定了最佳合成条件:微波功率10W,反应温度120℃,反应时间15min,催化剂用量:n(丙交酯)∶n(辛酸亚锡)=1000∶1。通过红外光谱、元素分析、核磁共振氢谱、X射线衍射和热分析测试技术对接枝共聚物的结构与性能进行了表征和测试。结果表明,在微波条件下,能快速、有效地合成壳聚糖接枝聚乳酸共聚物,单位糖环上聚乳酸支链的平均乳酰单元数大于17.46;聚乳酸支链的引入有效削弱了壳聚糖分子间和分子内较强的氢键作用,与壳聚糖相比较,共聚物的结晶性能下降,热分解发生在246℃,低于壳聚糖的253℃;随n(D,L-LA)/n(CS糖环数)值增大,共聚物中平均乳酰单元数逐渐增大,共聚物的结晶性能、起始分解温度逐渐下降。