星形聚乙二醇-聚乳酸嵌段共聚物的合成与表征

以不同臂数和分子量的星型聚乙二醇(sPEG)和L-丙交酯为原料,采用开环聚合法合成了以星型聚乙二醇为内部嵌段、聚L-乳酸为外部嵌段的多臂星形聚乙二醇-聚乳酸嵌段共聚物(sPEG-b-PLLA)。研究了sPEG的臂数、分子量及L-丙交酯/sPEG投料比等参数对产物结构与性能的影响。并分别用红外光谱(FT-IR)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)、差示扫描量热(DSC)对产物进行了表征,证实所合成的嵌段共聚物具有预期的结构。结果表明,sPEG-b-PLLA为结晶性聚合物,且表现出与PLLA相似的晶型,随着PLLA链段的增加,产物的结晶度也呈增大的趋势;与PLLA相比,sPEG-b-PLLA的接触角随着PEG链段的增多而增大,表明其亲水性明显改善。     

聚乙二醇改性聚乳酸嵌段共聚物的合成与亲水性研究

以DL-丙交酯和分子量Mn=400、1000和2000聚乙二醇(PEG)为原料,在辛酸亚锡催化下开环聚合制备了聚乳酸(PLA)-聚乙二醇-聚乳酸三嵌段共聚物(PLEG)。考察了催化剂用量、反应时间对产率和[η]的影响。用FT-IR、1 H-NMR、GPC、DSC、XRD、静态水接触角等对共聚物进行了表征和性能测试。结果表明,催化剂用量为0.2%、反应时间分别为PLEG400共聚物2～4h、PLEG1000共聚物4～8h和PLEG2000共聚物8～12h较宜;共聚物组成比与投料比较一致,共聚物的数均分子量与理论计算值较一致;共聚物为无定形态,PEG的引入使共聚物Tg明显低于PLA均聚物,且随PEG的Mn减小,共聚物的Tg随之降低;而且PEG的引入明显提高了PLA的亲水性,PEG的Mn越小,PLA亲水性的提高程度越大。通过控制催化剂用量和反应时间,150℃可以得到分子量符合投料组成比要求、亲水性有明显提高的PLA-PEG-PLA三嵌段共聚物。     

端羧基聚乳酸共聚物的合成及表征

以乳酸为原料,辛酸亚锡为催化剂,采用梯度升温法,在168℃、0.098MPa下直接熔融缩聚生成端羧基聚乳酸共聚物P(LA/SA)、P(LA/CA)和P(LA/AC).用乌氏粘度法、FT-IR、1H-NMR、DSC、TGA及XRD等对共聚物进行了表征.结果表明和PLA相比,3种端羧基共聚物Tg均有不同程度的降低,说明端羧...     

端羟基聚乳酸共聚物的合成及表征

以乳酸为原料,辛酸亚锡为催化剂,采用梯度升温法,在168℃、0.098 MPa下直接熔融缩聚合成端羟基改性聚乳酸共聚物聚（乳酸/1,4丁二醇）[P（LA/BDO）]、聚（乳酸/二乙醇胺）[P（LA/DEA）]和聚（乳酸/ε-己内酯）[P（LA/CL）]。用乌氏黏度法、红外光谱（FT-IR）、核磁共振（1H-NMR）、差...     

聚乙二醇改性聚乳酸的合成与性能表征

以外消旋乳酸(D,L-LA)和不同数均分子量(Mn)的聚乙二醇(PEG)为原料,通过熔融缩聚法,合成了系列聚乳酸聚乙二醇(PLEG)。最佳工艺条件为:以(Sn(Oct)2)为催化剂,m(Sn(Oct)2)为0.8%,n(PEG)∶n(D,L-LA)=1∶600,聚合温度170℃,压力0.096 MPa条件下,反应8h。用特性粘度测试、FT-IR、XRD、接触角等对其进行表征,实验结果表明系列PLEG中PLEG-800接触角为63°,表明其亲水性能最好;PEG-800和乳酸共聚合成的PLEG的粘均分子量最大,可达48997,与PDLLA相比,结晶度有较大提高,亲水性得到改善。     

熔融缩聚合成聚乳酸-聚乙二醇共聚物及其性能研究

采用羧基封端乳酸预聚物与聚乙二醇熔融缩聚合成了聚乳酸-聚乙二醇共聚物,并用GPC、FTIR、1H-NMR等方法表征了预聚物与共聚物,结果表明,预聚物的羧基封端率高于95%,预聚物的相对分子质量可由投料比(物质的量比)控制.热分析结果表明,共聚物中聚乳酸链段呈无规分布,而聚乙二醇链段能够形成结晶微区.力学性能测试结果表明,共聚物的断裂伸长率达371%,有望在聚乳酸韧性改性方面得到应用.     

聚乙二醇-聚丁二烯-聚乙二醇三嵌段共聚物的制备及性能

以活性阴离子聚合所得端羟基聚丁二烯(HTPB)及聚乙二醇(PEG)为原料,依次通过苯磺酰化和亲核取代反应制备聚乙二醇-聚丁二烯-聚乙二醇(PEG-b-PB-b-PEG)三嵌段共聚物。利用红外光谱、核磁共振氢谱、核磁共振碳谱及凝胶渗透色谱-激光光散射联用仪证实所得三嵌段共聚物结构与设计相一致。差示扫描量热分析及热重分析对PEG、HTPB及PEG-b-PB-b-PEG热性能对比研究显示,PEG-b-PB-b-PEG的玻璃化转变温度(T_g)为-82.8℃,其结构中PEG链段的结晶行为被无定形PB链段所限制,且PEG-b-PB-b-PEG具有较好的热稳定性。动态光散射粒度分析及透射电子显微镜对PEG-b-PB-b-PEG组装特性研究表明,PEG-b-PB-b-PEG在水溶液中形成稳定分布的点状胶束。     

赖氨酸改性聚乳酸/聚乙二醇共聚物的制备及表征

在丙交酯与聚乙二醇开环共聚的基础上进行了二次聚合,利用具有生物相容性的赖氨酸对聚乳酸/聚乙二醇低聚物进行改性,制备出了赖氨酸改性聚乳酸/聚乙二醇共聚物。通过红外光谱、核磁共振谱、X射线衍射分析仪、差示扫描量热仪、凝胶渗透色谱和接触角测量仪分析比较了聚乳酸、聚乳酸/聚乙二醇和赖氨酸改性聚乳酸/聚乙二醇3种聚合物之间存在的差异。结果表明,实验成功合成了赖氨酸改性聚乳酸/聚乙二醇共聚物;赖氨酸(L-lys)的引入使得共聚物的热焓(ΔH)和熔点(T_m)分别由纯PLLA的81.57 J/g和177.34℃降到46.02 J/g和151.34℃,有效地改善了分子链的柔性和结晶度;聚合物的数均相对分子质量(M_n)也由纯PLLA的7.7×10~4降到了3.2×10~4,且相对分子质量分布变宽,但亲水性却得到大幅提高,有望适用于组织工程领域。     

新型聚乳酸-聚酰亚胺嵌段共聚物的合成与表征

用氨基封端的PEG-800(ATPEG)与均苯四甲酸酐(PMDA)共聚得到一种新型的氨基封端的可溶性聚酰亚胺(PI)。氨基封端的PI在辛酸亚锡(Sn(Oct)2)的催化作用下引发丙交酯开环共聚,形成聚乳酸-聚酰亚胺(PLA-PI-PLA)嵌段共聚物。采用傅里叶变换红外光谱(FT-IR)、核磁氢谱(1H NMR)、凝胶渗透色谱(GPC)、水接触角等对PI和PLA-PI-PLA进行了表征。FT-IR、1H NMR、GPC的结果表明成功合成了PI及PLA-PI-PLA。水接触角结果显示PLA-PI-PLA相对于聚乳酸亲疏水性明显改善,同时PI主链上的酰亚胺环能在一定的条件下发生开环反应,可提供修饰聚乳酸材料的活性位点。     

超临界流体技术制备吗啡/聚乳酸-聚乙二醇共聚物缓释微球

以L-聚乳酸-聚乙二醇三嵌段共聚物(PLLA-PEG-PLLA)为载体材料,通过超临界流体强制溶液分散技术制备吗啡/聚乳酸-聚乙二醇共聚物(MF/PLLA-PEG-PLLA)的复合微球,考察了PEG分子量的变化对微球性能的影响。通过表面形貌,粒径及粒径分布,载药量,包封率及释放性能来表征复合微球的各项性能;利用气相色谱法测定二氯甲烷和甲醇的残留量;通过溶血实验来评价复合微球的血液相容性。实验表明,所制备的复合微球呈球形或类球形形貌,平均粒径在1.99～6.20μm之间,载药量达到17.92%,包封率最高可至69.57%,复合微球的药物释放呈先突释后缓释的释药模式;二氯甲烷和甲醇的残留量分别为0.0076%和0.0016%;微球溶血率<1%,远小于国家标准5%,证明复合微球具有较好的血液相容性。     

两亲性嵌段共聚物聚乳酸-聚亮氨酸-聚乙二醇的合成及性能研究

具有温度敏感的生物水凝胶因可根据温度变化发生相变而受到人们重视。采用直接熔融聚合法,先以外消旋乳酸(D,L-LA)和L-亮氨酸(Leu)为原料,辛酸亚锡为催化剂,合成了聚乳酸-聚亮氨酸;再以一定比例将上述两组分共聚物与一定分子量的聚乙二醇(PEG)混合,在辛酸亚锡为催化剂的情况下熔融聚合制备聚乳酸-聚亮氨酸-聚乙二醇三组分嵌段共聚物。采用傅里叶红外光谱(FTIR)、核磁共振波谱仪(1 H-NMR)和凝胶渗透色谱仪(GPC)对两组分和三组分共聚物进行了系统表征,所得三组分共聚物的一定浓度的水溶液在20～35℃时具有溶胶-凝胶转变特性,能够满足该生物友好材料在药物缓释领域中的应用。     

Synthesis and characterization of cholesterol-poly(ethylene glycol)-poly(D,L-lactic acid) copolymers for promoting osteoblast attachment and proliferation

A novel cholesterol-poly(ethylene glycol)-poly(D,L-lactic acid) copolymer (CPEG-PLA) has been synthesized as a potential surface additive for promoting osteoblast attachment and proliferation. The gel permeation chromatography (GPC) and nuclear magnetic resonance spectroscopy (NMR) results indicated the product had expected structure with low polydispersities in the range of 1.1–1.5. By blending the poly(D,L-lactic acid) (PLA) with CPEG-PLA, the surface of modified PLA membrane was investigated by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contact angle. The results revealed the enrichment of PEG chain on the surface. Osteoblast cell line (MC3T3) was chosen to test the cell behavior on modified PLA membranes. The osteoblast test about cell attachment, proliferation, cell viability and cell morphology investigation on CPEG-PLA modified PLA substrates showed the CPEG-PLA with 15 and 5 ethylene glycol units promoted osteoblast attachment and growth, while the CPEG-PLA with 30 ethylene glycol units prevent osteoblast adhesion and proliferation. This simple surface treatment method may have potentials for tissue engineering and other biomedical applications.     

Synthesis and characterization of polyester copolymers based on poly(butylene succinate) and poly(ethylene glycol)

A series of polyester copolymers was synthesized from 1,4-succinic acid with 1,4-butanediol and poly(ethylene glycol) through a two-step process of esterification and polycondensation in this article. The composition and physical properties of copolyesters were investigated via GPC, ¹HNMR, DSC and PLM. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), and crystallinity (X_c) of these copolyesters decreased gradually as the content of PEG unit increased. Otherwise, experimental results also showed that the contents of PEG in copolymers had an effect on the molecular weight, distribution, thermal properties, hydrolysis degradation properties, and crystalline morphology of polyester copolymers.     

Nano-sized micelles of block copolymers of methoxy poly(ethylene glycol)-poly(epsilon-caprolactone)-graft-2-hydroxyethyl cellulose for doxorubicin delivery

The amphiphilic block copolymers methoxy poly(ethylene glycol)-poly(epsilon-caprolactone) was grafted to 2-hydroxyethyl cellulose to produce the water-soluble copolymers. Doxorubicin loaded nanoparticles were prepared by dialysis method and the sizes of nanoparticles were determined by dynamic light scattering in solution and atomic force microscopes. As results the sizes were detected in a range of 197.4 to 340.7 nm. The in-vitro release of Dox was studied in phosphate and acetate buffered solution at 37 degrees C. The results showed that 43 and 53% of Dox remained after an incubation period of 7 days. The cytotoxicity of Dox loaded micelles was investigated in two different human MCF-7/wild type and MCF-7/Adriamycin drug resistant cells lines. The Dox-loaded micelles showed reduced cytotoxicity compared to free Dox in MCF-7/wild type and MCF-7/Adriamycin drug resistant cells.     

Synthesis and characterization of conjugated poly (amino benzyl alcohol) and poly (ethylene glycol) for solid polymer electrolyte

A solid polymer electrolyte chemically bonded to a π-conjugated polymer was prepared for the use as a designed ladder-type structure by the graft copolymerization of poly (aminobenzyl alcohol) (PABA) with poly (ethylene glycol) (PEG). PABA was used as the frame for the ladder and the PEG as the rungs. The expected synergic effect afforded by the introduction of the ionic salts into the crosslinked conjugated polymer and PEG network was investigated as a function of its structure, morphology, and ionic conductivity. The insertion of the ionic salts into the PABA-PEG-PABA network led to the enhancement of the ionic conductivity compared to that of PEG/LiClO₄. The synergic effect may be explained by the more efficient segmental motion of the polymer chains or better ion mobility in the network due to the interrupted crystallization of the PEG chains. The fine tuning of the crosslinked conjugated polymer gel might enable it to show a faster response to electrochemical stimuli.     

去甲斑蝥素PLA-PEG纳米微球的制备研究

采用复乳法和相分离法两种方法制备去甲斑蝥素的聚乳酸-聚乙二醇嵌段共聚物(PLA-PEG)纳米微球.对比了两种不同方法对制得的含药微球在粒径、包封率以及缓释性能方面的差异.用激光粒度分析仪表征了微球的粒径及其分布,并用透射电镜观察了微球的形貌,其结果表明:复乳法与相分离法制备的微球粒径均在100nm左右,并且成球性好;相对于复乳法,相分离法制备的微球分布较宽,包封率较高,可达到50%左右;体外释放实验表明两种方法制备的微球都具有缓释作用.     

Synthesis, characterization and hydrolytic degradation of degradable poly(butylene terephthalate)/poly(ethylene glycol) (PBT/PEG) copolymers

Hydrolytic degradable PBT/PEG copolymer was synthesized by macromolecular transesterification method from PBT and PEG macromonomers. The resultant copolymers were characterized by ¹H-NMR and GPC. The non-isothermal crystallization behavior of these copolymers was studied by differential scanning calorimetry (DSC). The water absorption and hydrolytic degradation behavior of PBT/PEG copolymers were also studied in detail. This work was partly presented in 6^th ASBM, July 19–22, 2004, Emei City, Chingdu, China. Fan LY is the co-first author for this work.     

Preparation and characterization of poly(vinyl alcohol)/poly(epsilon-caprolactone)-poly(ethylene glycol)-poly(epsilon-caprolactone)/nano-hydroxyapatite composite membranes for tissue engineering

In this paper, the poly(vinyl alcohol)/poly(epsilon-caprolactone)-PEG-poly(epsilon-caprolactone)/nano-hydroxyapatite (PVA/PCEC/n-HA) composite membranes were prepared by solution casting and evaporation methods. The effect of n-HA content on the properties of the composite membranes was studied. The PVA/PCEC/n-HA composite membranes were analyzed by FTIR spectroscopy, X-ray diffraction, water content measurement, contact angle, mechanical test, scanning electron microscopy. The results showed that the surface roughness of the composite membranes increased with the increase of n-HA contents. The n-HA content had obvious influence on the swelling ratio, tensile strength and elongation rate of the composite membranes. With the increase of n-HA contents, the swelling ratio increased at first, and then decreased; tensile strength and elongation rate decreased gradually. The PVA/PCEC/n-HA composite membranes may be applied in the field of tissue engineering.