熔融共聚法用外消旋乳酸直接合成聚乙醇酸-乳酸及其表征

以乙醇酸(GA)、廉价的外消旋乳酸(D,L-LA)为原料,以氯化亚锡(质量分数0.5％)为催化剂,在165℃、70 Pa下熔融聚合10 h,通过熔融共聚法直接合成了不同配比的系列生物降解材料聚乙醇酸-乳酸(PGLA),用凝胶渗透色谱、傅里叶变换红外光谱、核磁共振氢谱、差示扫描量热分析、X射线衍射等系统地对其进行了表征。当n(GA):n(D,L-LA)=1:1,直接熔融聚合法获得的D,L-PGLA 50／50的重均相对分子质量为24 300,比相同条件下合成的L-PGLA 50／50的18 000要高。     

生物降解材料聚乳酸的直接法合成与表征

分别以外消旋乳酸(D,L-LA)和左旋乳酸(L-LA)为原料,通过熔融聚合法直接合成了生物降解材料聚外消旋乳酸(PDLLA)和聚左旋乳酸(PLLA),并用特性粘度[η]、凝胶渗透色谱(GPC)、傅立叶红外光谱(FTIR)、核磁共振氢谱(1H NMR)、差热分析(DSC)、X-射线衍射等手段.对PLLA、PDLLA的相对分子质量、结构、性能等进行了系统的表征与比较,发现相同合成条件下PLLA的相对分子质量、熔融温度、熔融热、结晶度等明显比PDLLA高。     

生物降解材料聚乳酸-聚乙二醇的直接熔融共聚法合成与表征

直接以外消旋乳酸(D,L-LA)单体为原料,使其与数均相对分子质量(Mn)为1000的聚乙二醇(PEG)[m(LA)：m(PEG)=9]共聚,通过直接熔融共聚法合成了生物降解材料聚乳酸-聚乙二醇(PELG),用特性黏数[η]、凝胶渗透色谱(GPC)、傅立叶红外光谱(FTIR)、核磁共振氢谱(^1H NMR)、差热分析(DSC)、X-射线衍射、接触角测试等手段,对其相对分子质量、结构、性能等进行了系统的表征。相同合成条件下,PELG与聚乳酸相比,其相对分子质量高,亲水性能也有所改善。在相近的合成条件下,D,L-LA与PEG直接熔融共聚能获得比D,L-丙交酯开环共聚高的相对分子质量,并达到与L-丙交酯开环共聚相当的相对分子质量。     

直接熔融聚合法合成生物降解材料PLEG研究 V反应机理

直接以乳酸(LA)单体和聚乙二醇(PEG)为原料,通过直接熔融共聚法,合成了生物降解材料聚乳酸-聚乙二醇(PLEG),用特性粘数[η]、GPC、FTIR1、H NMR、DSC和X-射线衍射等手段对其进行了系统的表征,发现许多因素对PLEG存在一定的影响,如不同的预聚方式时PLEG的组成不同、左旋乳酸(L-LA)获得的共聚物相对分子质量不如外消旋乳酸(D,L-LA)等。在此基础上,初步探讨了LA与PEG直接熔融共聚的反应机理。     

异佛尔酮二异氰酸酯溶液扩链合成聚乳酸类药物缓释剂

以外消旋乳酸(D,L-LA)直接熔融聚合得到的低相对分子质量聚外消旋乳酸(PDLLA)为原料,通过二异氰酸酯扩链合成了聚乳酸类药物缓释材料。当采用异佛尔酮二异氰酸酯(IPD I)为扩链剂,反应在四氢呋喃溶液中进行时,扩链反应工艺条件为:扩链剂用量n(NCO)∶n(OH)=2∶1时,66℃下回流反应2 h,相对分子质量增加近2.92倍。与2,4-甲苯二异氰酸酯(TD I)扩链法相比,IPD I溶液扩链法不仅提高产物相对分子质量的效果非常接近,具有反应温和、条件易调控等优点,而且使所得聚乳酸类药物缓释材料具有较高的生理安全性。     

医用纤维材料PGLA910的直接熔融聚合法研究

分别以D,L-乳酸(D,L-LA)、L-乳酸(L-LA)为原料,与乙醇酸(GA)通过熔融聚合法进行共聚,在催化剂SnCl2用量0.5％(wt)、反应温度165℃、反应压力70Pa、反应时间10h的条件下直接合成了生物降解的医用纤维材料聚乙醇酸-乳酸(90/10)(PGLA 910)。产品用IR、DSC、X-射线衍射等进行了表征,并与乙交酯开环聚合二步法合成的PGLA910进行了比较。直接熔融聚合产品的结晶度接近于二步法,D,L-PGLA910的结晶度和微晶尺寸比L型的大。直接熔融共聚工艺流程短、简单易行、耗时少、成本低,有利于医用纤维材料PGLA910的规模开发。     

催化剂对L-乳酸和乙醇酸共聚物结构性能的影响

以L-乳酸(LA)和乙醇酸(GA)(LA:GA摩尔比为20:80)为原料,在170℃、压力小于70 Pa下反应10 h,直接熔融聚合合成乳酸-乙醇酸共聚物(PLGA),研究了催化剂种类、催化剂用量以及复配催化剂比例对PLGA特性粘数的影响。结果表明,使用复合催化剂氯化亚锡(SnC l2)与对甲基苯磺酸(TSA),摩尔比为1:1,其中SnC l2相对LA与GA的总质量的质量分数为0.4%时,所得PLGA产物的特性粘数较高,为0.352 dL/g。红外光谱和核磁共振氢谱表明,PLGA为LA与GA共聚物,共聚产物中GA比例大于投料值,由差示扫描量热分析和X射线衍射分析表明,PLGA为非结晶高聚物。     

L-乳酸和乙醇酸共聚物的直接合成与微结构分析

采用直接法熔融缩聚制备L-乳酸(L-LA)和乙醇酸(GA)共聚物.先是以摩尔比为90/10的L-LA和GA为原料生成低聚物,然后L-LA和GA低聚物在双催化剂二水合氯化亚锡和对甲苯磺酸的催化下进一步反应.在反应中,未使用任何有机溶剂.反应最终产物的性能和结构通过核磁共振(NMR)、差示扫描量热 (DSC)等手段进行表征.结果表明,GA显示了比L-LA更高的反应活性,聚合过程中可能通过酯交换减少了GA和LA嵌段长度,而且随着GA含量和反应时间的增加会使共聚物产生更多的消旋,并使结晶度下降.目前反应条件下进行了嵌段共聚而非随机共聚.结果也表明,相对分子质量较高的L-LA和GA共聚物是可以通过直接聚合在适宜的工艺条件下制得.     

胆固醇-聚(D,L-乳酸)的直接熔融聚合法制备与表征

取代传统的丙交酯开环共聚法,直接以外消旋乳酸(D,L-LA)为原料,以廉价的氯化亚锡为催化剂,采用熔融聚合法合成胆固醇-聚(D,L-乳酸)共聚物。分别考察不同投料比、预聚时间和熔融共聚时间的影响,并用FT-IR1、HNMR、GPC、DSC等进行了系统表征。当投料比n(胆固醇)∶n(乳酸)=1∶66、预聚4 h、熔融共聚10 h、催化剂用量0.3%时,以85%的产率生成了重均相对分子质量(Mw)达3 600(分散度Mw/Mn=1.24)的共聚物。新方法步骤少、路线简捷,相对分子质量可以达到丙交酯开环共聚法的水平,且成本更加低廉。     

直接熔融聚合法合成生物降解材料PLEG研究Ⅴ反应机理

直接以乳酸（LA）单体和聚乙二醇（PEG）为原料,通过直接熔融共聚法,合成了生物降解材料聚乳酸-聚乙二醇（PLEG）,用特性粘数[η]、GPC、FTIR、1H NMR、DSC和X-射线衍射等手段对其进行了系统的表征,发现许多因素对PLEG存在一定的影响,如不同的预聚方式时PLEG的组成不同、左旋乳酸（L-LA）获得的共聚物相对分子质量不如外消旋乳酸（D,L-LA）等.在此基础上,初步探讨了LA与PEG直接熔融共聚的反应机理.     

Molecular and morphological characterization of poly<Emphasis>(L-</Emphasis>lactic acid<Emphasis>-</Emphasis>co<Emphasis>-</Emphasis>glycolic acid<Emphasis>)</Emphasis> P(L-LA/GA) copolymers prepared by Azeotropic distillation

The synthesis and molecular/morphological characterization of poly(L-lactic acid-co-glycolic acid) P(L-LA/GA) copolymers were investigated. The optimum reaction conditions were first determined by azeotropic distillation polymerization of poly(L-lactic acid) P(L-LA) homopolymers. Once the best reaction conditions were determined, the P(L-LA/GA) copolymers were synthesized by increasing the glycolic acid (GA) proportion in the reaction mixture from 0 to 7.5 mol%. The ¹³C NMR technique allowed inferring the formation of a copolymer with increasing segmental GA characteristics. These last with the potential to be rejected from the main crystals, assumption that was supported by the convergence of the crystallization and melting temperatures as the molar ratio of GA increased. The diffraction patterns of the copolymers demonstrated the gradual formation of α-α” crystal blends with the GA content and the crystallization and meting results allowed conclude that the increasing number of GA units in the main chain was related to molecular rejection, which resulted in a secondary exclusion phase, the major contribution to melting at the first melting endotherm. This behavior was in correlation with the step-like crystallization and melting mechanism previously proposed for high temperature engineering polymers.     

外消旋乳酸直接聚合-二异氰酸酯溶液扩链反应机理

以2,4-甲苯二异氰酸酯（TDI）为扩链剂,以外消旋乳酸（D,L-LA）直接熔融聚合合成的低分子量聚外消旋乳酸（PDLLA）为预聚体,在四氢呋喃（THF）溶液中进行扩链,使用不同的沉淀剂终止扩链反应,用黏均分子量、红外光谱（IR）、核磁共振氢谱（1H NMR）、DSC等对扩链产物进行了表征和对比,探索外消旋乳酸直接熔融聚合-二异氰酸酯溶液扩链的反应机理。结果表明,二异氰酸酯溶液扩链中,前期的机理与二异氰酸酯熔融扩链类似,但溶液扩链结束时,使用不同的沉淀剂,有不同的终止机理：用甲醇沉淀时,残余NCO与甲醇OH反应,可保持原有聚合物结构基本不变;用水沉淀时,残余NCO与水反应较复杂,易引起交联产物形成。     

Impact modification of lactic acid based poly(ester-urethanes) by blending

Branched biodegradable poly(ester-urethane)(PEU) was blended with two elastic biodegradable copolymers in proportions 5, 10, 15, and 20 wt % to investigate their effect on this hard and brittle polymer. Copolymer of L-lactide and ϵ-caprolactone, P(L-LA50/CL50), was synthesized by ring-opening polymerization and the other elastic poly(L-lactic acid-co-ϵ-caprolactone)urethane, P(LA50/CL50)U, was prepared by direct polycondensation of L-lactic acid and ϵ-caprolactone, followed with urethane bonding. In addition, four elastic biodegradable copolymers, three of them P(L-LA/CL) and one P(LA/CL)U, were blended with linear PEU to investigate their modifying effect on PEU. These compositions studied were 10, 15, and 20 wt % of P(L-LA40/CL60), P(L-LA60/CL40), P(L-LA80/CL20), and P(LA40/CL60)U in PEU. Blending was done in a batch mixer. PEU became more ductile when blended with P(L-LA/CL) and P(LA/CL)U, and its impact resistance improved markedly. In general, an addition of 15 wt % of copolymer appeared to give the most desirable mechanical properties. Moreover, the more L-lactide in the P(L-LA/CL) copolymer, the better was the miscibility of the blends, as shown by dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). One P(L-LA/CL) was also blended with poly(DL-lactide) (PDLLA) to see if the dispersion of rubbery copolymer particles was the same in PDLLA and PEU. A well-known commercial nonbiodegradable rubber [styrene/ethylene/butylene copolymer (SEBS)] was blended with linear PEU to compare its effect on impact strength. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1335–1343, 1997     

D,L-乳酸-肌醇星形聚合物的合成与表征

以廉价易得的D,L-乳酸和无毒的肌醇(Ins)为原料,采用工艺简单、成本低廉的直接熔融聚合法合成了肌醇聚乳酸酯——以肌醇为核的星形聚D,L-乳酸(SPDLLA)。当n(Ins)∶n(LA)=1∶120时,SPDLLA较合适的合成工艺为:140℃预聚8 h后,在w(SnCl2)=0.3%催化下,170℃熔融聚合8 h,可获得最大特性黏数[η]为1.208 dL/g的共聚物。改变投料摩尔比,合成了系列SPDLLA,并用[η]、FTIR、1HNMR、GPC、XRD等手段进行了结构与性能表征,发现不同投料比所得的SPDLLA均为无定形态,它们的Tg(35~42℃)均低于线形聚D,L-乳酸(LPDLLA),最高Mw可达8 600,可望应用于药物缓释等领域。     

Poly(Lactic Acid)-Based Blends With Tailored Physicochemical Properties for Tissue Engineering Applications: A Case Study

Binary blends of poly(L-lactic) acid (PLLA: 201790 Da) and poly(lactide-co-glycolide) (PLGA) (LA:GA = 50:50 mol:mol; 32030 Da) with various compositions were prepared. Physicochemical properties of PLLA/PLGA blends were analyzed. Blends showed a biphasic morphology, with distinct glass transition temperatures, which only slightly approximated compared to pure polymers. Analysis of tensile mechanical properties through the Kerner-Uemura-Takayanagi model showed compatibility for PLLA/PLGA 75/25 blend. Rapid degradation of PLGA phase (2–8 weeks) in PLLA/PLGA 75/25 blend led to porous samples, which appear promising for drug delivery and tissue engineering. A limited inflammatory reaction resulted from subcutaneous implantation of PLLA/PLGA 75/25 in Balb-c mice.     

Syntheses of poly(lactic acid‐co‐glycolic acid) serial biodegradable polymer materials via direct melt polycondensation and their characterization

The optimal synthetic conditions of poly(lactic acid‐co‐glycolic acid) (PLGA) via melt copolycondensation directly from L ‐lactic acid (L ‐LA) and glycolic acid (GA) with a feed molar ratio of 50/50 are discussed; the important drug‐delivery carrier PLGA50/50 is used as a special example. With reaction conditions of 165°C and 70 Pa and with 0.5 wt % SnCl₂ as the catalyst, 10 h of polymerization gave the L ‐PLGA50/50 with the biggest intrinsic viscosity ([η]), 0.1993 dL/g. The optimal synthetic conditions were verified by the synthesis of D,L ‐PLGA50/50 with D,L ‐lactic acid (D,L ‐LA) instead of L ‐LA, but the biggest [η] was 0.2382 dL/g. Under the same synthetic conditions with L ‐LA and D,L ‐LA as starting materials, serial PLGA with different molar feed ratios, including 100/0, 90/10, 70/30, 50/50, 30/70, 10/90, and 0/100, were synthesized via simple and practical direct melt copolycondensation, and their solubilities were investigated. When the glycolic acid feed molar percentage was equal to or more than 70%, solubilities in tetrahydrofuran and CHCl₃ became worse, and some samples were even wholly insoluble. These biodegradable polymers were also systematically characterized with gel permeation chromatography, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, differential scanning calorimetry, and X‐ray diffraction. PLGA synthesized from L ‐LA and D,L ‐LA had many differences in weight‐average molecular weight (M_w), glass‐transition temperature, crystallinity, and composition. When the molar feed ratio of LA to GA was 50/50, both the [η] and M_w values of D,L ‐PLGA were higher than those of L ‐PLGA. With D,L ‐LA as the starting material, the structure of the PLGA copolymer was relatively simple, and its properties were apt to be controlled by its GA chain segment. When the feed molar percentage of the monomer (LA or GA) was more than or equal to 90%, the copolymer was apt to be crystalline, and the aptness was more obvious for the L ‐LA monomer. The composition percentage of GA in PLGA was not only higher than the feed molar percentage of GA, but also, the GA percentage in D,L ‐PLGA was higher than in L ‐PLGA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 244–252, 2006