生物可吸收材料PDLLA的聚合条件研究

通过乳酸脱水合成出高纯度的D,L 丙交酯。以辛酸亚锡为引发剂,进行丙交酯开环聚合为聚乳酸(PDL LA)的实验研究。讨论了D,L 丙交酯开环聚合的影响因素和PDLLA聚合条件。     

乙酰丙酮钯催化丙交酯聚合及丙交酯-己内酯共聚合研究

丙交酯由乳酸二聚脱水再减压蒸馏而得。以丙交酯或一定配比的丙交酯-己内酯共混物为单体,采用乙酰丙酮钯催化丙交酯的聚合或丙交酯-己内酯的共聚合。研究结果表明:当m(催化剂)∶m(单体)=0.010∶1、聚合时间为15 h和聚合温度为140~℃时,丙交酯的聚合效果相对最佳;此时,聚合转化率(为98.4%)相对最大、聚乳酸的Mη(黏均相对分子质量)(为2.178×104)较适宜且分散度为2.45。当m(催化剂)∶m(单体)=0.010∶1、聚合时间为15 h、聚合温度为140℃和m(丙交酯)∶m(己内酯)=3∶2[即n(丙交酯)∶n(己内酯)=1.19∶1]时,丙交酯-己内酯的共聚合效果相对最佳;此时,转化率(为99.2%)相对最大、聚乳酸的Mη(为4.688×104)较适宜且分散度为2.19,并且共聚物中n(丙交酯)∶n(己内酯)=0.92∶1与共聚前的单体配比(1.19∶1)相近。     

纳米氧化锌催化丙交酯开环聚合的研究

采用纳米氧化锌为催化剂进行L-丙交酯(L-LA)的开环聚合,研究了催化剂用量、反应温度和反应时间对聚合反应的影响.结果表明,纳米氧化锌在催化聚合转化率和聚合产物分子量上,均显示出较好的催化性能.采用了FTIR、DSC、WAXD等方法对聚乳酸的结构进行了表征,结果表明聚乳酸是L-丙交酯开环聚合产物.     

PLA-g-GMA的制备及其对PLA/PPC共混体系性能的影响

采用双螺杆挤出机将甲基丙烯酸缩水甘油酯(GMA)接枝到聚乳酸(PLA)上,而后将接枝产物(PLA-g-GMA)与聚乳酸(PLA)、聚碳酸亚丙酯(PPC)反应性共混,考察了接枝物中GMA加入量变化对PLA/PPC/PLA-g-GMA共混体系的力学性能、热稳定性能的影响,并对共混体系的断裂机理进行了研究。结果表明,PLA-g-GMA的引入能够在一定程度上改善PLA与PPC的相容性。随着接枝物中GMA加入量的增加,共混物的冲击强度、断裂伸长率及拉伸强度均呈现出先升高后降低的趋势,并在接枝物中GMA加入量为3%时达到最大值。扫描电镜结果显示,PLA-g-GMA引入后共混物的韧性断裂特征越发显著,其冲击断裂方式由脆性断裂过渡为韧性断裂。热失重分析结果显示,加入PLA-g-GMA后共混物的起始分解温度和完全分解温度均有一定程度的提高。     

新型环境友好材料聚乳酸合成工艺研究

以工业乳酸为原料,采用开环聚合法对聚乳酸合成工艺进行系统研究,对传统工艺中的催化剂及投加方式作了改进。在丙交酯合成工艺中,采用ZnO/La2O3作催化剂并分2次顺序加入,明显提高了丙交酯的产率(达52%);在丙交酯开环聚合工艺中,采用辛酸亚锡甲苯溶液作催化剂,在反应温度为130—180℃,反应时间8h,体系真空度控制在0.098MPa的条件下,制备出聚乳酸的分子质量达到2.4×104g/mol,优于文献报道。     

丙交酯接枝淀粉提高聚乳酸/淀粉共混物透明性的研究

合成了丙交酯接枝淀粉(STL),采用红外光谱(FTIR)和核磁共振(NMR)表征了其结构。分别制备了聚乳酸(PLA)与塑化淀粉(TPS)、马来酸酐改性淀粉(MTPS)、STL质量比为90/10、70/30、50/50的熔融共混物,通过扫描电子显微镜(SEM)、雾度、透光率和拉伸测试表征了共混物的微观形貌、透明性和力学性能。结果表明:PLA/STL共混物中淀粉分散相尺寸更小,透明性与力学性能均明显大于PLA/TPS和PLA/MTPS。PLA/STL(90/10)共混物的透光率达到72.3%,力学性能接近纯PLA。     

淀粉/聚乳酸共混材料的性能研究

对比研究了淀粉/聚乳酸(starch/PLA)和淀粉/聚乳酸接枝马来酸酐(starch/PLA-gMAH)共混体系的主要性能。结果表明:淀粉与聚乳酸直接共混时相容性较差,而将聚乳酸接枝马来酸酐则实现了对共混物的增容,使starch/PLA-g-MAH体系的力学性能和耐水性能显著提高。同时,不同配比的starch/PLA-g-MAH共混物仍具备良好的可生物降解性能。     

马来酸酐接枝聚乳酸增容聚碳酸亚丙酯/聚乳酸共混体系的结构与性能研究

采用熔融接枝技术将马来酸酐(MAH)接枝到聚乳酸(PLA)上,制备不同MAH含量的PLA-g-MAH接枝共聚物,将聚碳酸亚丙酯(PPC)、PLA、PLA-g-MAH熔融共混,制备PPC/PLA/PLA-g-MAH共混物,分析接枝物中MAH含量对PPC/PLA/PLA-g-MAH共混体系的热学性能以及力学性能的影响。结果表明:PLA-g-MAH可以改善PPC与PLA二者的相容性,使PLA在降温过程中更容易结晶。引入接枝物后,共混物的起始分解温度及完全分解温度分别提高30℃和60℃。共混物的力学性能随着接枝物中MAH含量的增加呈现先增加后减小的趋势,当MAH的加入量为3%,共混体系力学性能最佳,冲击断面塑性形变程度更加显著,呈现褶皱状韧性断裂特征,拉伸强度达到42.8 MPa,断裂伸长率为120%左右,同时冲击强度最大。     

聚乙丙交酯和二乙酸纤维素化学共混物的制备和初步表征

以辛酸亚锡(SnOct2)为催化剂,将溶有二乙酸纤维素(CDA)的乙/丙交酯 (GA/LLA)熔体进行开环接枝反应,制得二乙酸纤维素和聚乙丙交酯的共混物,并提纯得到接枝共聚物CDA-g-Poly(LLA-co-GA)s.用IR和GPC对提纯所得接枝共聚物进行了初步表征,用TGA和DSC对共混物的玻璃化温度、熔点和热失重行为进行了测定,并与相应的机械共混物进行了比较.结果表明,接枝共聚物具有较短的聚L-丙交酯(PLLA)和聚乙交酯(PGA)侧链.共混物具有较好的热稳定性,玻璃化温度和熔点可通过改变投料比调节.通过化学接枝反应所得共混物的性能与机械共混物不同的原因可能是由于PLLA和PGA侧链的内增塑作用.     

扩链法合成赖氨酸改性聚乳酸的研究

以D,L-丙交酯为原料,辛酸亚锡为催化剂,赖氨酸为引发剂,丙交酯开环聚合制备双端羟基聚乳酸（HO-PLA-Lys-PLA-OH）寡聚体,经16,-六亚甲基二异氰酸酯（HDI）扩链获得赖氨酸改性的聚乳酸材料。用傅里叶红外光谱、核磁共振、接触角、粘度法等手段对赖氨酸改性聚乳酸结构和性能等进行了表征。结果表明：赖氨酸可以引发丙交酯聚合,产物为含赖氨酸的双端羟基聚乳酸寡聚体;扩链产物的粘均分子量是寡聚体的3.6倍,其接触角变大,亲水性降低。     

Preparation and characterization of nanocomposites based on polylactides tethered with polyhedral oligomeric silsesquioxane

A series of polylactides tethered with polyhedral oligomeric silsesquioxane (POSS–PLAs) were synthesized via the ring‐opening polymerization of L ‐lactide with 3‐hydroxypropylheptaisobutyl polyhedral oligomeric silsesquioxane (3‐hydroxypropylheptaisobutyl POSS) at a concentration of 0.02–2.00 mol % in the presence of a stannous(II) octoate catalyst. 1 H‐NMR spectra and a composition analysis of the POSS–PLA hybrids confirmed that 3‐hydroxypropylheptaisobutyl POSS served as an initiator for L ‐lactide in the ring‐opening polymerization. X‐ray diffraction patterns evidenced that polyhedral oligomeric silsesquioxane (POSS) molecules of POSS–PLA hybrids were well dispersed without the formation of their crystalline aggregates. The POSS–PLA hybrid with 0.50 mol % POSS content was solution‐blended with a neat polylactide (PLA) homopolymer to obtain PLA/POSS–PLA nanocomposites with various POSS–PLA contents of 1–30 wt %. The X‐ray diffraction results of the PLA/POSS–PLA nanocomposites demonstrated that the POSS–PLA was well dispersed in the neat PLA matrix. The thermal and thermooxidative degradation properties of the nanocomposites were found to be improved at POSS–PLA contents of 1–20 wt %, compared to the neat PLA. The crystallization rates and crystallinities of the PLA/POSS–PLA nanocomposites were faster and higher, respectively, with increasing POSS–PLA content because of the nucleation effect of the POSS molecules in the neat PLA matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of polylactide/poly(ethylene glycol) diblock copolymers with functional endgroups

Amphiphilic polylactide/poly(ethylene glycol) (PLA–PEG) diblock copolymers with functional groups at the PEG chain ends were synthesized by coupling PLA and PEG homopolymers using different coupling agents. PLA precursors with different endgroups were synthesized by ring‐opening polymerization of l ‐lactide in the presence of different initiators such as octanol, acetic acid or benzoic acid, or water, using non‐toxic zinc lactate as catalyst. The mechanism of the ring‐opening polymerization of lactide initiated by carboxyl groups was investigated and discussed in comparison with the literature. N,N'‐carbonyldiimidazole was used to couple the two hydroxyl groups of PLA and PEG, using 4‐dimethylaminopyridine (DMAP) as catalyst. Dicyclohexylcarbodiimide (DCC) and DMAP were adopted to couple the carboxyl group and the hydroxyl group of PLA and PEG, respectively, while DCC and N‐hydroxysuccinimide were used to connect PLA and PEG by coupling their carboxyl and amine groups. Comparison of different coupling routes shows that the DCC/DMAP one exhibits the highest efficiency. A common tumor targeting ligand, folic acid, was attached to PLA–PEG with hydroxyl endgroups using the DCC/DMAP route. The resulting PLA–PEG copolymers bearing folic acid present great interest for targeted delivery of anti‐cancer drugs. © 2012 Society of Chemical Industry     

mPEG⁃PLA嵌段共聚物及其胶束的降解行为研究

采用开环聚合法制备了聚乙二醇单甲醚（mPEG）与D,L⁃丙交酯的嵌段共聚物,并以此共聚物为载体制备了紫杉醇胶束,研究了mPEG⁃聚丙交酯（PLA）与载药胶束（DMs）在不同条件下的降解特点。结果表明,在低温下（4 ℃）,mPEG⁃PLA聚合物和DMs均能长时间（24个月）保持稳定,未发生明显降解;当温度升高,mPEG⁃PLA和DMs降解速度明显增加,但降解机理有所不同,这种差异在40 ℃以上的环境中更明显;mPEG⁃PLA聚合物的高温（60 ℃）降解以链段内部无规则断裂为主,分子量显著降低;DMs在高温（60 ℃）下则更多遵循“末端降解机理”,生成更多的丙交酯和乳酸。     

Ring‐opening graft polymerization of L‐lactide onto starch granules in an ionic liquid

A room temperature ionic liquid 1‐allyl‐3‐methylimidazolium chloride ([AMIM]Cl) was a promising direct solvent for starch and nonderivitizing solvent for starch‐effective dissolution, in which the ring‐opening graft polymerization (ROGP) of L ‐lactide (L ‐LA) onto starch chains was carried out homogeneously. The obtained starch grafted poly(L ‐lactide) (starch‐g‐PLLA) was characterized by FTIR, ¹³C NMR, DSC, and WAXD, and the good adhesion between the two components was evidenced by SEM observations although the chains of grafted PLLA were not long. The grafting efficiency of PLLA reached 30% when the ROGP proceeded at 100°C for 10 h with L ‐LA/starch 0.5 : 1 (wt/wt) and stannous octoate (Sn(Oct)₂) as a catalyst, which was calculated according to a standard curve newly created by FTIR method. The homopolymerization of L ‐LA and the disconnection of grafted PLLA from starch‐g‐PLLA were the main competition reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚乳酸高效催化剂的研究进展

聚乳酸作为一种生物可降解塑料,具有绿色环保、原料来源广泛等优点,近年来对于聚乳酸的合成和应用研究越来越多。聚乳酸的合成方法可分为直接法和间接法(丙交酯的开环聚合)。在聚乳酸的合成过程中,催化剂起着非常关键的作用,不同的合成过程催化剂的选择也存在一定的差异,主要对聚乳酸的合成过程中所用到的高效催化剂进行综述。     

Synthesis of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) and poly(vinyl alcohol)‐graft‐poly(lactide) in melt with magnesium hydride as catalyst

Grafting of poly(ε‐caprolactone) (PCL) and poly(lactide) (PLA) chains on poly(vinyl alcohol) backbone (PVA degree of hydrolysis 99%) was investigated using MgH₂ environmental catalyst and melt‐grown ring‐opening polymerization (ROP) of ε‐caprolactone (CL) and L ‐lactide (LA), that avoiding undesirable toxic catalyst and solvent. The ability of MgH₂ as catalyst as well as yield of reaction were discussed according to various PVA/CL/MgH₂ and PVA/LA/MgH₂ ratio. PVA‐g‐PCL and PVA‐g‐PLA were characterized by ¹H‐ and ¹³C‐NMR, DSC, SEC, IR. For graft copolymers easily soluble in tetrahydrofuran (THF) or chloroform, wettability and surface energy of cast film varied in relation with the length and number of hydrophobic chains. Aqueous solution of micelle‐like particles was realized by dissolution in THF then addition of water. Critical micelle concentration (CMC) decreased with hydrophobic chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Microwave‐assisted preparation of polylactide/organomontmorillonite nanocomposites via in situ polymerization

Microwave technology was introduced to assist the synthesis of polylactide (PLA)/organomontmorillonite (OMMT) nanocomposites in bulk by the in situ ring‐opening polymerization of D,L ‐lactide. Factors that influenced the polymerizing effects, such as the microwave power, irradiation time, and dosages of the catalyst and OMMT, were studied in terms of tensile strength. The polymerization time was decreased dramatically to 10 min under 90 W of microwave irradiation, and the mechanical and thermal properties of the PLA/OMMT nanocomposites were significantly improved. The composite with the highest mechanical properties was obtained when the dosages of the OMMT and the catalyst were 1.0 and 0.6 wt % of the lactide, respectively. The initial decomposition temperature of the PLA/OMMT(1.0 wt % OMMT) nanocomposite was heightened 11.5°C compared with that of pure PLA. The results of scanning electron microscopy confirmed an improvement in the toughness with the addition of OMMT. The transmission electron microscopy and X‐ray diffraction results indicate that an exfoliated and intercalated nanocomposite was successfully prepared. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of poly(ϵ‐caprolactone)–poly(L‐lactide) diblock copolymers with an organic amino calcium catalyst

The quasiliving characteristics of the ring‐opening polymerization of ?‐caprolactone (CL) catalyzed by an organic amino calcium were demonstrated. Taking advantage of this feature, we synthesized a series of poly(?‐caprolactone) (PCL)–poly(L ‐lactide) (PLA) diblock copolymers with the sequential addition of the monomers CL and L ‐lactide. The block structure was confirmed by ¹H‐NMR, ¹³C‐NMR, and gel permeation chromatography analysis. The crystalline structure of the copolymers was investigated by differential scanning calorimetry and wide‐angle X‐ray diffraction analysis. When the molecular weight of the PLA block was high enough, phase separation took place in the block copolymer to form PCL and PLA domains, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2654–2660, 2006     

The ring‐opening polymerization of D,L‐lactide catalyzed by new complexes of Cu,Zn, Co,and Ni Schiff base derived from salicylidene and L‐aspartic acid

D ,L ‐lactide (LA) was first successfully ring‐opening polymerized in melt by Schiff base complexes K[ML]nH₂O [M = Cu(II), Zn(II), Co(II), Ni(II); n = 2, 2, 3, 3.5; H₃L = L‐aspartic acid‐salicylidene Schiff base], which were prepared by Schiff base ligand derived from salicylidene and L‐aspartic acid and corresponding acetates. The effects of various complexes, the molar ratio of K[ML]nH₂O/LA, the polymerization temperature, and time were studied in detail. The results show that all complexes studied have the ability to initiate the ring‐opening polymerization of D ,L ‐lactide in melt. More than 90% high polymerization conversion and narrow molecular weight distribution (MWD) can be obtained very easily. However, the Ni(II) complex shows better catalytic property than other complexes on the polymerization and the molecular weight (MW) of poly(D ,L ‐lactide) (PLA) produced. With a rise in temperature and a prolongation of time, the MW of PLA decreased remarkably. The MW of PLA prepared by all complexes is not very high, which might be related to the crystalline water of complexes. X‐ray study indicated that PLA produced by Ni(II) complex is an amorphous polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3312–3315, 2002     

Synthesis of polylactide with varying molecular weight and aliphatic content: Effect on moisture sorption

Polylactide (PLA) is a bio‐based, biodegradable polymer, which is derived from lactic acid and has numerous potential applications, some of which are limited by its moisture barrier and thermal properties. Prior studies have been inconsistent about how moisture sorption in PLA varies with crystallinity and molecular weight. This research is a systematic study of how moisture sorption in PLA depends on molecular weight and aliphatic content via end‐group modification. PLA with varying aliphatic content was synthesized by ring‐opening polymerization of L ‐lactide initiated with different long‐chain aliphatic alcohols. The terminating end groups were also modified from hydroxyl to acetoxy to eliminate hydrophilic end groups. Molecular weight was controlled by varying the ratio of L ‐lactide monomer to alcohol initiator, and triethylaluminum was used as the catalyst for precise control over molecular weight. The molecular weight and end‐group compositions were verified by gel permeation chromatography and nuclear magnetic resonance. Moisture sorption of the modified PLA samples was measured with a quartz crystal microbalance. Quartz crystal microbalance experiments revealed that both molecular weight and aliphatic content contributed to the sorption properties of PLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011