Preparation of monomer of degradable biomaterial poly(L-lactide)

L-lactide was prepared from L-lactic acid with stannous octoate as the catalyst. The effects of reaction temperature and pressure on the ingredient of crude lactide were investigated. The results show that the mass fraction of meso-lactide increases with the increasing reaction temperature. Crude lactide containing 85.4% L-lactide is obtained when the reaction temperature is 200 ℃. High purity of L-lactide with a yield of 40.6 % is obtained by synthetic purifying method. The properties of L-lactide are characterized by optical purity, infrared spectrum and gas chromatogram/mass spectrum. The L-lactide samples purified by recrystallization and synthetic purifying methods are polymerized with the catalyst of stannous octoate, and the corresponding viscosity average relative molecular masses of poly(L-lactide) are 2.85 × 105 and 5.05 × 105 , respectively. This indicates that the optical purity of Llactide has great influence on the relative molecular mass of poly(L-lactide).

The Syntheses and Properties of Poly(L- Lactide)

Poly (L-lactide) was prepared by bulk polymerization ofL-lactide at 140°C in the presence of stannous octoate. The polymer products were characterized by number average molecular weight Mn, weight average molecular weight Mw and molecular weight distribution MWD (M w/M n) respectively. The results showed that stannous octoate was a high effective catalyst, and coordinated insertion mechanism of the reaction was proposed.

Preparation and characterization of poly(D,L-lactide) and its porous biomaterials

Poly(D,L-lactide) was synthesized by indirect method from D,L-lactic acid and characterized by infrared spectrum and proton nuclear magnetic resonance. The influences of monomer purity, initiator concentration, polymerization temperature and polymerization time on the relative molecular mass of poly(D, L-lactide) were investigated. The polylactide was made into porous materials by using solvent-casting particulate-leaching method. Under the optimized conditions, polylactides with a viscosity average molecular mass up to 1.82×105 are obtained and the results are fairly reproducible. Scanning electron microscope observation indicates that the sample is highly porous and well-distributed with good interconnections between pores and the pore size of porous materials is in the range from 200 μm to 500 μm and it can be used as scaffold for bone tissue engineering.

Synthesis and characterization of biodegradable polymer:Poly (ethene maleic acid ester-co-D,L-lactide acid)

A novel biodegradable polymer--poly （ethene maleic acid ester-co-D,L-lactide acid） was synthesized by copolymerizing lactide and prepolymer, which was prepared by the condensation of maleic anhydride and glycol, using p-toluene sulphonic acid as a catalyst, attempting to improve the hydrophilicity, increase flexibility and modulate the degradation rate. FTIR,^1H NMR, MALLS and DSC were employed to characterize these polymers.

Synthesis of optically active lactide catalyzed by nanocrystals of La-Ti composite oxides

With sol-gel method,nanometer La-Ti composite oxides were prepared.By means of atomic force microscope,the surface pattern,particle size distribution and specific surface area were studied.The newly prepared nanocrystals of La-Ti composite oxides were used as the catalysts to catalyze the dehydration of external compensated lactic acid to lactide.The lactide product was measured by polarimeter and micropolariscope.The results demonstrate that the ratio between D-lactide and L-lactide will not be equal to 1-1 if nanocrystals of La-Ti composite oxides are used as the catalysts,which implies,that nanocrystals of La-Ti composite oxides may be potential catalysts with a good selectivity.

Biodegradation of Absorbable Hydroxyapatite/Poly-DL-lactide Composites in Different Environment

To develop a new generation of absorbable fracture fixation devices with enhanced biocompatibility, the biodegradation mechanism and its influence on the cellular response at the tissue/implant interface of hydroxyapatite/ poly DL lactide (HA/PDLLA) composites were investigated in vitro and in vivo.HA/PDLLA rods were immersed in phosphate buffered saline,or implanted in muscle and bony tissue for 52 weeks.Scanning electron microscopic and histological studies were done.The degradation rate was the slowest in vitro,slower in muscle tissue and fast in bone.In vitro, the composites degraded heterogeneously and a hollow structure was formed.In bone,the limited clearing capacity leads to the accumulation of oligomeric debris,which contribute totally to the autocatalytic effect.So,the fastest degradation and intense tissue response were seen.In muscle tissue,oligomeric debris migrated into vicinal fibers over a long distance from the original implant cavity and the tissue reactions were,however, quite moderate.For the same size organic/inorganic composite,the environment where it was placed is the major factor in determining its biodegradation process and cellular reaction.In living tissue,factors such as cells,enzymes and mechanical stress have an obvious influence on the biodegradation and biological process at the tissue/implant interface.The biocompatibility of the HA/PDLLA composites is enhanced with the incorporating of the resorbable HA microparticles.

MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF BIODEGRADABLE BLEND OF POLY(β—HYDROXYBUTYRATE)AND POLY(D,L—LACTIDE)—CO—POLY(ETHYLENE GLYCOL)

Studies on the miscibility of PHB/PELA blends showed that PHB and PELA were miscible in amorphous state.The crystallization behavior of PHB in the blend was strongly de- pendent on the addition of PELA component.

Preparation and biocompatibility evaluation of poly(D,L-lactide-co-glycine)

D,L-lactide was prepared from D,L-lactic acid by means of polymerization and depolymerization at low vacuum level.Morpholine-2,5-dione(MD) was synthesized from the cyclization of chloroacetyl glycine which was made from chloroacetyl chloride and glycine in the basic condition.A novel copolymer(PLAMD) with D,L-lactide(D,L-LA) and morpholine-2,5-dione(MD) was synthesized using stannous octoate as initiator,and characterized with FT-IR and 1HNMR.The biocompatibility of PLAMD and PLA was investigated by MTT and microscope.The results show that amino acid is introduced into PDLLA main chain.PLAMD has better cell affinity than PLA,so it is a promising biomaterial.

MISCIBILITY AND MORPHOLOGICAL STRUCTURE OF BIODEGRADABLE BLEND OF POLY(β—HYDROXYBUTYRATE)AND POLY(D,L—LACTIDE)

The poly(β-hydroxybutyrate)/poly(d,1-lactide)(PHB/PLA)blend was found to be immiscible,the melting point and the phase crystallinity of PHB were independent of the blend composition.Comparing with plain PHB,the blend exhibited the crystallization change and a certain improvement of the mechanical property.

Synthesis of L-Lactide from Butyl Lactate： Selection of Catalyst

The process of production of lactide from butyl lactate was investigated. The process consists of two stages： oligomerisation of butyl lactatean and depolymerisation of oligomers. The type catalysts of the series of Lewis acid were tested. It was found that SnCI4 is the most efficient catalyst for both stages.

Zinc Complexes of New Chiral Aminophenolate Ligands: Synthesis, Characterization and Reactivity toward Lactide

The syntheses of a library of new chiral aminophenolate bidentate O,N-type ligands HOC6H4(2-R- 4-R′)CH2N(Me)CH(Me)C6H5 [R = R′ = But, 1;R = R′ = Pent, 2;R = But, R′ = Me, 3;R = Me, R′ = But, 4;R = R′ = Me, 5] and tridentate O,N,O-type ligands HOC6H4(2,4-But)CH = NCH(R′′)C6H5 [R′′ = Me, 6;R′′ = CH2OMe, 7] are reported. These ligands were characterized by elemental analysis, nuclear magnetic resonance spectroscopy (1H & 13C), and single crystal X-ray diffraction. These ligands serve as chiral auxiliaries for inorganic chemists to design chiral metal-based complexes for asymmetric catalysis and stereoselective polymerization reactions. Three new heteroleptic zinc complexes based on these ligands have been synthesized in moderate yields via a ligand-exchange transamination reaction between homoleptic [Zn(N(SiMe3)2)2] and one equivalent of corresponding ligands to afford [L3ZnN- (SiMe3)2] (3a), [L4ZnN(SiMe3)2] (4a), and [L7ZnN(SiMe3)2] (7a). Solvent-free polymerization of raclactide at 130°C using these zinc compounds yielded atactic polylactides with Mw 10,000 g/mol and narrow polydispersity of 1.3.

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.

Lightweight,Strong and High Heat-Resistant Poly(lactide acid)Foams via Microcellular Injection Molding with Self-Assembly Nucleating Agent

Poly(lactide acid)(PLA)foams have shown considerable promise as eco-friendly alternatives to nondegradable plastic foams,such as polystyrene(PS)foams.Nevertheless,PLA foam typically suffers from low heat-resistance and poor cellular structure stemming from its inherent slow crystallization rate and low melt strength.In this study,a high-performance PLA foam with well-defined cell morphology,exceptional strength and enhanced heat-resistance was successfully fabricated via a core-back microcellular injection molding(MIM)process.Differential scanning calorimetry(DSC)results revealed that the added hydrazine-based nucleating agent(HNA)significantly increased the crystallization temperature and accelerated the crystallization process of PLA.Remarkably,the addition of a 1.5 wt%of HNA led to a significant reduction in PLA’s cell size,from 43.5µm to 2.87µm,and a remarkable increase in cell density,from 1.08×10^(7)cells/cm^(3)to 2.15×10^(10)cells/cm^(3).This enhancement resulted in a final crystallinity of approximately 55.7%for the PLA blend foam,a marked improvement compared to the pure PLA foam.Furthermore,at 1.5 wt%HNA concentration,the tensile strength and tensile toughness of PLA blend foams demonstrated remarkable improvements of 136%and 463%,respectively.Additionally,the Vicat softening temperature of PLA blend foam increased significantly to 134.8°C,whereas the pure PLA foam exhibited only about 59.7℃.These findings underscore the potential for the preparation of lightweight injection-molded PLA foam with enhanced toughness and heat-resistance,which offers a viable approach for the production of high-performance PLA foams suitable for large-scale applications.

Chemical upcycling of poly(lactide) plastic waste to lactate ester,lactide and new poly(lactide) under Mg-catalysis condition

Chemical upcycling of end-of-life poly(lactide) plastics to lactide,lactate ester and new poly(lactide)has been achieved by using magnesium bis[bis(trimethylsilyl)amide][Mg(HMDS)_(2)]as promoter.Mg(HMDS)2 showed high efficiency in L-lactide polymerization and poly(lactide) depolymerization.Mg(HMDS)_(2)/Ph_(2) CHOH catalytic system displayed high ring-opening selectivity and the characteristic of immortal polymerization.Taking advantage of transesterification,depolymerizations of end-oflife poly(lactide) plastics to lactate ester (polymer to value-added chemicals) and lactide (polymer to monomer) were achieved with high yields.Besides,a new“depolymerization-repolymerization”strategy was proposed to directly transform poly(lactide) into new poly(lactide).This work provides a theoretical basis for the design of polymerization and depolymerization catalysts and promotes the development of degradable polymers.

Mechanically Robust Polylactide Fibers with Super Heat Resistance via Constructing in situ Nanofibrils

All-PLA fibers with excellent comprehensive performance and recycling convenience are realized efficiently.High molecular weight poly(D-lactide)(HPDLA)is incorporated into poly(L-lactide)(PLLA)matrix to construct in situ nanofibrils structure by taking advantages of the microphase separation between HPDLA and PLLA.The tensile strength of HPDLA/PLLA composite fibers(HDL-8)is enhanced from 2.1 cN/dtex of neat PLLA-8 fibers up to 2.9 cN/dtex.Its boiling water shrinkage(BWS)and shrinkage in hot air(HAS)significantly decrease to 7.8%and 2.8%,respectively.The abundance of in situ nanofibrils creates a grille-like structure that is crucial for both heat and hydrolysis resistance.More strikingly,a hybrid shish-kebab structure induced by the in situ nanofibrils serves as a mechanical reinforcement.This work paves a new way for heat resistance and self-reinforcement modification of PLA materials.

Polymerization of lactide and synthesis of block copolymer catalyzed by copper(Ⅱ) Schiff base complex

In the present investigation, the novel copper Schiff base complex was synthesized and its catalytic activity was evaluated for the ring-opening polymerization （ROP） of lactide and block polymerization of poly（lactide） with po/y（ethylene glycol）methyl ether,

Synthesis and characterization of aminophenolate-ligated rare-earth metal amide complexes and their catalytic activity for lactides polymerization

Amine elimination of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with aminophenol H[ON]{H[ON]=2-(CH2 NC5 H10)-4,6-tBu2-C6 H3OH}in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]2 LnN(SiMe3)2(Ln=Yb(1),Y(2),Gd(3),Sm(4),Nd(5))in 57%-73%isolated yields.All these complexes were characterized by elemental analysis.The molecular structures of complexes 1-4 were determined by single crystal X-ray diffraction.These complexes are highly active for L-Iactide polymerization to give high molecular weight polymers with unimodal molecular weight distributions.In addition,these complexes can also initiate rac-lactide polymerization with high activity to afford heterotactic-rich polylactides.

Enolic Schiff Base Zinc Amide Complexes： Highly Active Catalysts for Ring-Opening Polymerization of Lactide and ε-Caprolactone

A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-caprolactone, exhibiting notably high activity at ambient temperature, The influence of imine bridge length and substituents of diketone over the course of polymerization was investigated in details. Remarkably, 4a was confirmed to be a rare example of exceedingly active and robust zinc catalysts, achieving major transformation of lactide under extremely low loading （0.025 mol%） within 18 rain. The influence of various monomers as well as the polymerization mechanism have also been discussed.

Effect of Plasticizer Poly(Ethylene Glycol)on the Crystallization Properties of Stereocomplex-Type Poly(Lactide Acid)

The effects of the plasticizer poly（ethylene glycol） （PEG） on crystallization properties of equimolar poly（L-lactide） （PLLA）/poly（D-lactide） （PDLA） blends were investigated. Forma- tion of the stereocomplex-type poly（lactide acid） （sc-PLA） crystallites was confirmed by Wide-angle X-ray diffraction （WAXD） and differential scanning calorimetry （DSC） analyses. Sc-PLA crystallites without any homochiral poly（lactide acid） （hc-PLA） formed, as the result of the incorporation of the plasticizer PEG （more than or equal to 10%（wt）） at a processing temperature （240 ℃）. More-over, when the Mw of PEG reached 1 000 g · mol^-1, the crystal- lizability of stereocomplex crystallites was the best. Isothermal crystallization kinetics further revealed that PEG could accelerate the crystallization rate of sc-PLA, with the optimum crystallization kinetic parameters being obtained at 10% （wt） PEG. Several crys- tallization kinetics equations were applied to describe the effect of PEG on the crystallization behavior of sc-PLA. The influence of PEG on the spherocrystal morphologies of sc-PLA was also inves- tigated using polarized optical microscopy.

Salen-iron Complexes: Synthesis, Characterization and Their Reactivity with Lactide

Schiff-base metal complexes as efficient catalysts are widely used in ring-opening polymerization of cycle esters. The salen Fe complexes were formed with their excellent biocompatibility and less toxicity. A series of salen Fe complexes were designed in this work in order to study the activity and control of polymerization of lactide. The salen Fe complexes＇ activities changed with the ligands configuration and substituent groups.