乳丝的加工、性能及其应用

乳丝学名为聚乳酸纤维,是一种可生物降解的新型绿色纤维,目前制备方法主要有熔融纺丝、溶液纺丝和静电纺丝等3种方法。作为一种新型的可降解纤维材料,其环保性、吸湿性、透气性、生物相容性以及优良的力学性能决定了其在生物医用、织物面料、非织造材料(如一次性卫生用品、过滤材料等)等很多方面都将得到广泛应用。     

Polylactic acid (PLA): research, development and industrialization

Polylactide (PLA) is a biodegradable, aliphatic polyester derived from lactic acid. It has similar mechanical properties to polyethylene terephthalate, but has a significantly lower maximum continuous use temperature. PLA products can be recycled after use either by remelting and processing the material a second time or by hydrolyzing to lactic acid, the basic chemical. In this review, the technologies for polymerization of the lactic acid and the comparison of physical, thermal and mechanical properties, biodegradability, and biocompatibility of the PLA and copolymers with other similar polymers are described.     

聚乳酸成核剂研究进展

聚乳酸是以乳酸为原料而合成得到的一种高分子材料,具有良好生物相容性、可生物降解性。目前工业规模化生产的聚乳酸主要是以左旋乳酸合成得到的聚乳酸,制得的制品透明性好,但缺点是不能耐热。添加成核剂可以提高聚乳酸的结晶度,从而提高它的耐热性能。本文综述了有机成核剂和无机成核剂的研究进展。     

Functional lactide monomers: methodology and polymerization

Side-chain-functionalized lactide analogues have been synthesized from commercially available amino acids and polymerized using stannous octoate as a catalyst. The synthetic strategy presented allows for the incorporation of any protected amino acid for the preparation of functionalized diastereomerically pure lactide monomers. The resulting functionalized cyclic monomers can be homopolymerized and copolymerized with lactides and then quantitatively deprotected forming new functional poly(lactide)-based materials. This strategy allows for the introduction of functional groups along a poly(lactide) (PLA) backbone that after deprotection can be viewed as chemical handles for further functionalization of PLA, yielding improved biomaterials for a variety of applications.     

Recent advances in lactic acid production by microbial fermentation processes

Fermentative production of optically pure lactic acid has roused interest among researchers in recent years due to its high potential for applications in a wide range of fields. More specifically, the sharp increase in manufacturing of biodegradable polylactic acid (PLA) materials, green alternatives to petroleum-derived plastics, has significantly increased the global interest in lactic acid production. However, higher production costs have hindered the large-scale application of PLA because of the high price of lactic acid. Therefore, reduction of lactic acid production cost through utilization of inexpensive substrates and improvement of lactic acid production and productivity has become an important goal. Various methods have been employed for enhanced lactic acid production, including several bioprocess techniques facilitated by wild-type and/or engineered microbes. In this review, we will discuss lactic acid producers with relation to their fermentation characteristics and metabolism. Inexpensive fermentative substrates, such as dairy products, food and agro-industrial wastes, glycerol, and algal biomass alternatives to costly pure sugars and food crops are introduced. The operational modes and fermentation methods that have been recently reported to improve lactic acid production in terms of concentrations, yields, and productivities are summarized and compared. High cell density fermentation through immobilization and cell-recycling techniques are also addressed. Finally, advances in recovery processes and concluding remarks on the future outlook of lactic acid production are presented.     

Technological and economic potential of poly(lactic acid) and lactic acid derivatives

Abstract: Lactic acid has been an intermediate-volume specialty chemical (world production ∼ 40,000 tons/yr) used in a wide range of food processing and industrial applications. Lactic acid has the potential of becoming a very large volume, commodity-chemical intermediate produced from renewable carbohydrates for use as feedstocks for biodegradable polymers, oxygenated chemicals, plant growth regulators, environmentally friendly 'green' solvents, and specialty chemical intermediates. The recent announcements of new development-scale plants for producing lactic acid and polymer intermediates by major U.S. companies, such as Cargill, Ecochem (DuPont/ConAgra), and Archer Daniels Midland, attest to this potential.
In the past, efficient and economical technologies for the recovery and purification of lactic acid from crude fermentation broths and the conversion of lactic acid to the chemical or polymer intermediates had been the key technology impediments and main process cost centers. The development and deployment of novel separations technologies, such as electrodialysis (ED) with bipolar membranes, extractive distillations integrated with fermentation, and chemical conversion, can enable low-cost production with continuous processes in large-scale operations. The use of bipolar ED can virtually eliminate the salt or gypsum waste produced in the current lactic acid processes. Thus, the emerging technologies can use environmentally sound processes to produce environmentally useful products from lactic acid. The process economics of some of these processes and products can also be quite attractive. In this paper, the recent technical advances in lactic and polyactic acid processes are discussed. The economic potential and manufacturing cost estimates of several products and process options are presented. The technical accomplishments at Argonne National Laboratory (ANL) and the future directions of this program at ANL are discussed.     

Laboratory composting of extruded poly(lactic acid) sheets

Composting of extruded poly(lactic acid) (PLA) in combination with pre-composted yard waste in a laboratory composting system was studied. Yard waste and PLA mixtures containing 0%, 10%, or 30% PLA (dry weight basis) were placed in composting vessels for four weeks. Exhaust gases were analyzed for carbon dioxide concentration twice per week. After the first week, significantly greater (P < 0.05) amounts of carbon dioxide were generated in vessels with 10% or 30% PLA than in control (0% PLA) vessels. Data indicated that microbial degradation of PLA occurred. There was no significant difference (P > 0.05) in carbon dioxide emission between 10% and 30% PLA mixtures. Compost pH dropped (from 6.0 to 4.0) after 4 weeks of composting for 30% PLA, but remained unchanged (6.3) for 0% or 10% PLA. Most likely, in the case of 30% PLA, substantial chemical hydrolysis and lactic acid generation lowered the compost pH. The lowered pH likely suppressed microbial activity, thus explaining the lack of difference in carbon dioxide emissions between 10% and 30% PLA mixtures. Gel permeation chromatography showed a notable decrease in PLA molecular weight as a result of composting. It was demonstrated that PLA can be efficiently composted when added in small amounts (<30% by weight) to pre-composted yard waste.     

Lipase-catalyzed enantioselective synthesis of (R,R)-lactide from alkyl lactate to produce PDLA (poly D-lactic acid) and stereocomplex PLA (poly lactic acid)

R-lactide, a pivotal monomer for the production of poly (D-lactic acid) (PDLA) or stereocomplex poly (lactic acid) (PLA) was synthesized from alkyl (R)-lactate through a lipase-catalyzed reaction without racemization. From among several types of lipase, only lipase B from Candida antarctica (Novozym 435; CAL-B) was effective in the reaction that synthesized (R,R)-lactide. Enantiopure (R,R)-lactide, which consisted of over 99% enantiomeric excess, was synthesized from methyl (R)-lactate through CAL-B catalysis. Removal of the methanol by-product was critical to obtain a high level of lactide conversion. The (R,R)-lactide yield was 56% in a reaction containing 100 mg of Novozym 435, 10 mM methyl (R)-lactate and 1500 mg of molecular sieve 5 A in methyl tert-butyl ether (MTBE). The important monomer (R,R)-lactide that is required for the production of the widely recognized bio-plastic PDLA and the PLA stereocomplex can be obtained using this novel synthetic method.     

Use of poly(lactic acid) amendments to promote the bacterial fixation of metals in zinc smelter tailings

The ability of poly(lactic acid) (PLA) to serve as a long-term source of lactic acid for bacterial sulfate reduction activity in zinc smelter tailings was investigated. Solid PLA polymers mixed in water hydrolyzed abiotically to release lactic acid into solution over an extended period of time. The addition of both PLA and gypsum was required for indigenous bacteria to lower redox potential, raise pH, and stimulate sulfate reduction activity in highly oxidized smelter tailings after one year of treatment. Bioavailable cadmium, copper, lead and zinc were all lowered significantly in PLA/gypsum treated soil, but PLA amendments alone increased the bioavailability of lead, nickel and zinc. Similar PLA amendments may be useful in constructed wetlands and reactive barrier walls for the passive treatment of mine drainage, where enhanced rates of bacterial sulfate reduction are desirable.     

Citrate metabolism in lactic acid bacteria

Abstract: Citrate metabolism plays an important role in many food fermentations involving lactic acid bacteria. Since citrate is a highly oxidized substrate, no reducing equivalents are produced during its degradation, resulting in the formation of metabolic end products other than lactic acid. Some of these end products, such as diacetyl and acetaldehyde, have very distinct aroma properties and contribute significantly to the quality of the fermented foods. In this review the metabolic pathways involved in product formation from citrate are described, the bioenergetic consequences of this metabolism for the lactic acid bacteria are discussed and detailed information on some key enzymes in the citrate metabolism is presented. The combined knowledge is used for devising strategies to avoid, control or improve product formation from citrate.     

Microbial production of lactic acid: the latest development

Lactic acid is an important platform chemical for producing polylactic acid (PLA) and other value-added products. It is naturally produced by a wide spectrum of microbes including bacteria, yeast and filamentous fungi. In general, bacteria ferment C5 and C6 sugars to lactic acid by either homo- or hetero-fermentative mode. Xylose isomerase, phosphoketolase, transaldolase, l- and d-lactate dehydrogenases are the key enzymes that affect the ways of lactic acid production. Metabolic engineering of microbial strains are usually needed to produce lactic acid from unconventional carbon sources. Production of d-LA has attracted much attention due to the demand for producing thermostable PLA, but large scale production of d-LA has not yet been commercialized. Thermophilic Bacillus coagulans strains are able to produce l-lactic acid from lignocellulose sugars homo-fermentatively under non-sterilized conditions, but the lack of genetic tools for metabolically engineering them severely affects their development for industrial applications. Pre-treatment of agriculture biomass to obtain fermentable sugars is a pre-requisite for utilization of the huge amounts of agricultural biomass to produce lactic acid. The major challenge is to obtain quality sugars of high concentrations in a cost effective-way. To avoid or minimize the use of neutralizing agents during fermentation, genetically engineering the strains to make them resist acidic environment and produce lactic acid at low pH would be very helpful for reducing the production cost of lactic acid.     

Synthesis and characterization of poly(d,l-lactic acid) via enzymatic ring opening polymerization by using free and immobilized lipase

Abstract

Polylactic acid is an interesting biodegradable and bioabsorbable material, and is produced from lactic acid, either by the direct polycondensation of lactic acid or via the ring-opening polymerization (ROP) of lactide. A future target of it is to improve some of the polyester properties for specific biomedical applications. The biocatalytic ROP of lactide is attractive as a route to polymer synthesis due to its lack of toxic reactants, mild reaction requirements, and recyclability of immobilized enzyme. Therefore, the use of immobilized enzymes is also being investigated.

The aim of this work was to develop a methodology to synthesize high molecular weight polylactic acid via enzymatic ROP method using free enzyme and Candida antarctica lipase B (CALB) immobilized onto chitin and chitosan. The efficiency of the two approaches has been compared, with polymerization kinetics and resulting products fully characterized by FT-IR, NMR, DSC, XRD, and TGA analyses.     

Preparation and properties of plasticized poly(lactic acid) films

Poly(lactic acid), PLA, was blended with monomeric and oligomeric plasticizers in order to enhance its flexibility and thereby overcome its inherent problem of brittleness. Differential scanning calorimetry, dynamic mechanical analysis, transmission electron microscopy, and tensile testing were used to investigate the properties of the blends. Monomeric plasticizers, such as tributyl citrate, TbC, and diethyl bishydroxymethyl malonate, DBM, drastically decreased the T(g) of PLA, but the blends showed no morphological stability over time since rapid cold crystallization caused a size reduction of the amorphous domains in PLA. Consequently, the ability of PLA to accommodate the plasticizer diminished with the increase in crystallinity and migration of the plasticizer occurred. Increasing the molecular weight of the plasticizers by synthesizing oligoesters and oligoesteramides resulted in blends that displayed T(g) depressions slightly smaller than with the monomeric plasticizers. The compatibility with PLA was dependent on the molecular weight of the oligomers and on the presence or not of polar amide groups that were able to positively interact with the PLA chains. Aging the materials at ambient temperature revealed that the enhanced flexibility as well as the morphological stability of the films plasticized with the oligomers could be maintained as a result of the higher molecular weight and the polar interactions with PLA.     

Solid state microcellular foamed poly(lactic acid): morphology and property characterization

Poly(lactic acid) or PLA is a plant-based biodegrable plastic which exhibits many properties that are equivalent to or better than many petroleum-based plastics. However, there have been few commercial applications due to its lower impact resistance and higher cost than synthetic plastics. In this paper, the concept of creating microcellular foamed structures in PLA as a means to improve its shortcomings is presented. The effect of the foaming conditions (temperature and time) on the void fraction, volume expansion ratio, impact strength and tensile properties of foamed PLA is discussed. Each step of microcellular processing is addressed including: the manufacture of PLA film; the saturation of the samples with gas; the microcellular foaming of PLA; the void fraction determination, volume expansion ratio calculation, impact and tensile property characterization of foamed samples. The microcellular morphologies developed in PLA samples were a strong function of the foaming conditions. Due to the presence of foamed microcells, a twofold expansion ratio and significant improvements in the impact resistance (twofold increase over unfoamed PLA), strain at break (up to twofold increase over unfoamed PLA) and toughness (up to fourfold increase over unfoamed PLA) were achieved in PLA.     

Antifungal and physicochemical properties of Ocimum essential oil loaded in poly(lactic acid) nanofibers

Poly(lactic acid) (PLA) nanofibres containing different proportions of the essential oils from Ocimum basilicum L. and Ocimum gratissimum L. were prepared by solution blow spinning method. The essential oils were extracted by hydrodistillation and characterized by gas chromatography. MEV, contact angle, DSC and FTIR were used to characterize the nanofibres. The effect of bioative nanofibres on the growth of the fungus and on the production of ochratoxin A were evaluated using the fumigation test. Linalool, 1·8-cineole and camphor were the principal components of the essential oil from O. basilicum, and eugenol was the principal constituent in the oil from O. gratissimum. An increase in the average diameter of the nanofibres was observed with the addition of the essential oils. The essential oils acted as a plasticizer, resulting in a reduction in the crystallinity of the PLA. The encapsulation of essential oils in PLA nanofibres was verified by FTIR. An effective antifungal and antimicotoxygenic activity against Aspergillus ochraceus and Aspergillus westerdjikiae was observed for the bioative nanofibres. These results confirm the potential of PLA nanofibres containing the essential oils for the control of toxigenic fungi that cause the deterioration of food and are harmful to human health.     

A convenient preparation of 6-oligo(lactic acid)cyclomaltoheptaose as kinetically degradable derivative for controlled release of amoxicillin

6-Oligo(lactic acid)cyclomaltoheptaose (6-OLA-βCD) with an average substitution of about 7.0 lactic acid units was prepared as a new water-soluble cyclomaltoheptaose (βCD) derivative (solubility of about 70.7-fold that of βCD), based on the ring-opening polymerization of 3,6-dimethyl-1,4-dioxane-2,5-dione (lactide). The product was characterized by ¹H NMR, ¹³C NMR, IR, and MS spectroscopy. The complexation of amoxicillin with 6-OLA-βCD was found to be much stronger than that with βCD at first, and then 6-OLA-βCD was shown to decompose moderately into βCD and lactic acid. 6-OLA-βCD might be greatly valuable in a controlled release system for Amoxicillin (AMX).     

Compatible ternary blends of chitosan/poly(vinyl alcohol)/poly(lactic acid) produced by oil-in-water emulsion processing

Ternary compatible blends of chitosan, poly(vinyl alcohol), and poly(lactic acid) were prepared by an oil-in-water (O/W) emulsion process. Solutions of chitosan in aqueous acetic acid, poly(vinyl alcohol) (PVA) in water, and poly(lactic acid) (PLA) in chloroform were blended with a high-shear mixer. PVA was used as an emulsifier to stabilize the emulsion and to reduce the interfacial tension between the solid polymers in the blends produced. It proved to work very well because the emulsions were stable for periods of days or weeks and compatible blends were obtained when PVA was added. This effect was attributed to a synergistic effect of PVA and chitosan because the binary blends PVA/PLA and chitosan/PLA were completely incompatible. The blends were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), stress-strain tests, and Fourier transform infrared spectroscopy (FTIR). The results indicated that despite the fact that the system contained distinct phases some degree of molecular miscibility occurred when the three components were present in the blend.     

Stereocomplexes of enantiomeric lactic acid and sebacic acid ester-anhydride triblock copolymers

A systematic study on the synthesis, characterization, degradation, and drug release of d-, l-, and dl-poly(lactic acid) (PLA)-terminated poly(sebacic acid) (PSA) and their stereocomplexes is reported. PLA-terminated sebacic acid polymers were synthesized by melt condensation of the acetate anhydride derivatives of PLA oligomers and sebacic anhydride oligomers to yield ABA triblock copolymers of molecular weights between 3000 and 9000 that melt at temperatures between 35 and 80 degrees C. Pairs of the corresponding enantiomeric ABA copolymers composed of l-PLA-PSA-l-PLA and d-PLA-PSA-d-PLA were solvent mixed to form stereocomplexes. The formed stereocomplexes exhibited higher crystalline melting temperature than the enantiomeric polymers, which indicate stereocomplex formulation. The PLA terminals had a significant effect on the polymer degradation and drug release rate. PSA with up to 20% w/w of PLA terminals degraded and released the incorporated drug for more than 3 weeks as compared with 10 days for PSA homopolymer.     

Use of low MW polylactic acid and lactide to stimulate growth and yield of soybeans

Polylactic acid (PLA) is an environmentally friendly, degradable polymer which has been suggested for use as a matrix for controlled release of herbicides. The growth stimulation and yield improvement potential of low molecular weight (MW), poly(D,L-lactic acid) and D,L-lactide were evaluated using preplant soil incorporation with soybeans (Glycine max (L.) Merrill). Greenhouse studies confirmed that both lactide and PLA increased soybean leaf area, pod number, bean number and bean and plant dry weight. Soybean seed yield was increased most dramatically (130%; 2.3 fold) by weekly 30 ppm lactide addition and also by single addition of low MW (3500 Daltons) PLA (40.6%; 1.4 fold). Low levels of PLA were stimulatory (15–30 ppm), while higher levels were inhibitory, with some interaction with growth conditions being evident. The stimulatory component was most readily provided by weekly lactide addition, but was also provided by slow-release, hydrolytic breakdown of PLA in the soil, with 3500 Daltons MW being better than higher MW PLA. In field studies at two locations, PLA (16.8 and 45.8 kg ha^–1) increased soybean plot yield as much as 18%, being reflected in increases in both growth and per plant yield components (plant dry wt, seed number, seed dry wt, and number of branch pods and seeds). The levels used in field studies were selected to be similar to the level of a typical carrier used in slow release of herbicides. This study suggests that use of PLA as an encapsulation matrix for herbicides could provide reduced environmental impact and improved weed control, while at the same time increasing yield of soybeans through release of a plant growth stimulant in the form of oligomeric or monomeric lactic acid.     

Poly-lactic acid synthesis for application in biomedical devices - a review

Bioabsorbable polymers are considered a suitable alternative to the improvement and development of numerous applications in medicine. Poly-lactic acid (PLA,) is one of the most promising biopolymers due to the fact that the monomers may produced from non toxic renewable feedstock as well as is naturally occurring organic acid. Lactic acid can be made by fermentation of sugars obtained from renewable resources as such sugarcane. Therefore, PLA is an eco-friendly product with better features for use in the human body (nontoxicity). Lactic acid polymers can be synthesized by different processes so as to obtain products with an ample variety of chemical and mechanical properties. Due to their excellent biocompatibility and mechanical properties, PLA and their copolymers are becoming widely used in tissue engineering for function restoration of impaired tissues. In order to maximize the benefits of its use, it is necessary to understand the relationship between PLA material properties, the manufacturing process and the final product with desired characteristics. In this paper, the lactic acid production by fermentation and the polymer synthesis such biomaterial are reviewed. The paper intends to contribute to the critical knowledge and development of suitable use of PLA for biomedical applications.