Humidity sensor based on poly(lactic acid)/PANI–ZnO composite electrospun fibers

The electrospinning technique has been successfully used to prepared micro-fibers of the poly(lactic acid)/polyaniline–zinc oxide (PLA/PANI–ZnO) composite. The polyaniline–zinc oxide (PANI–ZnO) nanocomposites are synthesized by hydrothermal and in situ polymerization methods. X-ray diffraction techniques are used to study the structural properties of the PLA/PANI–ZnO composite fibers and the PANI–ZnO nanocomposite. The average crystallite size of the PANI–ZnO nanocomposite is found to be 36 nm. The morphology and diameter of the composite fibers are analyzed by scanning electron microscopy (SEM). The average fiber diameter of the pure poly(lactic acid) (PLA) fiber is around 2.5 μm and that of the PLA/PANI–ZnO composite fiber is around 1.4 μm. Differential scanning calorimetry (DSC) provides the thermal properties of the PLA/PANI–ZnO composite fibers. The melting temperature (T_m) for the pure PLA is observed at 149.3 °C, and it is shifted to 153.0 °C for the PLA/PANI–ZnO composite fibers. The enhanced thermal properties of the composite fibers are due to the interaction between the polymer and the nanoparticles. The water contact angle measurements probe the surface hydrophilicity of the PLA/PANI–ZnO composite fibers. The role of the PANI–ZnO nanocomposite on the sensing behavior of PLA fibers has also been investigated. The humidity sensing properties of the composite fiber based sensor are studied in the relative humidity (RH) range of 20–90% RH. The experimental results show that the composite fiber exhibited good response (85 s) and recovery (120 s) times. These results indicate that the one-dimensional (1D) fiber structure enhances the humidity sensing properties.

The electrospinning technique has been successfully used to prepared micro-fibers of the poly(lactic acid)/polyaniline–zinc oxide (PLA/PANI–ZnO) composite for humidity sensor application.     

Cotton-like micro- and nanoscale poly(lactic acid) nonwoven fibers fabricated by centrifugal melt-spinning for tissue engineering

Biodegradable materials in the form of nonwoven fibers have attracted increasing attention for tissue engineering applications because they offer large surface areas and interconnected networks. In this study, cotton-like nonwoven poly(lactic acid) (PLA) fibers were successfully fabricated by centrifugal melt-spinning. The effects of centrifugal speed and secondary melt-spinning processing on the morphology, mechanical properties, and cell compatibility of the fibers were investigated. Scanning electron microscopy, differential scanning calorimetry, and Fourier-transform infrared spectroscopy (FTIR), as well as cell culturing of MC3T3-E1 were used in this study. The results showed that centrifugal speeds from 350 to 1500 rpm satisfied the needs for fiber formation. The PLA fibers we prepared had three-dimensional structures with extensive diameter distribution from the nanoscale to several tens of micrometers, large pore sizes, and high porosities, significantly different from fibers produced by electrospinning. The fiber diameters and mechanical properties could be manipulated by controlling the centrifugal speed. The finest fibers were generated at 900 rpm with average diameters of 3.47 ± 3.48 μm. The fibers created by centrifugal melt-spinning exhibited lower cytotoxicity and higher cell proliferation than those obtained by electrospinning.

Schematic of the centrifugal melt spinning apparatus, consisting of (a) a rotary disk, (b) heating circuit, (c) electromotor, (d) filling inlet and (e) rotary collector on a drum.     

Modification of release rates of cyclosporin A from polyl(L-lactic acid) microspheres by fatty acid esters and in-vivo evaluation of the microspheres.

Biodegradable microspheres containing cyclosporin A (CyA, cyclosporine) were prepared using poly(L-lactic acid) (PLA) and poly(lactide-co-glycolide)(PLGA) by a solvent evaporation method. CyA was efficiently entrapped in PLA, PLGA(50/50) and PLGA(75/25) microspheres in a range of 81-85%. CyA released constantly from PLA microspheres without any lag time, whereas the drug from PLGA(50/50) and PLGA(75/25) microspheres was released after lag time of about 1 and 3 weeks, respectively. Addition of fatty acid esters enhanced the release rates of CyA from PLA microspheres. In-vivo study was performed using rats with adjuvant-induced arthritis. PLA microspheres with ethyl myristate sustained high blood levels of CyA compared with the microspheres with no additives over 4 weeks. In addition, the PLA microspheres improved the symptoms such as the decrease in body weight and the increase in paw swelling occurred by adjuvant-induced arthritis in rats. Consequently, the release rate of CyA from PLA microspheres can be improved by adding fatty acid esters and PLA microspheres with fatty acid esters seem to be a useful dosage form for autoimmune disease therapy.     

Construction of carbon-based flame retardant composite with reinforced and toughened property and its application in polylactic acid

To simultaneously improve the flame retardancy, strength and toughness of polylactic acid (PLA) fibers, a composite flame retardant CNTs-H-C was prepared with carbon nanotubes (CNTs) as the core, hexachlorocyclotriphosphazene as linker, and chitosan grafted on the surface. The prepared CNTs-H-C was introduced into a PLA matrix to obtain CNTs-H-C/PLA composites and fibers via a melt-blending method. The morphology, structure, flame retardant properties and mechanical properties were thoroughly characterized, and the flame retardant mechanism was studied. Results showed that the prepared CNTs-H-C displayed a nanotube-like morphology with good compatibility and dispersion in the PLA matrix. After blending with PLA, CNTs-H-C/PLA composites exhibited outstanding flame retardancy with limiting oxygen index (LOI) increasing from 20.0% to 27.3%, UL94 rating reaching V-0. More importantly, the introduction of CNTs-H-C did not affect the spinnability of PLA. Compared with pure PLA fibers, the LOI of CNTs-H-C/PLA fibers with a CNTs-H-C content of 1.0 wt% increased by 32.5%, and meanwhile the breaking strength and elongation increased by 28.2% and 30.4%, respectively. Mechanism study revealed that CNTs-H-C/PLA possessed a typical condensed phase flame retardancy mechanism. In short, we have developed a CNT-based composite flame retardant with reinforced and toughened properties for the PLA matrix. The prepared CNTs-H-C showed great potential in polymer flame retardancy and mechanical enhancement.

A CNT-based flame retardant was synthesized and introduced into PLA to simultaneously improve the flame retardancy, strength and toughness of PLA.     

Effectiveness of silane treatment on absorbable microfibers.

Preliminary experiments suggest pretreatment of absorbable crystalline, calcium-sodium-metaphosphate (CSM) microfibers with trimethoxy-based silane coupling agents yields a polysiloxane film barrier which protects the fiber surface from early dissolution due to water. Compared to thermoplastic poly(L-lactic acid) (PLLA) composites reinforced with untreated fibers, PLLA composites reinforced with a variety of silane pretreated microfibers showed increased mechanical properties, suggesting improved adhesion was achieved at the fiber/matrix interface. Unfortunately, the silane pretreated CSM/PLLA composite showed no increase in wet strength retention after short-term in vitro exposure. This may be due to plasticization from water entering the composite at areas of incomplete fiber wetting by the highly viscous molten PLLA. However, when a nonabsorbable, low viscosity unsaturated polyester thermoset resin was reinforced with methacryloxy-silane pretreated CSM microfibers, there was no decrease in flexural strength and less than a 10% decrease in flexural modulus after 7 days exposure to 7.4 pH Tris-buffered saline at 37 degrees C.     

Mechanical properties of biodegradable polymers and composites proposed for internal fixation of bone.

The mechanical properties of biodegradable polymers and composites proposed for use in internal fixation (in place of stainless steel) are crucial to the performance of devices made from them for support of healing bone. To assess the reported range of properties and degradation rates, we searched and reviewed papers and abstracts published in English from 1980 through 1988. Mechanical property data were found for poly(lactic acid), poly(glycolic acid), poly(epsilon-caprolactone), polydioxanone, poly(ortho ester), poly(ethylene oxide), and/or their copolymers. Reports of composites based on several of these materials, reinforced with nondegradable and degradable fibers, were also found. The largest group of studies involved poly(lactic acid). Mechanical test methods varied widely, and studies of the degradation of mechanical properties were performed under a variety of conditions, mostly in vitro rather than in vivo. Compared to annealed stainless steel, unreinforced biodegradable polymers were initially up to 36% as strong in tension and 54% in bending, but only about 3% as stiff in either test mode. With fiber reinforcement, reported highest initial strengths exceeded that of stainless steel. Stiffness reached 62% of stainless steel with nondegradable carbon fibers, 15% with degradable inorganic fibers, but only 5% with degradable polymeric fibers. The slowest-degrading unreinforced biodegradable polymers were poly(L-lactic acid) and poly(ortho ester). Biodegradable composites with carbon or inorganic fibers generally lost strength rapidly, with a slower loss of stiffness, suggesting the difficulty of fiber-matrix coupling in these systems. The strength of composites reinforced with (lower modulus) degradable polymeric fibers decreased more slowly. Low implant stiffness might be expected to allow too much bone motion for satisfactory healing. However, unreinforced or degradable polymeric fiber reinforced materials have been used successfully clinically. The key has been careful selection of applications, plus use of designs and fixation methods distinctly different from those appropriate for stainless steel devices.     

Construction of a ternary system: a strategy for the rapid formation of porous poly(lactic acid) fibers

Combining electrospinning technology with nonsolvent induced phase separation (ESP-NIPS), 10 wt% poly(lactic acid) (PLA) spinning solutions are prepared by using chloroform as a good solvent and absolute ethanol as a nonsolvent. The “PLA/CHCl₃/C₂H₅OH” ternary system is constituted to realize the rapid preparation of porous-structured PLA fibers. The morphologies, thermal properties and crystalline structures of the obtained fibers are characterized and the rapid forming mechanism of PLA porous fibers is investigated and discussed. The interaction parameters between the substances of the “PLA/CHCl₃/C₂H₅OH” ternary system, binodal line, spinodal line and critical point are obtained by theoretical calculation and experiment, and the “PLA/CHCl₃/C₂H₅OH” ternary phase diagram model is established. The results show that, when the mass ratio of chloroform/ethanol is around 75/25, the rapid “in situ” formation of the PLA fibers can be realized with porous structures within 5–10 s. The establishment of a “nonsolvent-solvent–polymer” ternary phase diagram model has laid a theoretical foundation for the rapid formation of polymer porous fibers by ESP-NIPS. The ESP-NIPS for the porous PLA fibers preparation provides a new resolution for the rapid formation of porous polymer materials, which is vital to further expand the application of electrospun fibers in emergency situations such as isolation, protection, insulation and flame retardant usage.

Combining electrospinning technology with ESP-NIPS, using chloroform as a solvent and absolute ethanol as a nonsolvent, poly(lactic acid) porous fibres are prepared within 5–10 s. This preparation provides a new resolution for the rapid formation of porous polymer materials.     

Simultaneously enhancing the crystallization rate and fire retardancy of poly(lactic acid) by using a novel bifunctional additive trimethylamine phenylphosphonate

Simultaneously regulating the crystallizing and combustion behaviors of poly(lactic acid) (PLA) will be conducive to its further development in the fields of electronic appliances, automotive and rail transit materials. To achieve this goal, a novel bifunctional additive triethylamine phenylphosphonate (TEAP) was synthesized through acid–base neutralization reaction between trimethylamine and phenylphosphonic acid. When TEAP was added into PLA, the crystallization behaviors of PLA/TEAP assessed by differential scanning calorimetry (DSC) and polarized optical microscopy (POM) suggested that TEAP acted as a nucleating agent and plasticizer for PLA, which effectively increased the crystallization rate of PLA. However, PLA with 3 wt% TEAP showed a slower crystallization rate than that of PLA with 1 wt% TEAP due to the filler aggregation of TEAP. Thus, the crystallization rate increased first and then slightly decreased with increasing content of TEAP. Compared with the variation of the crystallization rate, the long period (L) and amorphous layer thickness (L_a) resulting from SAXS showed opposite trends, while the average crystal thickness (L_c) changed slightly; the reason may relate to the variation of the number of lamellae with increasing the content of TEAP. Meanwhile, the results of WAXD and Raman spectra showed the crystal structure of PLA was not affected by the addition of TEAP. The combustion behaviors of PLA and PLA/TEAP were evaluated by the limiting oxygen index (LOI), UL-94 test, cone calorimetry test (CCT) and thermal gravimetric analyses coupled to Fourier transform infrared spectroscopy (TGA-FTIR). According to the results, TEAP mainly promotes the removal of melt dripping, hence brings away heat and delays the combustion. Besides, the production of phosphorus-containing free radicals can quench hydrogen or oxygen free radicals in the fire. Thus, the fire safety of PLA is significantly improved by adding a very low content of TEAP (1–3 wt%). Only 1 wt% loading of TEAP can increase the LOI value of PLA from 19.5 vol% to 28.6 vol%, pass the UL-94 V-0 rating and have a low peak heat release rate of 404 kW m⁻².

Simultaneously regulating the crystallizing and combustion behaviors of poly(lactic acid) (PLA) will be conducive to its further development in the fields of electronic appliances, automotive and rail transit materials.     

电纺丝技术制备生物活性复合纤维支架及其体外降解性

背景:聚乳酸/羟基磷灰石类复合材料支架常用的制备方法主要有冷压法、粒子沥滤法、热致相分离法等,但是在增强材料界面的结合、调节材料的降解速率、改善材料的强度等方面仍不能满足要求。目的:制备左旋聚乳酸/羟基磷灰石复合纳米纤维支架。方法:采用静电纺丝法制备聚乳酸/羟基磷灰石复合纳米纤维支架。以扫面电镜对纤维的结构形态进行分析,并观察其在PBS中浸泡不同时间的体外降解过程。结果与结论:羟基磷灰石纳米粒子与聚乳酸/基体间存在化学键合,纳米粒子使纤维直径增大且表面粗糙程度增加,这种结构将有利于细胞在纤维膜上的伸展和和繁殖。羟基磷灰石的引入,抑制了聚乳酸降解过程中的自催化作用,减缓了聚乳酸的降解速度。说明电纺丝技术制备的聚乳酸/羟基磷灰石复合支架在组织工程支架材料方面具有潜在的应用前景。     

电纺丝技术制备生物活性复合纤维支架及其体外降解性

背景：聚乳酸/羟基磷灰石类复合材料支架常用的制备方法主要有冷压法、粒子沥滤法、热致相分离法等,但是在增强材料界面的结合、调节材料的降解速率、改善材料的强度等方面仍不能满足要求。目的：制备左旋聚乳酸/羟基磷灰石复合纳米纤维支架。方法：采用静电纺丝法制备聚乳酸/羟基磷灰石复合纳米纤维支架。以扫面电镜对纤维的结构形态进行分析,并观察其在PBS中浸泡不同时间的体外降解过程。结果与结论：羟基磷灰石纳米粒子与聚乳酸/基体间存在化学键合,纳米粒子使纤维直径增大且表面粗糙程度增加,这种结构将有利于细胞在纤维膜上的伸展和和繁殖。羟基磷灰石的引入,抑制了聚乳酸降解过程中的自催化作用,减缓了聚乳酸的降解速度。说明电纺丝技术制备的聚乳酸/羟基磷灰石复合支架在组织工程支架材料方面具有潜在的应用前景。     

Rheological behavior,crystallization properties,and foaming performance of chain-extended poly (lactic acid) by functionalized epoxy

The inherently linear poly (lactic acid) suffers unsatisfying foaming behavior due to its low melt strength and poor crystallization properties. To overcome this drawback, a random terpolymer of ethylene, acrylic ester and glycidyl methacrylate (EGMA) was employed to improve the rheological behavior, crystallization properties, and foaming performance of poly (lactic acid) (PLA) through a chain extension reaction. The branched/micro-crosslinked structure formed by the chain extension reaction between EGMA and PLA effectively improved the dynamic rheological properties of PLA. As the content of EGMA increased from 0 wt% to 20 wt%, the crystal nucleation and crystal growth rate of various PLA samples have been significantly accelerated, resulting in a larger number and smaller size of spherulites, and the crystallinity of various PLA samples increased from 7.9% to 38.54%. The cell size of various PLA foams decreased from 53.5 to 22.0 μm and the cell density increased from 3.5 × 10⁶ cells per cm³ to 2.5 × 10⁷ cells per cm³, meanwhile, the cellular morphology of PLA foam was obviously improved. Moreover, the actual weight loss of PLA foams reached 26.1%, which is higher than the theoretical weight loss.

The branched/micro-crosslinked structure formed by chain extension reaction between EGMA and PLA improved the rheological behavior and crystallization properties of PLA, which ameliorated the foaming performance of various PLA samples.     

Influence of poly(lactide) stereocomplexes as nucleating agents on the crystallization behavior of poly(lactide)s

The influence of the addition of linear and four-arm poly(lactide) (PLA) stereocomplexes (scPLAs) on the non-isothermal and isothermal crystallization behavior of poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) from the molten state was investigated. The linear PLAs and four-arm PLA with a similar chain length for each arm were synthesized by ring-opening polymerization. The linear and four-arm scPLAs were then prepared by solution blending and characterized by ¹H-NMR, FTIR, and WAXD analysis. Various mass ratios of the scPLAs were subsequently added to PLLA and PDLA as nucleating agents and specimens were prepared by solution casting. The isothermal and non-isothermal crystallization behavior of the specimens was examined by differential scanning calorimetry and polarized optical microscopy. The SC crystallites effectively promoted the nucleation of the PLAs, thereby increasing the general crystallization rate of the matrix. A 10% content of stereocomplex nucleating agent increased the crystallization rate of PDLA and PLLA by more than 55% and 70%, respectively. Compared with the linear scPLA, the four-arm scPLA more strongly promoted crystallization at higher temperatures. This might be because the greater degree of branching and larger steric hindrance of the four-arm scPLA led to the formation of defective SC crystallites, which was more beneficial for adsorption of the matrix on the crystal surface and permitted the nucleation and growth at higher temperatures. These results demonstrate that scPLAs can potentially be used as nucleating agents to improve the performance and transparency of PLA films.

The influence of the addition of linear and four-arm poly(lactide) stereocomplexes on the crystallization behavior of poly(l-lactide) and poly(d-lactide) from the molten state was investigated.     

凝固浴温度与相转化聚醚砜中空纤维膜的结构与性能

以聚醚砜为膜材料、N,N-二甲基乙酰胺为溶剂、聚乙烯吡咯烷酮为添加剂配成稳定溶液,使用水为凝固浴,采用干/湿法溶液相转化制备聚醚砜中空纤维膜。分析了凝固浴温度及空气间隙距离对膜的表面孔结构、断面结构和其他性能的影响。发现升高凝固浴温度的同时,增大空气间隙,可以有效的增大膜外表面的孔径,膜断面近外皮层下结构由指状孔向海绵状孔转化。     

Melting centrifugally spun ultrafine poly butylene adipate-co-terephthalate (PBAT) fiber and hydrophilic modification

This paper demonstrates that melt centrifugal spinning could be used to effectively fabricate degradable poly (butylene adipate-co-terephthalate) (PBAT) fibers with uniform fiber diameter. The hydrophobic PBAT fibers were modified into hydrophilic fibers using the hyperbranched polyesters (HBP) with three-dimensional molecular chain structures and a large number of functional groups at the chain ends. The structures and properties of the obtained fibers were characterized with SEM, XRD, DSC, contact angle, and tensile strength analyses. Results indicate that fibers with uniform diameters can be conveniently fabricated by designing a spinneret. The obtained fibers showed no apparent change in crystallization compared to PBAT pellets, while the thermal stability and mechanical properties of PBAT/HBP fibers were dependent on the HBP ratio in fibers. More importantly, the obtained fibers gradually changed from hydrophobic to super-hydrophilic with increasing HBP content in fibers up to 30%. The modified hydrophilic PBAT/HBP presents a greatly significant potential for application in biomedical fields.

The PBAT fibers were fabricated by using our own designed melting centrifugal spinning setup, and followed by improving the fiber wettability with hyperbranched polyesters (HBP).     

头发纤维聚集态结构与拉伸性能的研究

目的：分析头发纤维聚集态结构与拉伸性能的关系,为毛发疾病治疗和头发护理提供理论基础。方法：收集42例汉族人的头发样品,使用X-射线衍射仪测量头发纤维的结晶度和取向度,使用强力试验机检测头发纤维分别在干湿状态下的断裂强度和断裂伸长率。结果：头发纤维的结晶度为（28.82±2.60）%,取向度为（76.0±1.5）%。头发纤维在干态下断裂强度为（1.84±0.28）cN/dtex,断裂伸长率为（72.774±4.272）%;湿态下断裂强度为（1.46±0.21）cN/dtex,断裂伸长率为（70.018±4.412）%。干态与湿态下头发断裂强度、断裂伸长率之间的差异具有统计学意义。头发纤维的结晶度、取向度与断裂强度、断裂伸长率呈正相关。结论：头发纤维的聚集态结构与其拉伸性能呈正相关,结晶度、取向度越高的头发样品其断裂强度和断裂伸长率越高,具有更强的力学性质。     

Release of tetracycline hydrochloride from electrospun poly(ethylene-co-vinylacetate), poly(lactic acid), and a blend.

Electrospun fiber mats are explored as drug delivery vehicles using tetracycline hydrochloride as a model drug. The mats were made either from poly(lactic acid) (PLA), poly(ethylene-co-vinyl acetate) (PEVA), or from a 50:50 blend of the two. The fibers were electrospun from chloroform solutions containing a small amount of methanol to solubilize the drug. The release of the tetracycline hydrochloride from these new drug delivery systems was followed by UV-VIS spectroscopy. Release profiles from the electrospun mats were compared to a commercially available drug delivery system, Actisite (Alza Corporation, Palo Alto, CA), as well as to cast films of the various formulations.     

Role of zinc in formulation of PLGA/PLA nanoparticles encapsulating betamethasone phosphate and its release profile.

The purpose of this study was to develop poly(D,L-lactic/glycolic acid) (PLGA) or poly(D,L-lactic acid) (PLA) nanoparticles of less than 200 nm in diameter that encapsulated water-soluble corticosteroid derivatives for sustained release and targeting to inflammatory sites. Nanoparticles were prepared with PLGA (or PLA), zinc, betamethasone phosphate and surfactant by an oil-in-water solvent diffusion method. With this method, the efficiency of encapsulating betamethasone phosphate in the nanoparticles and the particle size were significantly affected by various factors, such as the concentration of PLGA (or PLA) and the amount of zinc added. Nanoparticles ranging from 80 to 250 nm in diameter could be prepared, with a maximum betamethasone phosphate content of 8% (w/w). Betamethasone phosphate was gradually released from the nanoparticles in diluted serum, and the release rate depended on the glycolic/lactic acid ratio and on the molecular weight of PLGA or PLA. Betamethasone was gradually released over at least 8 days from murine macrophages that had internalized betamethasone phosphate-encapsulated nanoparticles in vitro, and the rate of release was slower than from nanoparticles prepared without zinc. These results suggest that zinc increases the efficiency of encapsulating betamethasone phosphate in nanoparticles and also promotes sustained release of betamethasone phosphate from the nanoparticles.     

Multiple actions of poly(ethylene octene) grafted with glycidyl methacrylate on the performance of poly(lactic acid)

Poly(ethylene octene) grafted with glycidyl methacrylate (POE-g-GMA) was employed to improve the rheological and thermal properties, toughness, and foaming behaviors of poly(lactic acid) (PLA) through a chain extension effect. The dynamic rheological properties of PLA were improved significantly with increasing content of POE-g-GMA, due to the chain extension reaction between PLA and POE-g-GMA. As the content of POE-g-GMA increased, the cold crystallization temperature of PLA decreased by more than 10 °C and the crystallinity of PLA increased slightly from 1.2% to 4.7%, respectively. The impact strength of PLA with a POE-g-GMA content of 10 wt% increased by more than 4 times, compared with that of pure PLA. A sea-island structure could be observed in the PLA/POE-g-GMA blends and the distribution of POE-g-GMA was uniform. PLA foams with various POE-g-GMA contents were prepared in a stainless-steel autoclave using supercritical CO₂ as a physical blowing agent. The cellular morphology of PLA foam was obviously improved when the concentration of POE-g-GMA increased from 5 wt% to 10 wt%.

Poly(ethylene octene) grafted with glycidyl methacrylate (POE-g-GMA) was employed to improve the rheological and thermal properties, toughness, and foaming behaviors of poly(lactic acid) (PLA) through a chain extension effect.     

生物降解材料聚L-乳酸的熔融缩聚合成

背景:通过对合成工艺和催化剂的优化和选择,合成较高相对分子质量的聚乳酸生物降解材料.方法:实验于2003-02/2004-10在哈尔滨工业大学市政环境工程学院绿色化学与技术研究中心完成.以L-乳酸为原料,通过熔融缩聚的一步法合成可生物降解的聚L-乳酸.乳酸首先在无催化剂存在条件下发生自催化缩聚反应,生成较低相对分子质量的预聚物OLLA;然后将催化剂加入到OLLA中继续反应,最后得到较高相对分子质量的聚乳酸.实验考察了预聚条件、催化剂种类和用量、催化剂溶解程度、聚合温度及反应时间对聚乳酸分子量的影响.采用傅立叶变换红外光谱仪和核磁共振氢谱对聚合物结构进行了分析确认,通过凝胶气相色谱测定了聚合物的相对分子质量分布.结果:L-乳酸在140 ℃下,先在30 kPa下脱水反应2 h;然后减压至5 kPa继续反应4 h,可得到黏均相对分子质量(Mη)为6 500左右的OLLA.以SnCl2-TSA复合体系为催化剂,按SnCl2与OLLA质量比= 0.4%,TSA:SnCl2=1.0(mol/mol)的用量和配比,将催化剂加入OLLA中并充分溶解后,在165 ℃左右,5 kPa下搅拌反应8 h左右,至反应物出现爬杆现象时终止反应,可得到Mη约为65 000的聚L-乳酸.结论:在优化的工艺条件和催化剂下,能够在较短时间(8 h)内获得较高相对分子质量的聚L-乳酸,使该生物降解材料具备了一定的实用价值.     

Phosphorylation/caproylation of cornstarch to improve its adhesion to PLA and cotton fibers

To investigate the influence of phosphorylation/caproylation on the adhesion of cornstarch to polylactic acid (PLA) and cotton fibers for improving its applications, such as in PLA and cotton sizing, herein, a series of phosphorylated and caproylated cornstarch (PCS) samples with different total degrees of substitution (DS) were synthetized by the phosphorylation of acid-converted cornstarch (ACS) with sodium tripolyphosphate (STP) and subsequent caproylation with caproic anhydride (CA). The PCS granules were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The adhesion was evaluated by determining the bonding forces of the impregnated PLA and cotton roving. The results of the adhesion measurements were also analyzed, especially for the wetting and spreading of the pastes on the fiber surfaces as well as the failure type and internal stress of the adhesive layers among the fibers. In addition, the viscosity stabilities of the pastes were determined. The results showed that phosphorylation/caproylation was capable of obviously improving the adhesion of starch to PLA and cotton fibers. As the total DS increased, the bonding forces gradually increased. The two substituents improved the wetting and spreading, reduced the internal stress, lowered the layer brittleness, and decreased the probabilities of interfacial failure and cohesive failure, thereby favoring the improvement of the adhesion. The PCS samples with stabilities above 85% could meet the stability requirement for sizing. Based on the experimental results of the adhesion and the analysis of the results, it can be concluded that PCS shows potential for applications in PLA and cotton sizing.

PCS samples were prepared for improving the adhesion of starch to PLA and cotton fibers.