Star-shaped polylactic acid-based triazine dendrimers: the catalyst type and time factors influence on polylactic acid molecular weight

Nowadays, extensive environmental problems due to the use of synthetic polymers have provoked efforts for their replacement with biopolymers as the most important research priorities. Polylactic acid (PLA) is one of the well-known biodegradable biopolymers. In this work, for the first time, PLA was modified with hydrophilic triazine-based dendrimers to obtain PLA with improved hydrophilic properties. In this regard, at first, dl-lactic acid (DLLA) was polymerized through the melt polycondensation to obtain poly-dl-lactic acid (PDLLA). The effects of reaction time and catalyst types on the molecular weight of the PDLLA were investigated. Also, the thermal behavior of PDLLAs with different molecular weights was evaluated using differential scanning calorimetry (DSC) technique. The obtained results from the DSC analysis showed that the PDLLA with higher molecular weight has a higher glass transition temperature (T_g) and melting point (T_m). In the following, various generations (G) of the triazine-based dendrimers were synthesized. To increase the hydrophilicity of the prepared PDLLA, chemical modification of PDLLA with the different generations of triazine-based dendrimer (G₁, G_1.5 and G₂) was performed. Due to the modification of PDLLA with dendrimers, the number of functional groups and hydrophilicity of PDLLA increased. Based on the obtained results, it is expected that the prepared systems could be a good and promising candidate for the production of biocompatible plastics with more hydrolytic degradation ability.

     

PBT固相缩聚的影响因素分析

通过PBT切片固相缩聚(SSP)实验,分析讨论了温度、时间、氮气流量和基础切片性能指标等因素对PBT固相缩聚反应的影响。结果表明温度、氮气流速、端羧基值对于PBT固相缩聚有显著影响,并均有明显的拐点:温度为190℃,氮气流速为50 m L/min,端羧基值为17.33 mol/t。     

双螺杆反应器制备高分子量聚乳酸的研究

利用双螺杆挤出机将低分子量的乳酸预聚物在挤出机上进一步缩聚,制备出较高分子量的聚乳酸.研究了反应挤出温度、催化剂用量及螺杆转速等因素对该缩聚反应的影响.结果表明,当反应温度为160℃,催化剂用量为0.5％,螺杆转速为30 r/min时,聚乳酸的分子量能得到最大程度的提高.     

Contribution of the solid phase polymerization to the molecular weight distribution in acrylonitrile precipitation copolymerization

Molecular weight distribution of copolyacrylonitrile, which was obtained from precipitation copolymerization without and with using dispersants in mixed solution, is studied. The contribution ratio of liquid phase polymerization and solid phase polymerization under different polymerization conditions could be worked out through the formula, which has been deduced in literature. From the calculated results, common points of each reaction system are, i) contribution ratio (r) of solid phase to liquid phase decreases with the increase of water content; thus the solid phase polymerization is gradually strengthened, which is apt to form chain of high molecular weight, ii) the higher temperature leads to higher compatibility between water and DMSO; thus the solid phase polymerization contribution would decrease, while the value of r is considerably larger. The limit molecular weight distribution of the system without dispersants in 100% water is approaching to 2; thus the corresponding r becomes larger, the molecular weight distribution ratio (Q) decreases in the system with dispersants.     

共溶剂对聚乳酸相对分子质量及热性能的影响

以超临界二氧化碳(SC-CO2)为载体,分别以丙酮、无水乙醚、六氟异丙醇为共溶剂,合成聚乳酸(PLLA),并采用FT-IR、GPC和DSC等对所获得的聚合物进行了相对分子质量测定和结构性能表征,探讨了3种共溶剂对用SC-CO2为溶剂合成的PLLA相对分子质量及热性能的影响。结果表明,共溶剂对PLLA的相对分子质量、相对分子质量分布指数以及热性能影响较大;以丙酮为共溶剂时,可以获得最高相对分子质量为47 690且热性能较好的PLLA。     

Improving the properties of polylactic acid by blending with low molecular weight polylactic acid‐g‐natural rubber

The low molecular weight (M_w) polylactic acid‐g‐natural rubber (PLA‐g‐NR) was synthesized by grafting the maleated natural rubber (MNR) with low molecular weight PLA at a weight ratio of 1:1 in toluene at 80°C. Two types of MNR (MNR10 and MNR20) having anhydride moieties of 10 and 20 wt%, respectively, were prepared. The reaction was followed by IR analysis. Next, the obtained PLA‐g‐NR was blended with pristine PLA using a twin‐screw extruder at PLA to PLA‐g‐NR weight ratios of 90:10, 80:20, 70:30, and 60:40 followed by compression to obtain specimens for testing. In case of 10 wt% PLA‐g‐NR having MNR10, it was found that blending of PLA with PLA‐g‐NR resulted in a 200% improvement in impact strength and twofold percent elongation at break (flexibility). Further SEM analysis confirmed that PLA‐g‐NR was compatible with PLA matrix. In contrast, NR was present as disperse particles which exhibited poor adhesion to PLA. From these findings, it was also found that PLA‐g‐NR was capable of improving the properties of PLA more than NR due to the fact that it exhibited higher compatibility. POLYM. ENG. SCI., 54:2770–2776, 2014. © 2013 Society of Plastics Engineers     

聚四氢呋喃生产过程中分子量控制的影响因素

分析了美国英威达工艺生产PTMEG产品时的分子量控制影响因素。通过对聚合反应的醋酸、醋酸酐浓度、进料量及控制窄化工序(SPD)温度,具体介绍了PTMEG分子量影响因素及控制方法。     

溶液聚合直接合成聚乳酸的研究

研究了以乳酸单体为原料在联苯醚中共沸脱水直接缩聚合成乳酸的方法 ,确定了最佳工艺条件 ,即锡粉 0 .2 9% ,聚苯醚 /乳酸为 4,13 0℃ ,4k Pa,反应 40 h,0 .3 nm分子筛脱水。与由乳酸先合成丙交酯再开环聚合的二步法相比 ,一步法工艺简单 ,试剂用量少 ,收率较高 ,成本更低     

High molecular weight poly (L‐lactic acid) clay nanocomposites via solid‐state polymerization

We propose here, a novel technique to synthesize high molecular weight (MW) poly (L ‐lactic acid)‐clay nanocomposite (PLACN), via solid state polymerization (SSP). We synthesize prepolymer of PLACN (pre‐PLACN) from both, L ‐lactic acid and L ‐lactide, as starting materials. Synthesis of pre‐PLACN from L ‐lactic acid is carried out via in situ melt polycondensation (MP) of L ‐lactic acid oligomer, followed by SSP, to achieve high MW PLACN (M_w ∼ 138,000 Da). In case of L ‐lactide as the starting material, we prepare L ‐lactide–clay intercalated mixture which yields moderate MW pre‐PLACN during subsequent ring opening polymerization (ROP). Interestingly, ROP is performed by using hydroxyl functionalized ternary catalyst system (L ‐lactide–Sn(II) octoate–oligo (L‐lactic acid) complex), which provides the terminal hydroxyl end‐groups, required for step‐growth SSP. Pre‐PLACN MW is now increased to M_w ∼ 127,000 Da, by the subsequent SSP process. ¹H NMR analyses confirm that these end‐groups, are indeed consumed during SSP. During SSP, the PLACN also achieves up to 90% crystallinity, which may be due to the synchronization of the slow step‐growth SSP of poly(L ‐lactic acid) (PLA) with the crystallization kinetics. Optical purity of PLACNs is similar to that of neat PLA, whereas the thermal stability of PLACNs is significantly superior. As evidenced by wide‐angle X‐ray scattering/small‐angle X‐ray scattering analyses and in line with the literature, both, intercalated and exfoliated PLACN morphologies, have been synthesized, by suitable selection of clays. We also verify the correlation between the PLA semicrystalline morphology and the PLACN morphology, which is consistent with those of PLACN synthesized by other techniques. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Effects of molecular weight and grafted maleic anhydride of functionalized polylactic acid used in reactive compatibilized binary and ternary blends of polylactic acid and thermoplastic cassava starch

Polylactic acid (PLA) was reactively functionalized with maleic anhydride (MA) and 2,5‐bis(tert‐butylperoxy)?2,5‐dimethylhexane (Luperox 101 or L101) using a twin screw extruder (TSE). The effects of functionality (grafted MA level) and/or number average molecular weight of functionalized PLA (PLA‐g‐MA) as the reactive polymer pairs (binary blends) and reactive compatibilizer (ternary blends) were investigated. Due to the dominant side reaction during melt free radical grafting, polymer degradation or chain scission, PLA‐g‐MA having a higher grafted MA had lower molecular weights and intrinsic viscosity as well as broader molecular weight distribution values. The thermal, physical, mechanical, and morphological properties of binary blends produced by using the TSE and injection molding at a ratio of 70 wt % PLA‐g‐MA and 30 wt % thermoplastic cassava starch (TPCS) were analyzed. The reactive blends having grafted MA more than 0.4 wt % had poor tensile strength and elongation at break. Similar trends in morphology and tensile properties were observed in the reactive ternary blends. The use of PLA‐g‐MA strongly impacted the elongation at break but not the modulus or tensile strength. An increase of PLA‐g‐MA's number average molecular weight ( or M_n) improved the tensile properties of the blends. The reactive ternary blend having 0.1 wt % grafted MA on PLA and PLA‐g‐MA basis and PLA‐g‐MA's M_n of 45 kDa offered the highest elongation at break. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42230.     

In-source and post-irradiation polymerization of acenaphthylene in the solid state

Radiation-induced solid state polymerization of acenaphthylene was studied by using ⁶⁰Co γ-rays. The extent of polymerization at room temperature reached 68% when acenaphthylene was irradiated with a dose of 2–5 MGy. Prolonged exposure to the radiation decreased the molecular weight of the polymers. The post-polymerization of acenaphthylene was found to occur at relatively high temperatures close to the melting point of acenaphthylene. Absence of an effective termination step allows the enhancement of post-polymerization at higher temperatures after a limiting conversion is accomplished.     

Effects of various factors on the formation of high molecular weight polyamic acid

The reaction of pyromellitic dianhydride (PMDA) and aromatic diamine in an aprotic solvent such as dimethylacetamide (DMAc) gives a solution of poly(amic acid). The effects of certain variables on the polymerization and some additives on the stability and imidization of the poly(amic acid)s were studied. It was found that the addition of PMDA portionwise to the solution of diamine always keeps the excess diamine in solution and enables one to obtain the highest molecular weight of poly(amic acid). When the addition process was reversed, either by the change or dehydration of solvent, a high molecular weight was not attained. The inevitable water in the solvent or the reaction medium is the major factor, and the more the water content in the solvent or the reaction medium, the larger is the probability of destruction of PMDA during the reaction and hence low molecular weight is obtained. If very pure monomers were used in the polymerization, the 1:1 of molar ratio is the optimum value. Excess diamine or dianhydride results in the exchange reaction with poly(amic acid) and causes a rapid degradation of polymer chain. This exchange reaction was proved by NMR measurements. The presence of electrophilic agents or the nucleophilic agents containing active protons in the poly(amic acid) solution promotes the decomposition of polymer and causes the brittleness of polyimide film in the curing process. Using acetic anhydride (A) to convert the poly(amic acid) to polyimide, pyridine (P) can protect the polymer chain from the nucleophilic attack by the anhydride. The mixture with proper ratio of A/P (1/1–15/1) can be used as good dehydrating agents. Meanwhile, according to the results to the results of experiments, we suggested the probable reaction mechanisms about how the water, amine, and anhydride destroy the polyamic acid chains.     

The role of nanofillers on the degradation behavior of polylactic acid

This study examines the effect of type and content of various nanofillers on the aging behavior of polylactic acid (PLA)/nanocomposites compared with that of pristine PLA, under specific environmental conditions, namely 80% relative humidity, 40°C temperature, and exposure time up to 6 months. Two different types of nanosized fillers (silica and montmorillonite, MMT) at three different weight fractions as well their mixtures were used for this purpose. The role of the various nanofillers on the aging of pristine PLA and its nanocomposites was investigated in terms of several experimental techniques including Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), and tensile testing. All studied samples, except those of PLA/MMT/Si nanocomposites, exhibited the same trend in properties during aging. In particular, no significant changes are noted after 1 month of aging. The materials after 3 months of aging experienced a dramatic lowering of the stress–strain curve, whereas at 6 months a reverse effect was observed. Comparing the effect of nanofiller types on the degradation, one could conclude that PLA/MMT nanocomposites exhibit a more homogeneous degradation effect, having a higher impact on yield stress in comparison with silica. In contrast, silica has a greater effect in Young's modulus and strain at break, compared with MMT. The peculiar behavior of the PLA/MMT/Si nanocomposites during aging is explained by the hindering action of the mixture of the two nanofillers on the molecular reordering of the PLA chains in the amorphous region. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

PET recycling: Evaluation of the solid state polymerization process

Many studies have been carried out to make bottle‐to‐bottle recycling feasible. One of the difficulties found is the decrease in the polymer's molar mass, which damages the injection blow molding process. A method usually employed to increase the molar mass of virgin PET consists of solid‐state polymerization (SSP). In this work, we studied the SSP process applied to post‐consumer recycled PET by analyzing the inherent viscosity and amount of carboxylic end groups, and the results of dynamic flow rheometry. Although the results show that the recycling process decreases polymer molar mass, and this indicates degradative processes, SSP was successful in increasing molar mass in post‐consumer recycled PET. This made feasible bottle‐to‐bottle recycling. In addition, the parallel plate rheometry technique was powerful in assessing the degradative process and, therefore, that the SSP process was successful. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Photochromic films prepared by solid state processing of disentangled ultrahigh molecular weight polyethylene and photochromic dyes composites

Disentangled ultrahigh molecular weight polyethylene (DPE) is a special grade of polyethylene (molecular weight, >10⁶ Da) which can be processed by an environment friendly solid state process on counter rotating two roll mill (TRM) below the melt temperature of the polymer. This unique processing property of DPE was utilized to develop smart DPE photochromic films. Photochromic dye like 'Spirooxazine' or 'Spiropyran' has been mixed with DPE resin powder prior to film formation without altering the DPE properties. These films could change their optical appearances on exposure to UV-light of wavelength 365 nm and the color change phenomenon of the films could also be replicated by sunlight. The color change observed is found to be reversible, that is, films could return to colorless form either spontaneously in dark or by thermal stimuli. Such smart property was imparted to DPE even at very low concentration (2,000 ppm) of photochromic dyes. Spectrophotometric studies were used to measure the rate of forward reaction with UV radiation and the rate of backward reaction in dark. In fact, DPE powder and photochromic dye composite was used to produce the compression molded disc to understand the color change phenomena. Moreover, it was observed that the photo-degradation rate of dye, could be retarded ~30% by using amphoteric Zinc phthalate salt. TGA and DSC studies confirmed that the characteristics of DPE film remained almost unaltered even after with preparation of film photochromic dyes.     

Emulsion polymerization of tetrafluoroethylene: effects of reaction conditions on the polymerization rate and polymer molecular weight

The emulsion polymerization of tetrafluoroethylene (TFE) was carried out in a semibatch reactor using a chemical initiator (ammonium persulfate) and a fluorinated surfactant (FC-143). The effects of the reaction condition were investigated though the polymerization rate, molecular weight of polytetrafluoroethylene (PTFE), and stability of the dispersion. The emulsion polymerization of TFE was different from conventional emulsion polymerization. The polymerization rate was suppressed when the polymer particles were significantly coagulated. The polymerization rate increased with operating temperature, surfactant concentration, and agitation speed, due to the enhanced stability of the polymer particles. However, once the parameter value was reached, the rate decreased due to the coagulation of the particles. Stable PTFE dispersion particles were obtained when the surfactant concentration was in the range between 3.48 × 10⁻³ and 32.48 × 10⁻³ mol/liter, which is below critical micelle concentration (CMC). The molecular weight of the PTFE obtained was a function of the surfactant and initiator concentrations, and the polymerization temperature. The molecular weight increased as each parameter decreased. This is against the phenomena observed in a conventional emulsion polymerization. A stable PTFE dispersion polymer having a high molecular weight was obtained by optimizing the reaction conditions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 777–793, 1999     

影响固碱锅使用寿命的主要因素

着重分析影响固碱锅使用寿命的因素:碱液的起始浓度、最高熔碱温度、火焰加热方式、升温速度等,提出了延长固碱锅使用寿命的措施。     

聚合条件对P(AN-co-IA)分子质量分布影响的研究

采用凝胶色谱（GPC）法测定了丙烯腈与衣康酸共聚物P（AN—co—IA）的重均分子质量和数均分子质量,并通过已知聚丙烯腈的重均分子质量数据和数均分子质量数据对所测的分子质量进行校正,进一步计算得到共聚物的多分散系数。同时研究了引发剂用量、单体浓度、聚合温度、聚合时间对P（AN—co—IA）分子质量分布的影响。研究结果表明,P（AN-co-IA）分子质量分布随引发剂用量的增大、聚合单体浓度的增加而变宽,与聚合反应温度、聚合反应时间无明显的变化趋势。     

A multi-thread parallel computation method for dynamic simulation of molecular weight distribution of multisite polymerization

Molecular weight distribution (MWD) is an important quality index of polymer products. Many methods have been proposed to dynamically simulate the MWD of polymerization, but these methods are normally designed for serial computations. In this paper, a multi-thread parallel computation method was proposed for multisite free-radical polymerization. Analysis of the relationship among different subtasks revealed a combined parallel strategy by fully exploiting the parallel feature of the process. A good performance was obtained to accelerate the dynamic simulation of MWD based on Flory method. We theoretically analyzed the speedup ratio (SR) and parallel efficiency (PE). Results showed that software algorithm and hardware configuration exhibited a good match. The efficiency of the proposed parallel method was presented through industrial slurry processes that used high-density polyethylene (HDPE).     

Microwave-assisted polymerization process: A way to design new, high molecular weight poly(arylimidazole)s

In this paper, the microwave-assisted synthesis of high molecular weight poly(arylimidazole)s is described. These polymers were obtained by a one-pot polycondensation reaction involving a bis(α-diketone), an aromatic dialdehyde and ammonium acetate. Depending on the dialdehyde monomer, different poly(arylimidazole)s structures were synthesized. Structural characterization (¹H and ¹³C NMR), thermal properties (T_g, thermal stability) as well as a molecular weight determination of the polymers are reported.