An efficient solid‐state polycondensation method for synthesizing stereocomplexed poly(lactic acid)s with high molecular weight

Simultaneous solid‐state polycondensation (SSP) of the powdery prepolymers of poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) can produce entire stereocomplexed poly(lactic acid)s (sc‐PLA) with high molecular weight and can be an alternative synthetic route to sc‐PLA. Ordinary melt polycondensations of L ‐ and D ‐lactic acids gave the PLLA and PDLA prepolymers having medium molecular weight which were pulverized for blending in 1:1 ratio. The resultant powder blends were then subjected to SSP at 130–160 °C for 30 h under a reduced pressure of 0.5 Torr. Some of the products thus obtained attained a molecular weight (M_w) as high as 200 kDa, consisting of stereoblock copolymer of PLLA and PDLA. A small amount of the stereocomplex should be formed in the boundaries of the partially melted PLLA and PDLA where the hetero‐chain connection is induced to generate the blocky components. The resultant SSP products showed predominant stereocomplexation after their melt‐processing in the presence of the stereoblock components in spite of containing a small amount of racemic sequences in the homo‐chiral PLLA and PDLA chains. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3714–3722, 2008     

Effect of prepolymer molecular weight on solid state polymerization of poly(bisphenol a carbonate) with nitrogen as a sweep fluid

The effect of prepolymer molecular weight on the solid‐state polymerization (SSP) of poly(bisphenol A carbonate) was investigated using nitrogen (N₂) as a sweep fluid. Prepolymers with different number–average molecular weights, 3800 and 2400 g/mol, were synthesized using melt transesterification. SSP of the two prepolymers then was carried out at reaction temperatures in the range 120–190 °C, with a prepolymer particle size in the range 20–45 μm and a N₂ flow rate of 1600 mL/min. The glass transition temperature (T_g), number–average molecular weight (M_n), and percent crystallinity were measured at various times during each SSP. The phenyl‐to‐phenolic end‐group ratio of the prepolymers and the solid‐state synthesized polymers was determined using 125.76 MHz ¹³C and 500.13 MHz ¹H nuclear magnetic resonance (NMR) spectroscopy. At each reaction temperature, SSP of the higher‐molecular‐weight prepolymer (M_n = 3800 g/mol) always resulted in higher‐molecular‐weight polymers, compared with the polymers synthesized using the lower molecular weight prepolymer (M_n = 2400 g/mol). Both the crystallinity and the lamellar thickness of the polymers synthesized from the lower‐molecular‐weight prepolymer were significantly higher than for those synthesized from the higher‐molecular‐weight prepolymer. Higher crystallinity and lamellar thickness may lower the reaction rate by reducing chain‐end mobility, effectively reducing the rate constant for the reaction of end groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4959–4969, 2008     

Sonocrystallization of polycarbonate melts

In this paper, we showed the simplified continuous process to crystallize the polycarbonate (PC) melts using sonocrystallization which is based on ultrasonic cavitation and ‘hot spot’ theory. High power ultrasonic wave was introduced to crystallize the PC prepolymers which is generally used for solid‐state polymerization (SSP) to obtain the ultra‐high molecular weight PCs. The structure and properties of PC treated with ultrasonic wave such as torque changes and crystallinities were studied. The experimental results showed that ultrasonic wave could improve the crystallinities of PCs and sonication time was proportional to their crystallinity. This is attributed to the decrease of the specific volume and the resulting shrinkage is compensated by a flux of a polymer melt toward the crystallization front. Torque data were collected directly from the Haake internal mixer and crystallinities were evaluated from differential scanning calorimeter (DSC). This process is an environmentally benign process so that no additional solvents or treatments are needed and will be very useful in the conventional solid‐state process which is used industrially. Copyright © 2007 John Wiley & Sons, Ltd.     

Towards high molecular weight poly(bisphenol a carbonate) with excellent thermal stability and mechanical properties by solid-state polymerization

Poly(bisphenol A carbonate) (BPA-PC) was post-polymerized by solid-state polymerization (SSP) after supercritical CO₂-induced crystallization in low molecular weight particles prepolymerized via melt transesterification reaction. The effects of the crystallization conditions on melting behavior and SSP of BPA-PC were investigated with differential scanning calorimetry (DSC), Ubbelohde viscosity method and gel permeation chromatography (GPC). The reaction kinetics of the SSP of crystallized prepolymers was studied as a function of reaction temperatures for various reaction periods. As a result, the viscosity average molecular weight of BPA-PC particles (2 mm) increased from 1.9 × 10⁴ g/mol to 2.8 × 10⁴ g/mol after SSP. More importantly, the significantly enhanced thermal stability and mechanical properties of solid-state polymerized BPA-PC, compared with those of melt transesterification polymerized BPA-PC with the same molecular weight, can be ascribed to the substantial avoidance of undergoing high temperature during polymerization. Our work provides a useful method to obtain practical product of BPA-PC with high quality and high molecular weight.     

Molecular structure regulation of functional polylactic acid based on chain expansion reaction and its improved hydrolysis resistance

In this work, the functional polylactic acid (PLA) was synthesized using epoxy chain extender (ADR) as a chain extender agent through melt blending method. The effects of ADR content on the molecular structure, thermal properties, and tensile properties of the functional PLA were investigated. Meanwhile, the hydrolytic behavior of the PLA/ADR materials at different hydrolysis temperatures was explored. It was found that ADR effectively regulated the molecular structure of PLA in the molten state and significantly increased the relative molecular weight, storage modulus, and complex viscosity of PLA. In addition, the Cole-Cole diagram results suggested the branched structure of PLA chain expansion systems. Based on mechanical property tests, it was noted that the addition of ADR made the molecular chain form a micro-crosslinked structure. Additionally, the mass loss rate of PLA/1.6ADR (the dosage of ADR was 1.6 wt%) was 14.75% after 14 weeks of hydrolysis under hydrolysis conditions at 58°C, while that of pure PLA was 25.89%. Moreover, the functional PLA/ADR materials exhibited significantly slower decrease rates in molecular weight, melting temperature, and tensile strength, and still maintained intact morphology after 14 weeks of hydrolysis compared to pure PLA. Therefore, the molecular structure of PLA is effectively regulated by ADR, which greatly enhances the hydrolysis resistance and further promotes the range of application of PLA.     

Stabilization of poly(lactic acid) by polycarbodiimide

Polycarbodiimide (CDI) was used to improve the thermal stability of poly(l-lactic acid) (PLA) during processing. The properties of PLA containing various amounts of CDI were characterized by GPC, DSC, rheology, and tensile tests. The results showed that an addition of CDI in an amount of 0.1-0.7 wt% with respect to PLA led to stabilization of PLA at even 210 °C for up to 30 min, as evidenced by much smaller changes in molecular weight, melt viscosity, and tensile strength and elongation compared to the blank PLA samples. In order to examine the possible stabilization mechanism, CDI was reacted with water, acetic acid, l-lactic acid, ethanol and low molecular weight PLA. The molecular structures of the reaction products were measured with FTIR. The results showed that CDI could react with the residual or newly formed moisture and lactic acid, or carboxyl and hydroxyl end groups in the PLA samples, and thus hamper the thermal degradation and hydrolysis of PLA.     

Study of the degradation of a new PLA braided biomaterial in buffer phosphate saline,basic and acid media,intended for the regeneration of tendons and ligaments

The purpose of this study was to evaluate the effects of hydrolytic degradation on the properties of a PLA hollow braid designed as a new concept of biodegradable prosthesis for the regeneration of tendons and ligaments. The main function of the braided material is to bear mechanical loads while it is being replaced by the newly-generated tissue. The kinetics of braided material degradation is thus an important factor in determining the success of the product. In order to study this mechanism, PLA braid was subjected to a 12-month degradation process at 37 °C in PBS at pH 7.4 (to simulate the human physiological medium) and to accelerated degradation for one month in pH 12 and pH 3 solutions. Degradation of the braid subjected to hydrolysis was evaluated by weight loss, molecular weight distribution, mechanical properties, and calorimetric and morphologic analyses. The weight loss in a basic medium reached 21%, versus no significant change in the other media. Average molecular weight was reduced by approximately 50% in the three media, with loss of mechanical properties in all cases. The morphological changes were more evident in the PLA degraded in the basic medium. The crystallinity of the material increased at the first stages of degradation, regardless of the medium used.     

Acetylene-terminated resins: Mechanism of thermal polymerization and properties of cured polymers

The polymerization kinetics and mechanisms of model compounds (mono- and difunctional) characteristic of prepolymers of ATR (acetylene-terminated resins) have been studied by HPLC, FTIR, UV, NMR (liquid and solid) and HPLC in the temperature range of 150–220°C. Using monofunctional compounds, we were able to show that the thermal polymerization of acetylene functions is not a simple reaction. Initially, the majority of compounds formed have a low polymerization degree, followed by the formation of species with higher and progressive polymerization degrees. Spectroscopic techniques such as NMR and FTIR lead to the unambiguous determination of reaction conversion up to 95% in the case of bifunctional prepolymers. The understanding of network structures, on the other hand, is more delicate in polyaromatic systems, since the chains formed are very similar to the basic skeleton of the prepolymer. The kinetic curves obtained isothermally between 150–220°C have shown that while kinetic monitoring of the disappearance of the first 90% of ethynyl functions poses no particular problems, there is a considerable uncertainty for the last 10%, regardless of the technique chosen. We have demonstrated that me thermal properties are dependent on the molecular weight and the structure of the polymer.     

开环聚合-固相缩聚法制备立体嵌段聚乳酸

首先,采用乳酸为引发剂,辛酸亚锡为催化剂,引发丙交酯开环聚合制得具有缩聚活性的L-聚乳酸和D-聚乳酸;然后,将两者熔融共混后进行固相缩聚,合成了一系列立体嵌段聚乳酸。采用核磁共振(NMR)、凝胶渗透色谱(GPC)及差示扫描量热仪(DSC)分析了产物的链结构、重均分子量、热性能,并探讨了均相晶体和立体复合晶体共存情况下的固相缩聚机理。结果表明,固相缩聚产物分子量增长的适宜反应条件为:反应时间30h,较低的催化剂含量,L-聚乳酸质量分数为80%。L-聚乳酸和D-聚乳酸共混物较低的初始立体复合晶体结晶度有利于后续固相缩聚过程中产物分子量的增长;固相缩聚不仅发生在异链之间,而且也发生在同链之间。     

Synthesis and hydrolysis behaviour of poly(ester anhydrides) from polylactone precursors containing alkenyl moieties

Hydroxyl-group functional polylactones were prepared and converted to acid- terminated polyesters in a reaction with a series of alkenylsuccinic anhydrides containing 8, 12, or 18 carbons in their alkenyl chains. These polyester precursors were then linked into higher molecular weight poly(ester anhydrides) containing alkenyl moieties in their polyester blocks. The hydrolysis behaviour of the poly(ester anhydrides) was found to depend on the thermal properties of the polyester precursors. For poly(ester anhydrides) prepared from low molecular weight prepolymers with thermal transitions below 37 degrees C, the presence of hydrophobic alkenyl chains in the polyester precursors slowed the rate of weight loss. Poly(ester anhydrides) prepared from higher molecular weight prepolymers showed the opposite weight-loss behaviour; i.e., the crystallinity and thermal transitions of the alkenyl chain-containing poly(ester anhydrides) were low, and the weight loss was faster than for poly(ester anhydrides) without the alkenyl chains. The differences in length of the alkenyl chain, as such, had little effect on the hydrolysis behaviour and thermal properties of the poly(ester anhydrides).     

稀土催化体系催化PET固相缩聚的研究

研究了稀土催化体系对聚对苯二甲酸乙二酯固相缩聚反应的催化效果及对所得高分子量聚酯切片性能的影响,发现稀土催化体系可明显提高聚酯固相缩聚的反应速率,稀土催化体系对聚酯固相缩聚反应的催化活性明显高于传统催化体系,其中单一稀土催化体系与混合稀土催化体系在较低温度下具有相近的催化活性,而在较高温度下单一稀土催化体系的催化活性较高;加入稳定剂,不影响稀土催化的固相缩聚反应速率,稀土催化固相缩聚得到的PET样品具有较高的结晶度和较大的晶粒尺寸,其中单一稀土催化所得样品的晶粒尺寸最大,相应地,单一稀土催化的固相缩聚反应活化能也最大;稀土催化体系催化聚酯固相缩聚反应时添加适当稳定剂,可获得与采用传统催化体系得到的PET切片相近的热稳定性。     

固相聚合合成聚噻吩衍生物及烷基链对固相聚合的影响

New poly(bis-3, 4-ethylenedioxythiophene methine)s derivatives with typical electro-optical moieties of thiophene, carbazole and fluorene as the side chains are obtained by facile solid state polymerization (SSP) or melt state polymerization (MSP). Detail characterizations of these polymers are carried out and some key monomers' crystals are obtained for structures analysis. It is found that existence of alkyl chains decrease monomers onset temperatures for SSP (T_onset) due to the weakening of the intermolecular interaction in crystals.     

Synthesis of poly(l-lactic acid) with improved thermal stability by sulfonic acid-catalyzed melt/solid polycondensation

Melt/solid polycondensation (MP/SSP) is deemed as an alternative synthetic route besides ring-opening polymerization (ROP) in synthesizing poly(l-lactic acid) (PLLA). However, it is found that PLLA synthesized by MP/SSP has much poorer thermal stability than that by ROP due to more residual Sn(II) metallic catalyst in the former, but sulfonic acids does not show any detrimental effect on the thermal stability of PLLA. To synthesizing PLLA with good thermal stability by MP/SSP, a variety of commercially available sulfonic acids were screened as catalysts in MP/SSP of PLLA. Among these nonmetallic catalysts, it was found that 1,3-propanedisulfonic acid (PSA) and 1,5-naphthalene disulfonic acid (NSA) exhibited satisfactory catalytic reactivity and PLLAs with excellent thermal stability, high molecular weight, little coloration and good optical purity were successfully synthesized by MP/SSP. The decomposition temperature was increased by 80–100 °C in comparison to SnCl₂-catalyzed PLLA, and the thermal stability is comparable to commercial PLLA produced by ROP.     

A new approach to prepare high molecular weight poly(p-dioxanone) by chain-extending from dihydroxyl terminated propolymers

As poly(p-dioxanone) (PPDO) with a high molecular weight (viscosity-average molecular weight (M_ν) > 100,000 g/mol) is not easy to be obtained in a short time, a new approach has been developed to produce high molecular weight poly(p-dioxanone) (HPPDO-T) by chain-extending reaction of hydroxyl-terminated PPDO (HPPDO) prepolymers using toluene-2,4-diisocyanate (TDI) as chain extender. Here HPPDO prepolymers were synthesized via ring-opening polymerization of p-dioxanone (PDO) monomer initiated by 1,4-butanediol (BD) with Stannous octoate (SnOct₂) as catalyst. The resulting polymers, having a highest M_ν of 250,000 g/mol, were characterized by ¹H NMR, TG, DSC and WXRD. HPPDO prepolymers can react with TDI more effectively than the PPDO prepolymers initiated by mono-functional initiators, and the molecular weights of resulting chain-extended products increase several decade times in an hour comparing to the prepolymers. The chain extended products HPPDO-T have better thermal stability, and higher glass transition temperatures and lower crystallization rates than PPDO homopolymer.     

The use of melt rheology and solution viscometry for degradation study of post-consumer poly(ethylene terephthalate): The effects of the contaminants,reprocessing and solid state polymerization

Rheological measurements and intrinsic viscosity were performed to determine how the presence of contaminants, reprocessing and solid state polymerization (SSP) affects the degradation of post-consumer poly(ethylene terephthalate) (PET). First, post-industrial PET resin was contaminated with a series of surrogates according to a US-FDA protocol to simulate the worst-case scenario of misuse of PET packaging. The samples were submitted to recycling and SSP process in the presence of surrogates. The rheological data demonstrated that contaminated samples present degradation, even without any additional process. However, when the contaminated samples are submitted to melt extrusion the level of degradation increases. For the SSP process it was found that the surrogates do not interfere in the degradation process. In addition, an empirical analysis was derived based on the existing relationship. This analysis allowed the use of complex viscosity in higher frequencies, that is, out of the Newtonian plateau, and it shows to be as efficient as the zero-shear rate viscosity, allowing to associate the molar mass index of different samples. The data were corroborated from those obtained by the viscometric molar mass index, highlighting the importance of this new method to quantify the degradation in the polymer system.     

Copolymerization of poly(vinyl alcohol)‐graft‐poly(1,4‐dioxan‐2‐one) with designed molecular structure by a solid‐state polymerization method

Poly(vinyl alcohol)‐graft‐poly(1,4‐dioxan‐2‐one) (PVA‐g‐PPDO) with designed molecular structure was synthesized by a solid‐state polymerization. The solid‐state copolymerization was preceded by a graft copolymerization of PDO initiated with PVA as a multifunctional initiator, and Sn (Oct)₂ as a coininitiator/catalyst in a homogeneous molten state. The polymerization temperature was then decreased and the copolymerization was carried out in a solid state. The products prepared by solid‐state polymerization were characterized by ¹H NMR and DSC, and were compared with those synthesized in the homogeneous molten state. The degree of polymerization (D_p), degree of substitution (D_s), yield and the average molecular weight of the graft copolymer with different molecular structure were calculated from the ¹H NMR spectra. The results show that the crystallization process during the solid‐state polymerization may suppress the undesirable inter‐ or intramolecular side reactions, then resulting in a controlled molecular structure of PVA‐g‐PPDO. The results of DSC measurement show that the molecular structures determine the thermal behavior of the PVA‐g‐PPDO. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3083–3091, 2006     

Effect of activated carbon black nanoparticles on solid state polymerization of poly(ethylene terephthalate)

Solid state polycondensation (SSP) is a conventional method used to increase the molecular weight of poly(ethylene terephthalate) (PET) in order to become more suitable for applications as carbonated soft drink bottles, etc. In the present study, the effect of activated carbon black (ACB) nanoparticles, on the SSP kinetics is examined. TEM micrographs revealed that ACB was finely dispersed into PET matrix as individual nanoparticles without creating agglomerates. Intrinsic viscosity (IV) measurements revealed that at temperatures 210 and 220 °C the activated carbon black does not influence the IV increase. However, at 230 and 240 °C an accelerating effect was found and higher intrinsic viscosity values were measured, compared to neat PET. Furthermore, a simple kinetic model was employed to predict the time evolution of IV, as well as the carboxyl and hydroxyl content during SSP. The kinetic parameters of the transesterification and esterification reactions were estimated at different temperatures with or without the addition of ACB. From the experimental measurements and the theoretical simulation results it was proved that ACB enhances the esterification reaction at all studied temperatures acting as a co-catalyst. However, the transesterification reaction remains unaffected by the presence of ACB at elevated temperatures (230 or 240 °C), while it is reduced at lower values (210 and 220 °C). Finally, the activation energies of both transesterification and esterification were determined together with the concentration of inactive end-groups.     

Challenges in the experimental investigation of the caloric and thermomechanical behaviour of semi-crystalline polymers: A study on the example of polyethylene terephthalate (PET)

Investigations on industrial produced polyethylene terephthalate (PET) were carried out in the temperature range from the glassy to the liquid state. In differential scanning calorimetry (DSC) experiments, the sample passed through this temperature range several times at different speeds, interrupted by isothermal segments. Thereby the caloric behaviour observed in earlier publications could be confirmed. A closer look reveals variations in the behaviour, depending on the initial state of the sample. The thermal and mechanical boundary conditions seem to have a long-term influence on the semi-crystalline state. Independent of the initial state, a fundamental decrease in the crystallization tendency could be observed after each temperature loop. The most likely explanation for that is an increase in molecular weight in the higher temperature ranges. This leads to an increase in viscosity, as it occurs in the solid poly-condensation (SSP) process. Mechanical experiments were also carried out in the temperature range investigated, but only at different isothermal levels due to experimental limits. For these experiments, theoretical considerations were made on the basis of the viscoelastic generalization of Hooke’s law. These show the influence of the significant decrease of the ratio between shear- and bulk stiffness in the glass-transition range. While the uniaxial tensile mode fail, the uniaxial compression mode with suppressed transversal expansion needs the fluid like behaviour to determine the bulk modulus instead of the longitudinal modulus. The experimental investigations confirm these theoretical results. Concerning the actual purpose of the mechanical investigation, Struik’s protocol is used at higher isothermal levels. As a result, crystallization-related changes in the mechanical behaviour could be observed.     

固相缩聚法制备高粘度尼龙1111

采用固相缩聚工艺提高尼龙1111的相对粘度,是制备高粘度尼龙1111的有效方法之一。固相后缩聚法制备相对粘度高于2.5的高粘度尼龙1111,宜选择初始相对粘度为2.0的尼龙1111,反应时间12h,反应温度175℃。增粘后的尼龙1111具有更为优良的物理机械性能。     

Synthesis,characterization, and thermal stability of poly (lactic acid)/zinc oxide pillared organic saponite nanocomposites via ring‐opening polymerization of d,l‐lactide

Poly (lactic acid) (PLA) was synthesized using d , l ‐lactide monomer and zinc oxide (ZnO) pillared organic saponite as the green catalyst, through ring‐opening polymerization. The effects of stoichiometry of catalyst and polymerization conditions on molecular weight of PLA were evaluated by orthogonal experiment. The optimum polymerization parameters were: 0.5 wt% ZnO pillared organic saponite and reaction conditions of 170°C for 20 hr. Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance spectroscopy confirmed the PLA structure. Gel permeation chromatography showed that the average molecular weight of PLA was 48,442 g/mol, and its polydispersity index was 1.875. Differential scanning calorimetry, X‐ray diffraction, and polarized optical microscopy showed that ZnO pillared organic saponite improved the crystallinity of PLA. Thermal gravimetric analysis showed improved thermal stability of PLA because of ZnO pillared organic saponite. Thermal decomposition kinetics of PLA/ZnO pillared organic saponite nanocomposites was also studied. The activation energies (E_a) for thermal degradation of PLA and PLA/ZnO pillared organic saponite nanocomposites were evaluated by the Kissinger and Ozawa methods, which demonstrated that ZnO pillared organic saponite enhanced E_a of thermal degradation of PLA and significantly improved its thermal stability. Copyright © 2015 John Wiley & Sons, Ltd.