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1.
The presence of low molecular weight lactic acid derivatives in films enhanced the degradability of polylactide in a biotic medium. Two different biotic and abiotic series were investigated. The films used for the first abiotic and biotic series (a‐1 and b‐1 films) initially contained some lactic acid and lactoyl lactic acid, while the films used for the second abiotic and biotic series (a‐2 and b‐2 films) did not originally contain them. The b‐1 films decreased in molecular weight during 3 weeks in the biotic medium, while no molecular weight decrease was seen in the a‐1 films aged in a corresponding abiotic mineral medium. The molecular weight for the a‐2 and b‐2 films without lactic and lactoyl lactic acid remained almost constant. Scanning electron microscopy micrographs showed a larger amount of bacteria and fungi growing on the surface of b‐1 films compared to b‐2 films; thus, the presence of easily assimilated lactic acid and lactoyl lactic acid in the films improved the initial growth of microorganisms on the film surfaces. Gas chromatography and mass spectrometry analysis showed that lactic acid and lactoyl lactic acid were rapidly assimilated from the films aged in a biotic medium. New degradation products (e.g., ethyl ester of lactoyl lactic acid, acetic acid, and propanoic acid) were formed during aging in a biotic medium. Acetic acid and propanoic acid were formed as intermediate degradation products during the initial stages, but they were no longer detected after prolonged aging. The concentration of the ethyl ester of lactoyl lactic acid increased with aging time. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 228–239, 2000 相似文献
2.
Recycling is a thermal process in which polymers are melted to produce new products. It is possible that these thermal processes could modify their mechanical and thermal properties. Polymer degradation can be characterized with thermogravimetric analysis and differential scanning calorimetry. Recycled materials tested with these methods have shown variations in some thermal properties, such as the glass‐transition temperature and thermal degradation onset, but the sensitivity of these methods is not sufficient to investigate the changes in the characteristics of polymers when materials are exposed to moderate temperature conditions or several thermal cycles. To study these structural changes, a much more sensitive technique, such as pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS), is needed. Small variations in the structure can be determined by Py–GC/MS. Each pyrolysis product can be identified by its retention time and mass spectrum with the use of reference literature. In this work, we have studied structural changes in high‐impact polystyrene as a function of the injection‐molding temperature and pyrolysis cycles. The results do not show significant changes in samples processed at different temperatures with Py–GC/MS, but the values of the pyrolysis products differ as a function of the pyrolysis cycles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 相似文献
3.
Poly(D ,L ‐lactide) (PDLLA) was synthesized by microwave‐irradiated ring‐opening polymerization catalyzed by stannous octoate (Sn(Oct)2) under atmosphere. The effects of heating medium, monomer purity, catalyst concentration, microwave irradiation time, and vacuum level were discussed. Under the appropriate conditions such as carborundum (SiC) as heating‐medium, 0.15% catalyst, lactide with purity above 99.9%, 450 W microwave power, 30 min irradiation time, and atmosphere, PDLLA with a viscosity–average molecular weight (Mη) over 2.0 × 105 and a yield over 85% was obtained. The dismission of vacuum to ring‐opening polymerization of D ,L ‐lactide (DLLA) under microwave irradiation simplified the process greatly. The temperature under microwave irradiation and conventional heating was compared. The largely enhanced ring‐opening polymerization rate of DLLA under microwave irradiation was the coeffect of thermal effects and microwave effects. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2244–2247, 2006 相似文献
4.
Takayuki Honda Rong Lu Nobuhiko Kitano Yoshimi Kamiya Tetsuo Miyakoshi 《应用聚合物科学杂志》2010,118(2):897-901
Three lacquer samples taken from a “four‐eared” pottery container, which was designated an important National Cultural Property of Japan excavated in 16–17th century ruins of Kyoto City, were analyzed by pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS) and infrared (IR) spectroscopy to determine the source of the lacquer. It is an unexpected result that the lacquer in this pottery container is actually used by Melanorrhoea usitata. Alkylbenzene and alkenylbenzene as cleavage pieces of undecylbenzene (MW = 232 g/mol) and undecenylbenzene (MW = 230 g/mol), which are products of the pyrolysis of thitsiol, were detected in all three samples. Moreover, ω‐phenylalkylcatechols and ω‐phenylalkylphenols, which are the specific components of M. usitata, were also detected by Py‐GC/MS, suggesting that lacquer sap of M. usitata was used by the Japanese people in the 16–17th centuries. In addition, Japanese lacquer culture and the advantages of the Py‐GC/MS method for lacquer analysis are discussed in detail. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
5.
A series of triblock co‐polymers, consisting of a poly(ethylene glycol) (PEG) central block joined to two blocks of random p‐dioxanone‐co‐L ‐lactide copolymers were synthesized by ring‐opening polymerization of p‐dioxanone (PDO) and L ‐lactide (LLA) initiated by PEG in the presence of stannous 2‐ethylhexanoate catalyst. The resulting copolymers were characterized by various techniques including 1H and 13C NMR and FTIR spectroscopies, gel permeation chromatography, inherent viscosity, wide‐angle X‐ray diffractometry (WAXD) and differential scanning calorimetry (DSC). The conversion of PDO and L ‐lactide into the polymer was studied various mole ratios and at different polymerization temperature from 1H NMR spectra. Results of WAXD and DSC showed that the crystallinity of PEG macroinitiator was greatly influenced by the composition of PDO and L ‐lactide in the copolymer. The triblock copolymers with low molecular weight were soluble in water at below room temperature. © 2003 Society of Chemical Industry 相似文献
6.
This study reports a novel one‐step method to synthesize a new spherical support for Ziegler‐Natta catalyst under moderate condition. The support is obtained from a dispersion system where the particle stabilizer polyvinylpyrrolidone plays a main role to stabilize the spherical particles. The new chemical of the support is CH3CH2OMgOCH(CH2Cl)2, which is first reported here, has been approved by newly filed patents and also confirmed by solution NMR, solid state NMR, pyrolysis‐gas chromatography‐mass spectrometry (Py‐GC‐MS), and ICP‐MS. The support and catalyst particles have uniform distributions. The catalyst prepared from this support has been evaluated with high activity. The polypropylene obtained has high isotacticity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41014. 相似文献
7.
Hideto Tsuji Tamami Yamada Masakazu Suzuki Shinichi Itsuno 《Polymer International》2003,52(2):269-275
Blended films of poly(L ‐lactide) [ie poly(L ‐lactic acid)] (PLLA) and poly(?‐caprolactone) (PCL) without or mixed with 10 wt% poly(L ‐lactide‐co‐?‐caprolactone) (PLLA‐CL) were prepared by solution‐casting. The effects of PLLA‐CL on the morphology, phase structure, crystallization, and mechanical properties of films have been investigated using polarization optical microscopy, scanning electron microscopy, differential scanning calorimetry and tensile testing. Addition of PLLA‐CL decreased number densities of spherulites in PLLA and PCL films, and improved the observability of spherulites and the smoothness of cross‐section of the PLLA/PCL blend film. The melting temperatures (Tm) of PLLA and PCL in the films remained unchanged upon addition of PLLA‐CL, while the crystallinities of PLLA and PCL increased at PLLA contents [XPLLA = weight of PLLA/(weight of PLLA and PCL)] of 0.4–0.7 and at most of the XPLLA values, respectively. The addition of PLLA‐CL improved the tensile strength and the Young modulus of the films at XPLLA of 0.5–0.8 and of 0–0.1 and 0.5–0.8, respectively, and the elongation at break of the films at all the XPLLA values. These findings strongly suggest that PLLA‐CL was miscible with PLLA and PCL, and that the dissolved PLLA‐CL in PLLA‐rich and PCL‐rich phases increased the compatibility between these two phases. © 2003 Society of Chemical Industry 相似文献
8.
Anbanandam Parthiban Asawin Likhitsup Han Yu Christina LL Chai 《Polymer International》2010,59(2):145-154
Polystyrene terminated with benzyl alcohol units was employed as a macroinitiator for ring‐opening polymerization of ε‐caprolactone and L ‐lactide to yield AB‐ and ABC‐type block copolymers. Even though there are many reports on the diblock copolymers of poly(styrene‐block‐lactide) and poly(styrene‐block‐lactone), this is the first report on the poly(styrene‐block‐lactone‐block‐lactide) triblock copolymer consisting of two semicrystalline and degradable segments. The triblock copolymers exhibited twin melting behavior in differential scanning calorimetry (DSC) analysis with thermal transitions corresponding to each of the lactone and lactide blocks. The block derived from ε‐caprolactone also showed crystallization transitions upon cooling from the melt. In the DSC analysis, one of the triblock copolymers showed an exothermic transition well above the melting temperature upon cooling. Thermogravimetric analysis of these block copolymers showed a two‐step degradation curve for the diblock copolymer and a three‐step degradation for the triblock copolymer with each of the degradation steps associated with each segment of the block copolymers. The present study shows that it is possible to make pure triblock copolymers with two semicrystalline segments which also consist of degradable blocks. Copyright © 2009 Society of Chemical Industry 相似文献
9.
Copolymerization of mixtures of L ‐lactide and ε‐caprolactone has been initiated by diphenylzinc. The reaction conditions were investigated, to discover the effects on yield, molecular weight and microstructure of copolymers obtained. The temperature used varied between 50 and 120 °C, the molar ratio of monomer to initiator ranged between 90 and 1440 mol/mol, and the molar ratio of ε‐caprolactone to L ‐lactide employed was between 100/0 and 0/100 mol/mol. Copolymers were characterized by 1H‐NMR, 13C‐NMR, DSC and gel permeation chromatography. The results indicate that incorporation of L ‐lactide to the growing chain is preferred and ε‐caprolactone is copolymerized after most of the L ‐lactide has been depleted. The microstructure of obtained copolyesters was affected considerably by transesterification reactions. It was observed that increasing reaction temperature, reaction time and concentration initiator was advantageous to the transesterification. The crystallinity of copolyester obtained was determined by differential scanning calorimetry. The results are in good agreement with both molar composition and sequence distribution of copolyesters. Copyright © 2006 Society of Chemical Industry 相似文献
10.
α,ω‐Dihydoxy‐terminated poly(L ‐lactide)s (PLLA diols) with various molecular weights (1000, 2000 and 3000 g mol?1) were prepared by the ring‐opening polymerization of L ‐lactide using 1,6‐hexanediol as an initiator. These were subsequently chain‐extended with the diacyl chloride of 4,4′‐(adipoyldioxy)dicinnamic acid (CAC) to obtain high‐molecular‐weight photocurable polyesters (CAC/PLLAs). The resulting polyesters were characterized by gel permeation chromatography, Fourier‐transform infrared, ultraviolet–visible and proton nuclear magnetic resonance spectroscopies, differential scanning calorimetry and thermogravimetry. These photoreactive polyesters were irradiated with a high‐pressure mercury lamp (λ > 280 nm) for 30–180 min to produce the crosslinked polyesters. The gel fraction yield increased with photocuring time, and exceeded 80 % after 180 min. The photocuring process disturbed the crystallization of the CAC/PLLA films, while it enhanced their thermal stabilities. With increasing photocuring time, both the tensile strength and modulus increased markedly. The best mechanical properties (tensile strength = 41 MPa; tensile modulus = 1550 MPa) were obtained for a CAC/PLLA‐3000 film photocured for 180 min. The tensile modulus of this photocured film was larger than that of pure PLLA. The hydrolytic degradation rates of the CAC/PLLA films in a phosphate buffer solution (pH, 7.2) of proteinaze‐k at 37 °C were much slower than those of pure PLLA films. Copyright © 2004 Society of Chemical Industry 相似文献
11.
The thermal degradation and flame retardancy of poly(butylene terephthalate) (PBT) were studied with a focus on the effect of phosphorous compounds. Thermogravimetric analysis, pyrolysis/gas chromatography/mass spectrometry (Py/GC/MS), and elemental analysis were used to analyze the flame retardancy, which were observed by an Underwriters Laboratory UL‐94 test and a cone calorimeter. The 50% degradation temperatures of PBT blends with phosphorous compounds were the same as that of neat PBT. Six scission products were assigned by Py/GC/MS. The burning times of the UL test of several PBT blends were much shorter than that of neat PBT. The relation between flame retardancy and thermal degradation was analyzed with respect to the results of the scission products and the char in burned polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2326–2333, 2004 相似文献
12.
Aula Alwattar Athir Haddad Quan Zhou Tatiana Nascimento Ryan Greenhalgh Eliton Medeiros Jonny Blaker Adam Parry Peter Quayle Stephen Yeates 《Polymer International》2019,68(3):360-368
Fluorescent markers are critical for tracking the position and movement of molecules both in vivo and in vitro. Conventionally, synthetic dyes are non‐covalently added to polymers for fluorescent tracking, but often diffuse away. Here we demonstrate, for the first time, a facile method for the synthesis of fluorescent poly(lactic acid) nano‐/microfibres for biomedical applications using solution spin blowing. Pyrene‐end‐capped poly(l ‐lactide) (PLLA) derivatives were synthesised using the ring‐opening polymerisation of l ‐lactide and they were characterised using spectroscopic and thermal analyses. Submicrometre‐sized fluorescent fibres were produced from these PLLA derivatives using solution blow spinning techniques generating polymer blends and core–shell fibres. Such system could be further exploited to incorporate electrically conductive carbon allotropes via the pyrene aromaticity, producing fluorescent and electrically active fibres for in vitro monitoring and electrical stimulation. © 2018 Society of Chemical Industry 相似文献
13.
Xiaohong Li Xianmo Deng Minglong Yuan Chengdong Xiong Zhitang Huang Yanhua Zhang Wenxiang Jia 《应用聚合物科学杂志》2000,78(1):140-148
Poly‐DL ‐lactide (PLA) and poly‐DL ‐lactide‐poly(ethylene glycol) (PELA) were produced by bulk ring‐opening polymerization using stannous chloride as initiator. PLA, PELA microspheres, and PELA microspheres containing the outer membrane protein (OMP) of Leptospira interrogans with the size of 1.5–2 μm were prepared by a solvent evaporation process. In vitro degradation and release tests of PLA, PELA, and OMP‐loaded PELA microspheres were performed in pH 7.4 buffer solution at 37°C. Quantitatively, the degree of degradation was monitored by detecting the molecular weight reduction, by evaluating the mass loss and the apparent degradation rate constant, and by determining the intrinsic viscosity and poly(ethylene glycol) content of retrieved polymer, while the release profile was assessed by measuring the amount of protein presented in the release medium at various intervals. Qualitatively, the morphological changes of microspheres were observed with scanning electron micrography. The observed relative rates of mass loss versus molecular weight reduction are consistent with a bulk erosion process rather than surface erosion for PELA microspheres. The introduction of hydrophilic poly(ethylene glycol) domains in copolymer PELA and the presence of OMP within microspheres show critical influences on the degradation profile. The OMP‐loaded PELA microspheres present triphasic release profile and a close correlation is observed between the polymer degradation and the OMP release profiles. It is suggested that the polymer degradation rate, protein diffusion coefficient, and the water‐swollen structure of microspheres matrix commonly contribute to the OMP release from PELA microspheres. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 140–148, 2000 相似文献
14.
Compared with linear diblock or triblock poly(ethylene glycol)‐block‐poly(L ‐lactic acid) copolymer (PEG‐b‐PLLA), star‐shaped PEG‐b‐PLLA (sPEG‐b‐PLLA) copolymers exhibit smaller hydrodynamic radius and lower viscosity and are expected to display peculiar morphologies, thermal properties, and degradation profiles. Compared with the synthesis routine of PEG‐b‐PLLA form lactide and PEG, the traditional synthesis routine from LA and PEG were suffered by the low reaction efficiency, low purity, lower molecular weight, and wide molecular weight distribution. In this article, multiarm sPEG‐b‐PLLA copolymer was prepared from multiarm sPEG and L ‐lactic acid (LLA using an improved method of melt polycondensation, in which two types of sPEG, that is, sPEG1 (four arm, Mn = 4300) and sPEG2 (three arm, Mn = 3200) were chosen as the core. It was found the molecular weight of sPEG‐b‐PLLA could be strongly affected by the purity of LLA and sPEGs, and the purification technology of vacuum dewater and vacuum distillation could help to remove most of the impurities in commercial available LLA. The polymers, including sPEG and sPEG‐b‐PLLA with varied core (sPEG1 and sPEG2) and LLA/sPEG feeding ratios, were characterized and confirmed by 1H‐NMR and 13C‐NMR spectroscopy, Fourier transform infrared spectroscopy (FT‐IR) and gel permeation chromatography, which showed that the terminal hydroxyl group in each arm of sPEGs had reacted with LLA to form sPEG‐b‐PLLA copolymers with fairly narrow molecular weight distribution. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
15.
The production of smoke, carbon monoxide (CO), and carbon dioxide (CO2) were investigated with cone calorimetry testing when low‐density polyethylene (LDPE), LDPE treated with an intumescent flame retardant (IFR), and LDPE treated with an IFR and ultrafine zinc borate (UZB) combusted under irradiation. The results of the testing showed that UZB could depress smoke production and reduce the amount of CO and CO2. The components of the pyrolytic gas and its contents were identified and measured with pyrolysis–gas chromatography/mass spectrometry (Py–GC–MS) when LDPE, LDPE/IFR, and LDPE/IFR/UZB were pyrolyzed at 400°C for 20 s. The Py–GC–MS results implied that UZB had an important influence on the components and contents of the pyrolytic gas of LDPE/IFR. UZB mechanisms of smoke suppression and toxicity reduction with respect to LDPE/IFR are proposed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
16.
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 (Mw ∼ 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 Mw ∼ 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 相似文献
17.
An effective flame retardant for poly(ethylene terephthalate) synthesized by phosphaphenanthrene and cyclotriphosphazene
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A novel flame retardant [9,10‐Dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxideÔtriphosphazene (DOPO–TPN)] based on phosphaphenanthrene and cyclotriphosphazene was synthesized and used to improve the flame retardancy of poly(ethylene terephthalate) (PET). The structure of DOPO–TPN was characterized by nuclear magnetic resonance, Fourier transform infrared spectroscope (FTIR), and elemental analysis. PET/DOPO–TPN composites with different amount of DOPO–TPN were prepared and the flame retardancy was determined by limiting oxygen index (LOI) and vertical burning test (UL‐94). With the incorporation of 5 wt % DOPO–TPN, the composite achieved a LOI value of 34% and UL‐94 V‐0 rating. The thermal properties of the PET/DOPO–TPN composites were investigated by thermogravimetric analysis. The flame retardant mechanism was investigated by pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), FTIR, and scanning electron microscopy (SEM). The Py‐GC/MS results showed that DOPO based fragments would exist in the gas phase during the pyrolysis of PET/DOPO–TPN composites which demonstrated that DOPO–TPN could act through gas‐phase action to exert flame retardant effect. The results of FTIR and SEM demonstrated that DOPO–TPN could promote the formation of compact and intact char residues to inhibit the heat and combustible gas transmission in condensed phase. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45246. 相似文献
18.
BACKGROUND: Polymer/multi‐walled carbon nanotube (MWCNT) composites are one of the most promising alternatives to conventional polymer composites filled with micrometre‐sized fillers. This approach can also be applied for the improvement of mechanical properties and thermal stability of biodegradable aliphatic polyesters, such as poly(L ‐lactide) (PLLA), which have been receiving increasing attention due to environmental concerns. Thermal degradation behaviour provides useful information for the determination of the optimum processing conditions and for identification of potential applications of final products. RESULTS: The PLLA/MWCNT composites investigated showed a higher thermal degradation peak temperature and onset temperature of degradation along with a higher amount of residue at the completion of degradation than neat PLLA. Moreover, PLLA/MWCNT composites with a greater MWCNT content showed higher activation energy of thermal degradation than those with a lower MWCNT loading, which confirmed the positive effect of MWCNT incorporation on the enhancement of PLLA thermal stability. CONCLUSION: This study explored the thermal degradation behaviour of PLLA/MWCNT composites by observing the weight loss, molecular weight and mechanical properties during non‐isothermal and isothermal degradation. The incorporation of MWCNTs into the PLLA matrix enhanced considerably the mechanical properties and thermal stability. Copyright © 2009 Society of Chemical Industry 相似文献
19.
In this research, poly(L ‐lactide‐co‐ε‐caprolactone) (PLACL) reinforced with well‐dispersed multiwalled carbon nanotubes (MWCNTs) nanocomposites were prepared by oxidization and functionalization of the MWCNT surfaces using oligomeric L ‐lactide (LA) and ε‐caprolactone (CL). It is found that the surface functionalization can effectively improve the dispersion and adhesion of MWCNTs in PLACL. The surface functionalization will have a significant effect on the physical, thermomechanical, and degradation properties of MWCNT/PLACL composites. The tensile modulus, yield stress, tensile strength, and elongation at break of composite increased 49%, 60%, 70%, and 94%, respectively, when the concentration of functionalized MWCNTs in composite is 2 wt %. The in vitro degradation rate of nanocomposites in phosphate buffer solution increased about 100%. The glass transition temperature (Tg) of composites was decreased when the concentration of functionalized MWCNTs is 0.5 wt %. With further increasing the concentration of functionalized MWCNTs, the Tg was increased. The degradation kinetics of nanocomposites can be engineered and functionalized by varying the contents of pristine or functionalized MWCNTs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献