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1.
Wheat gluten (10 g) was crosslinked (XL) using 10 units of transglutaminase. Different blends of XL gluten and poly(lactic acid) (PLA) were mixed in a Brabender mixer at 180°C for 10 min. Neat PLA and blends were analyzed using modulated DSC (MDSC). Neat PLA displayed a glass transition (Tg) and exothermic (Cry) followed by endothermic (Mel) transitions. The profile showed a Tg of 0.46 J/g/°C, Cry with 29.9 J/g, whereas Mel exhibited 28.7 J/g. XL wheat gluten displayed one Tg with 0.45 J/g/°C. Samples were subjected to repeated heating and cooling cycles to show the level of compatibility between the two polymers. The activation energy (Ea) and pre‐exponential factor (Z) were determined according to Borchardt and Daniels (B/D) kinetics approach. The blends showed increased Ea values with an increase in the amount of XL gluten. In the presence of 5 and 20% XL gluten, the Ea of PLA increased from 150 to 200 kJ/mol, respectively. A higher number of cycles caused an increase in Ea. The Tg temperature of different PLA/XL gluten blends can be predicted by Gordon–Taylor equation and its modified forms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

2.
The optimal synthetic conditions of poly(lactic acid‐co‐glycolic acid) (PLGA) via melt copolycondensation directly from L ‐lactic acid (L ‐LA) and glycolic acid (GA) with a feed molar ratio of 50/50 are discussed; the important drug‐delivery carrier PLGA50/50 is used as a special example. With reaction conditions of 165°C and 70 Pa and with 0.5 wt % SnCl2 as the catalyst, 10 h of polymerization gave the L ‐PLGA50/50 with the biggest intrinsic viscosity ([η]), 0.1993 dL/g. The optimal synthetic conditions were verified by the synthesis of D,L ‐PLGA50/50 with D,L ‐lactic acid (D,L ‐LA) instead of L ‐LA, but the biggest [η] was 0.2382 dL/g. Under the same synthetic conditions with L ‐LA and D,L ‐LA as starting materials, serial PLGA with different molar feed ratios, including 100/0, 90/10, 70/30, 50/50, 30/70, 10/90, and 0/100, were synthesized via simple and practical direct melt copolycondensation, and their solubilities were investigated. When the glycolic acid feed molar percentage was equal to or more than 70%, solubilities in tetrahydrofuran and CHCl3 became worse, and some samples were even wholly insoluble. These biodegradable polymers were also systematically characterized with gel permeation chromatography, Fourier transform infrared spectroscopy, 1H‐NMR spectroscopy, differential scanning calorimetry, and X‐ray diffraction. PLGA synthesized from L ‐LA and D,L ‐LA had many differences in weight‐average molecular weight (Mw), glass‐transition temperature, crystallinity, and composition. When the molar feed ratio of LA to GA was 50/50, both the [η] and Mw values of D,L ‐PLGA were higher than those of L ‐PLGA. With D,L ‐LA as the starting material, the structure of the PLGA copolymer was relatively simple, and its properties were apt to be controlled by its GA chain segment. When the feed molar percentage of the monomer (LA or GA) was more than or equal to 90%, the copolymer was apt to be crystalline, and the aptness was more obvious for the L ‐LA monomer. The composition percentage of GA in PLGA was not only higher than the feed molar percentage of GA, but also, the GA percentage in D,L ‐PLGA was higher than in L ‐PLGA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 244–252, 2006  相似文献   

3.
The glass‐transition temperatures (Tg) of some polymers reported in the literature have always been a source of great uncertainty. The values reported for poly(methacrylonitrile) (PMAN, 100 and 120°C) are well above the value determined in this study (67°C). It is clearly shown by FTIR and DSC work that formation of cyclic structures during the drying of PMAN, even at low temperatures, is the main reason for the high Tg values observed. The contributions of naphthydrine type cyclic structures and intermolecular crosslinks in the increase of the Tg are determined over an aging temperature interval of 90–300°C. The combined effects of intra‐ and intermolecular linking cause an increase in the Tg from 67 to 116°C. The hardness measurements also confirm the value determined by DSC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1936–1943, 2001  相似文献   

4.
Resins containing plant oil‐based cross‐linkers were studied with two reactive diluents: a styrene and an acrylated fatty acid methyl ester‐based (AFAME) monomer. Acrylated epoxidized soybean oil and maleinated castor oil monoglyceride were bio‐based cross‐linkers used. The viscosity and mechanical properties of the resulting polymers were measured and analyzed. Both bio‐based cross‐linkers prepared using the modified AFAME as diluent had a fairly high viscosity, so blends of AFAME and styrene were needed to meet the viscosity requirements established by the composite industry (<1000 cP at room temperature). In addition, the glass transition temperature (Tg) and stiffness of bio‐based cross‐linker/AFAME polymers were significantly lower than the resin/styrene polymers. Ternary blends of maleinated castor oil monoglyceride with AFAME and styrene improved the mechanical properties to acceptable comparable values (storage modulus at 30°C ~ 1200 MPa and Tg ~ 100°C). The addition of 5 wt% of chemically modified lignin led to an improvement in the mechanical properties of the polymeric matrix but caused an increase in the viscosity. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers  相似文献   

5.
In the development of processable high‐temperature materials, six new aromatic poly(imide)s based on diamines containing ortho trifluoromethyl groups, ether linkages and R,R‐methylenes moieties (R = Me or Ph) and previously reported dianhydrides have been synthesized vía polycondensation reactions. All polymers were obtained with good yields, were soluble in a variety of polar aprotic solvents, and exhibited inherent viscosity (ηinh) values between 0.15 and 0.20 dL g?1, which is indicative of low molecular‐weight species. Preliminary studies of their physical properties were carried out. The new materials were transparent in the visible region and they exhibited thermal decomposition temperatures ranging from 475 to 545 °C and glass‐transition temperatures varying from 288 to 304 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46613.  相似文献   

6.
The melt polycondensation reaction of N‐protected trans‐4‐hydroxy‐L ‐proline (N‐Z‐Hpr) and ?‐caprolactone (?‐CL) over a wide range of molar fractions in the feed produced new and degradable poly(N‐Z‐Hpr‐co‐?‐CL)s with stannous octoate as a catalyst. The optimal reaction conditions for the synthesis of the copolymers were obtained with 1.5 wt % stannous octoate at 140°C for 24 h. The synthesized copolymers were characterized by IR spectrophotometry, 1H NMR, differential scanning calorimetry, and Ubbelohde viscometry. The values of the inherent viscosity (ηinh) and glass‐transition temperature (Tg) of the copolymers depended on the molar fractions of N‐Z‐Hpr. With an increase in the trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) feed from 10 to 90 mol %, a decrease in ηinh from 2.47 to 1.05 dL/g, and an increase in Tg from ?48 to 49°C were observed. The in vitro degradation of these poly(N‐CBz‐Hpr‐co‐?‐CL)s was evaluated from weight‐loss measurements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3176–3182, 2003  相似文献   

7.
Di(isononyl) cyclohexane‐1,2‐dicarboxylate (DINCH) was used as a new plasticizer for poly(lactic acid) (PLA), and the effects of DINCH and tributyl citrate ester (TBC) on the morphology, mechanical and thermal properties, and durability of PLA were compared. DINCH has limited compatibility with PLA, leading to PLA/DINCH blends with phase separation in which DINCH forms spherical dispersed phase. TBC is compatible with PLA and evenly distributed in PLA. Plasticized PLA with 10 and 20 phr DINCH have a constant glass transition temperature (Tg) of 50°C and are stiff materials with high elongation at break and impact strength. TBC could significantly decrease the Tg and increase the crystallinity of PLA, and PLA/TBC (100/20) blend is a soft material with a Tg of 24°C. The durability of plasticized PLA was characterized by weight loss measurement under water immersion, mechanical properties, and thermal analysis. The results reveal that PLA/DINCH blends have better water resistance and aging resistance properties than PLA/TBC blends, which is attributed to the relatively high hydrophobicity of DINCH and high Tg of PLA/DINCH blends. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers  相似文献   

8.
BACKGROUND: In the development of nonlinear optical (NLO) polymers for electro‐optic device applications, stabilization of electrically induced dipole alignment is one of the important criteria. Polyimides for NLO applications have attracted attention because of their high Tg values and high thermal stability. In this work we designed and synthesized a new type of NLO polyimide, in which the pendant NLO chromophores are parts of the polymer backbone. These mid‐type NLO polymers are expected to have the merits of both main‐chain and side‐chain NLO polymers: stabilization of dipole alignment and good solubility. RESULTS: 3,4‐Bis‐(3,4‐dicarboxyphenylcarboxyethoxy)‐4′‐nitrostilbene dianhydride was prepared and reacted with the corresponding aromatic diamine to yield unprecedented Y‐type polyimides containing 3,4‐dioxynitrostilbenyl groups as NLO chromophores, which constituted parts of the polymer backbones. The resulting polyimides are soluble in polar solvents such as dimethylformamide and dimethylsulfoxide. These polymers showed a thermal stability up to 320 °C in thermogravimetric thermograms with Tg values obtained from differential scanning calorimetry thermograms in the range 143–164 °C. The second harmonic generation (SHG) coefficients (d33) of poled polymer films at the 1064 nm?1 fundamental wavelength were around 9.45 × 10?18 C. CONCLUSION: The dipole alignment exhibited exceptionally high thermal stability even at 30 °C higher than Tg. There was no SHG decay below 180–190 °C because of the partial main‐chain character of the polymer structure, which is acceptable for NLO device applications. Copyright © 2007 Society of Chemical Industry  相似文献   

9.
A novel diamine monomer having pendant 4‐(quinolin‐8‐yloxy) aniline group was successfully synthesized via aromatic substitution reaction of 8‐quinolinol with p‐fluoronitrobenzene followed by Pd/C catalyzed hydrazine reduction, amidation reaction between 4‐(quinolin‐8‐yloxy) aniline and 3,5‐dinitrobenzoylcholoride followed by Pd/C catalyzed hydrazine reduction. The diamine monomer was fully characterized by using FTIR, 1H‐NMR, 13C‐NMR, and elemental analysis. The diamine monomer was polymerized with various aromatic and aliphatic dicarboxylic acids to obtain the corresponding polyamides. The polyamides had inherent viscosity in the range of 0.30–0.41 dL/g and exhibited excellent solubility in the polar aprotic solvents such as DMAc, NMP, N,N‐dimethylformamide, Pyridine, and DMSO. The glass transition temperatures (Tg) of the polymers are high (up to 313°C) and the decomposition temperatures (Ti) range between 200 and 370°C, depending on the diacids residue in the polymers backbone. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

10.
Terpolymerization of L‐lactide (LA) and bisphenol A derivatives was performed on few hundred gram scale, and the resultant terpolymer (TP) was characterized by gel permeation chromatography, infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis. Moderate molecular weight (Mn ~ 12 kg/mol) TP was achieved with glass transition temperatures about 100°C (DSC and DMA). The TP exhibited improved thermal stability compared with polylactide (PLA), with a thermal degradation temperature of about 80°C higher than PLA. Although the TP exhibited distinctly different surface morphology compared with that of PLA, both showed similar contact angle and surface energy (ca. 40 mN/m) properties. Blends of PLA and TP showed enhanced glass transition (~ 5°C change in Tg) temperatures compared with PLA homopolymer. This is due to the compatibility of PLA and TP. Thus, TP could be used as an additive for PLA‐based blends to enhance compatibility with phenolic‐based resins. TP electrospun fiber morphology is also reported. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
In this work, the isothermal crystallization of compounded polylactide (PLA) and PLA-flax fiber composites was investigated by means of rheometry using small amplitude oscillatory shear (SAOS). The rheological measurements were carried out in parallel plate flow geometry at a crystallization temperature (T c ) ranging from 110 to 140 °C. In addition, the effect of shear on polylactide crystallization was studied at 140 °C. Rheological behavior in the molten state was employed to predict the initial viscosity in the T c interval by applying time-temperature superposition, and results were found to be in agreement with experimental values at low crystallization rates. A simple empirical model was also used to determine the crystallization induction time in a wide range of supercooling conditions. The evolution of the complex viscosity under quiescent conditions of the PLA-based flax-fiber composite indicated an enhancement of the rate of crystallization due to the presence of cellulosic fibers, while shear flow effectively accelerated the crystallization of neat PLA. This work shows that rheometry is an accurate technique for analyzing the crystallization behavior of polymers in a temperature range which presents low to very low crystallization rates, which is the case for PLA at T ≥ 130 °C.  相似文献   

12.
A series of biodegradable polylactide‐based polyurethanes (PLAUs) were synthesized using PLA diol (Mn = 3200) as soft segment, 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI) as hard segment, and 1,4‐butanediol as chain extender. The structures and properties of these PLAUs were studied using infrared spectroscopy, differential scanning calorimetry, tensile testing, and thermomechanical analysis. Among them, the MDI‐based PLAU has the highest Tg, maximum tensile strength, and restoration force, the TDI‐based PLAU has the lowest Tg, and the IPDI‐based PLAU has the highest tensile modulus and elongation at break. They are all amorphous. The shape recovery of the three PLAUs is almost complete in a tensile elongation of 150% or a twofold compression. They can keep their temporary shape easily at room temperature (20 °C). More importantly, they can deform and recover at a temperature below their Tg values. Therefore, by selecting the appropriate hard segment and adjusting the ratio of hard to soft segments, they can meet different practical demands for shape memory medical devices. Copyright © 2007 Society of Chemical Industry  相似文献   

13.
Using D ,L ‐lactic acid (LA) and multifunctional group compound triethanolamine (TEA) as starting materials, a novel biodegradable material poly(D ,L ‐lactic acid‐triethanolamine) [P(LA‐TEA)] was directly synthesized by simpler and practical melt polycondensation. The appropriate synthetic condition was discussed in detail. When the molar feed ratio LA/TEA was 30/1, the optimal synthesis conditions were as follows: a prepolymerization time of 12 h; 0.5 weight percent (wt %) SnO catalyst; and melt copolycondensation for 8 h at 160°C, which gave a novel star‐shaped poly(D,L ‐lactic acid) (PDLLA) modified by TEA with the maximum intrinsic viscosity [η] 0.93 dL g−1. The copolymer P(LA‐TEA) as a different molar feed ratio was characterized by [η], Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H‐NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD). Increasing the molar feed ratio of LA/TEA, Tg and Mw increased. However, all copolymers were amorphous, and their Tg (12.2°C–32.5°C) were lower than that of homopolymer PDLLA. The biggest Mw was 9400 Da, which made the biodegradable polymer be potentially used as drug delivery carrier, tissue engineering material, and green finishing agent in textile industry. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

14.
A core-shell modifier with the cross-linked acrylate and silicone copolymer as the core and polymethyl methacrylate (PMMA) as the shell (PASi-g-PMMA) was used to toughen the brittle polylactide (PLA). In addition, the copolymer of methyl methacrylate (MMA) and glycidyl methacrylate (GMA) (MG) was utilized to further enhance the modification efficiency of the PASi-g-PMMA. The MG copolymer played the double roles of compatibilizer and chain extender, which not only improved the interfacial adhesion between the PLA and PASi-g-PMMA particles, but also increased the molecular weight and chain entanglement of the PLA. Compared with the PASi-g-PMMA toughened PLA blend, the PLA/PASi-g-PMMA/MG blends showed much higher heat-resistance, melt strength, transparency, toughness and stiffness balance. When the PASi-g-PMMA content was 20 wt%, 20 wt% MG increased the glass transition temperature (Tg), complex viscosity (η*), transparency, impact and tensile strength of PLA/PASi-g-PMMA blend from 60.1°C, 1.9 × 103 Pa·s, 76.1%, 748 J/m and 37 MPa to 71.5°C, 0.5 × 104 Pa·s, 78.4%, 860 J/m and 45 MPa for the PLA/PASi-g-PMMA/MG blend. This research provided a facile and practical method to overcome the shortcomings of the PLA and promoted its application in broader fields.  相似文献   

15.
Polyamides (PAs) containing fluorene, oxyether, and diphenyl‐silane moieties in the repeating unit were synthesized in > 85% yield by direct polycondesation between a diamine and four dicarboxylic acids. Alternatively, one PA was synthesized from an acid dichloride. The diamine 4‐[4‐[9‐[4‐(4‐aminophenoxy)‐3‐methyl‐phenyl]fluoren‐9‐yl]‐2‐methyl‐phenoxy]aniline ( 3 ) was obtained from the corresponding dinitro compound, which was synthesized by nucleophilic aromatic halogen displacement from p‐chloronitrobenzene and 9,9‐bis (4‐hydroxy‐3‐methyl‐phenyl)fluorene ( 1 ). Monomers and polymers were characterized by FTIR and 1H, 13C, and 29Si‐NMR spectroscopy and the results were in agreement with the proposed structures. PAs showed inherent viscosity values between 0.14 and 0.43 dL/g, indicative of low molecular weight species, probably of oligomeric nature. The glass transition temperature (Tg) values were observed in the 188–211°C range by DSC analysis. Thermal decomposition temperature (TDT10%) values were above 400°C due to the presence of the aromatic rings in the diamine. All PAs showed good transparency in the visible region (>88% at 400 nm) due to the incorporation of the fluorene moiety. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

16.
Porous membranes composed of the biodegradable polyesters poly(D,L ‐lactide) (PLA) and poly(D,L ‐lactide‐co‐glycolide) (PLGA) were prepared by a phase inversion process. The molecular weights of the polymers and the concentrations of the polymer solutions affected the pore size and structure of the PLA and PLGA membranes. The molecular weights and morphological changes of the membranes as a function of time were investigated under incubation at 37°C in a humidified 5% CO2 atmosphere. The pores that formed in the membranes changed dramatically with increasing time under these conditions. From the thermal characterization of the polymers in their dry and wet states, we found that the glass‐transition temperatures of PLA and PLGA affected morphological structure changes in the porous membranes. We also prepared a collagen‐coated membrane to improve the interaction between the cell and the substrate, and we observed that the collagen coating enhanced the attachment and growth of Chinese hamster ovary cells on the substrate. Finally, we found that only PLA was a suitable material to prepare a porous membrane scaffold with the phase inversion process with PLA, and a collagen coating was necessary for cell culture on the membrane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2082–2092, 2004  相似文献   

17.
3,6‐bi(4‐fluorobenzoyl)‐N‐methylcarbazole and 3,6‐bi(4‐fluorobenzoyl)‐N‐ethylcarbazole were synthesized and used to prepare poly(arylene ether ketone)s (PAEKs) with high glass transition temperatures (Tg) and good solubility. High molecular weight amorphous PAEKs were prepared from these two difluoroketones with hydroquinone, phenolphthalein, 9,9‐bis(4‐hydroxyphenyl)fluorene and 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, respectively. All these polymers presented high thermal stability with glass transition temperatures being in the range 239–303 °C and a 5% thermal weight loss temperature above 460 °C. Compared with the Tg of phenolphthalein‐based PAEK (PEK‐C), fluorene‐based PAEK (BFEK) and phthalazinone‐based PAEK (DPEK) not containing a carbazole unit, these polymers presented a 30–50 °C increase in Tg. Meanwhile, PAEKs prepared from N‐ethylcarbazole difluoroketone showed good solubility in ordinary organic solvents, and all polymers exhibited excellent resistance to hydrochloric acid (36.5 wt%) and sodium hydroxide (50 wt%) solutions. In particular, phthalazinone‐based PAEK bearing N‐ethylcarbazole afforded simultaneously a Tg of 301 °C with good solubility. Tensile tests of films showed that these polymers have desirable mechanical properties. The carbazole‐based difluoroketones play an important role in preparing soluble PAEKs with high Tg by coordinating the relationship between chain rigidity resulting from the carbazole unit and chain distance from the side alkyl. © 2014 Society of Chemical Industry  相似文献   

18.
A study of the recent literature emphasized the importance of blending polymers with oils for improving the performance characteristics (like flexibility, corrosion resistance, etc.) of adhesives, coatings and laminates. Investigation of the available data revealed that several properties of such oil‐polymer blends could be correlated by molar refraction (RM), with reasonable accuracies. The properties of the linseed oil‐polystyrene (PS) and linseed oil‐polymethyl methacrylate (PMMA) blends studied are iodine value (IV), hydroxyl value (HV), inherent viscosity (η), melting temperature (TM), and glass transition temperature (Tg). In the case of safflower, palm and peanut oil‐sucrose polyester formulations, the viscosity at 40 °C (η40) and the melting point TM have been correlated by RM with the average absolute deviations (ē) of 17.8% and 3.0%, respectively. Using the orientation polarization PO (to represent polarity) in addition to RM, η40 and TM of oil‐polyester formulations could be calculated with ē values of 8.9% and 1.7%, compared to 17.8% and 3.0% using RM alone. The results indicated the importance of PO in improving the accuracy of predictions for properties.  相似文献   

19.
A copolymer series was synthesized for migration imaging applications from isobutyl methacrylate and isobutyl styrene such that each homopolymer and all copolymers had glass transition temperature (Tg) near 55°C. The Tg of poly (p-isobutylstyrene) was predicted from literature values of similar polymers to be near 55°C. Poly (p-isobutylstyrene) was synthesised by acetylation of isobutyl benzene, reduction of p-isobutylacetoph-enone to the carbinol, dehydration to p-isobutylstyrene and free radical polymerisation to the polymer. The Tg of the homopolymer was 55°C, in excellent agreement with the predicted value. Copolymers of isobutyl methacrylate and p-isobutyl styrene were synthesised and their Tg's measured across the series by DSC (57°C ± 5°C). refractive index temperature coefficient (42°C ± 5°C). The copolymer series was also characterised by melt viscosity measurements.  相似文献   

20.
A new kind of aromatic unsymmetrical diamine monomer containing thiazole ring, 2‐amino‐5‐(4‐aminophenyl)‐thiazole (AAPT), was synthesized. A series of novel polyimides were prepared by polycondensation of AAPT with various aromatic dianhydrides by one‐step polyimidation process. The synthesized polyimides had inherent viscosity values of 0.36–0.69 dL/g and were easily dissolved in highly dipolar solvents. Meanwhile, strong and flexible polyimide films were obtained, which have good thermal and thermo‐oxidative stability with the glass transition temperatures (Tg) of 276.7–346.1°C, the temperature at 5% weight loss of 451–492°C in nitrogen and 422–440°C in air, as well as have outstanding mechanical properties with the tensile strengths of 94–122 MPa, elongations at breakage of 5–18%. These films also had dielectric constants of 3.12–3.38 at 10 MHz. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

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