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1.
Anna Finne Ann-Christine Albertsson 《Journal of polymer science. Part A, Polymer chemistry》2004,42(3):444-452
Following our continued interest in the production of bioerodible and biodegradable functional polymers for biomedical applications, we synthesized and characterized new unsaturated polyesters. The presence of functional groups in the polymer backbone provided sites for chemical modification, and through a variation in the structure, the physical properties, such as the hydrophilicity and solubility, could be affected. With 1,1-di-n-butyl-stanna-2,7-dioxacyclo-4-heptene as the initiator in the ring-opening polymerization of polyesters, a new set of functionalized polyesters was created. The polymerization of ϵ-caprolactone resulted in poly(ϵ-caprolactone) with a double bond incorporated into the structure. The polymers were obtained in a controlled manner with low molecular dispersities. The double bond was previously incorporated into L -lactide polymers, and the two reactions were compared in this study. The conversion of ϵ-caprolactone, with a degree of polymerization of 50, was completed within 140 min, whereas for L -lactide, only a 45% conversion took place in the same period of time. The dispersities were somewhat higher with ϵ-caprolactone because of the higher reaction rate and, therefore, lower selectivity. The incorporated CC double bond in the polyesters provided a variety of opportunities for further modifications. In this case, the double bond of the L -lactide macromonomers was oxidized into epoxides. Epoxidation was carried out with m-chloroperoxybenzoic acid as a chemical reagent. The conversion of the double bonds into epoxides was completed, and the obtained yields were good (>95%). As a result of the mild reaction conditions, the epoxidation of the double bond was carried out quantitatively without any side reactions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 444–452, 2004 相似文献
2.
Fukuji Higashi Kaori Kira 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2725-2733
The solution polyesterification of dicarboxylic acids in pyridine, the activated intermediates of which were difficult to dissolve in tosyl chloride/dimethylformamide/pyridine, was investigated in the presence of lithium chloride. The solubility of the activated dicarboxylic acids was largely improved by the presence of the salt, and the polycondensation with bisphenols was greatly facilitated. The salt was more effectively added to a pyridine solution of dicarboxylic acids than to the activated dicarboxylic acids in pyridine. The favorable additive effect on the improved solubility was attributed to a lowered degree of association of the activated dicarboxylic acids, which led to distributions of the resulting oligomers from bisphenols at an earlier stage closer to the theoretical ones and yielded better polycondensation results. The reaction, which proceeded through favorable distributions of the co‐oligomers, produced copolymers of higher inherent viscosities and slightly block sequence distributions determined by NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2725–2733, 2004 相似文献
3.
E.‐A. McGonigle J. J. Liggat R. A. Pethrick S. D. Jenkins J. H. Daly D. Hayward 《Journal of Polymer Science.Polymer Physics》2004,42(15):2916-2929
For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N2, and O2 in the range of polyesters. However, the permeability of CO2 was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004 相似文献
4.
Richard Kotek Kyeong Pang Ben Schmidt Alan Tonelli 《Journal of Polymer Science.Polymer Physics》2004,42(23):4247-4254
Poly(ethylene isophthalate) (PEI) was synthesized for this research with essentially a condensation polymerization of isophthalic acid and ethylene glycol catalyzed by zinc acetate and antimony trioxide. Several samples were obtained, and their characteristics were observed and compared with poly(ethylene terephthalate) (PET). The synthesized PEI samples were chemically identified by 1H NMR. Thermal analysis with differential scanning calorimetry (DSC) yielded results that indicate the samples were primarily amorphous, with a glass‐transition temperature of 55–60 °C. Molecular weights of these PEI samples were also obtained through intrinsic viscosity measurements (Mark–Houwink equation). Molecular weights varied with conditions of the polymerization, and the highest molecular weight achieved was 21,000 g/mol. Finally, the diffusion coefficient, solubility, and permeability of CO2 gas in PEI were measured and found to be substantially lower than in PET, as anticipated from their isomeric chemical structures. This is because in PET the phenyl rings are substituted in the para (1,4) positions, which allows for their facile flipping, effectively permitting gases to pass through. However, the meta‐substituted phenyl rings in PEI do not permit such ring flipping, and thus PEI may be more suitable for barrier applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4247–4254, 2004 相似文献
5.
R. Centore P. Riccio S. Fusco A. Carella A. Quatela S. Schutzmann F. Stella F. De Matteis 《Journal of polymer science. Part A, Polymer chemistry》2007,45(13):2719-2725
We have prepared new polyesters containing quadratic, nonlinear optical (NLO) active chromophores covalently incorporated into the main chain. In these polymers, the sequence of the chromophore units along the main chain is rigorously head to tail. All the polyesters are processable, both in the melt and in solution. For one polyester, a full second‐order NLO characterization has been performed. An out‐of‐resonance d33 coefficient of 21 pm/V at 1368 nm has been measured. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2719–2725, 2007 相似文献
6.
Niyazi Bicak Bunyamin Karagoz Umit Tunca 《Journal of polymer science. Part A, Polymer chemistry》2003,41(16):2549-2555
The controlled reaction of equimolar quantities of maleic anhydride and glycidol in dimethoxyethane gives soluble polyesters with one hydroxyl group in each repeating unit. The reaction proceeds with stepwise ring opening of the components and gives highly viscous clear solutions in relatively short periods. In the first step, monomaleate ester formation takes place around 80 °C. The ring opening of the oxirane group is the second step, and it occurs at 120 °C. The overall reaction is the formation of soluble polyesters with moderate molecular weights (6000–18,000), without the elimination of water. The soluble polyesters can be crosslinked tightly by direct heating at 190 °C without additional vinyl monomer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2549–2555, 2003 相似文献
7.
Z. J. Yu L. J. Liu R. X. Zhuo 《Journal of polymer science. Part A, Polymer chemistry》2003,41(1):13-21
The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by 1H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (Mw) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (Mw/Mn)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with Mw = 12,100 and Mw/Mn = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in Mw of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003 相似文献
8.
Distribution of melamine in polyester–melamine surface coatings cured under nonisothermal conditions
N. J. W. Gamage D. J. T. Hill C. A. Lukey P. J. Pomery 《Journal of polymer science. Part A, Polymer chemistry》2004,42(1):83-91
The influence of experimental cure parameters on the diffusion of reactive species in polyester–melamine thermoset coatings during curing has been investigated with X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared. The diffusion of melamine plays a vital role in the curing process and, therefore, in the ultimate properties of coatings. At a low (<20%) hexamethoxymethylmelamine (HMMM) crosslinker concentration, the matrix composition is uniform, but at high HMMM concentrations, excess HMMM rapidly segregates to the air–coating interface. The rate of migration is governed by the difference in the surface free energies of polyester and HMMM and the concentration gradient of HMMM between the bulk and the surface. An increased rate of energy absorption also increases the rate of migration of HMMM to the surface. A physical model has been proposed to explain this surface segregation phenomenon in terms of cocondensation and self‐condensation reactions. It suggests that an appropriate amount of melamine can be segregated on the surface and allowed to self‐condense to form a desired thickness of a melamine topcoat through the control of the binder composition and cure conditions. This technique can be implemented to apply a melamine topcoat during cure. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 83–91, 2004 相似文献
9.
Piotr Dobrzynski 《Journal of polymer science. Part A, Polymer chemistry》2004,42(8):1886-1900
Lactide polymerization using zirconium(IV) acetylacetonate [Zr(acac)4] as an initiator was investigated. In the reaction between Zr(acac)4 and the monomer molecule, lactide deprotonation and the release of acetylacetone occurred. The structures of the obtained complexes were analyzed with high‐resolution NMR spectroscopy. A computational method was used to calculate the hypothetical structures. The role of the obtained complexes in the initiation of polymerization and the reaction of chain growth was proposed. The influence of the reaction temperature on the structures of the complexes was investigated. Polylactide chain growth proceeded by an insertion‐coordination mechanism. The polymer chain grew on one ligand, which was formed in advance from a deprotonated lactide. The molecular masses of the obtained polymers were the same as the theoretical masses and were directly proportional to the reaction conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1886–1900, 2004 相似文献
10.
Auvergne R. Saint‐Loup R. Joly‐Duhamel C. Robin J. J. Boutevin B. 《Journal of polymer science. Part A, Polymer chemistry》2007,45(7):1324-1335
The synthesis and characterization of photopolymerizable unsaturated polyester resins based on PET waste are described. The resins came from a depolymerization process based on the glycolysis of PET by diethylene glycol (DEG). Different molecular weights of glycolysates were synthesized. Then, the latter was functionalized by a methyl hemiester of maleic acid to obtain unsatured α,ω‐bismaleate PET oligomers. In the presence of an electron donor monomer, such as triethylene glycol divinyl ether, these electron acceptor oligomers were copolymerized by way of charge‐transfer complexes under UV irradiation. The reaction was monitored in situ by real‐time IR spectroscopy to study the kinetics of photopolymerization. This one was studied in relation with the physical and chemical characteristics of oligoesters and the composition of mixtures containing divinyl ethers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1324–1335, 2007 相似文献