Synthesis,structure, and thermal property of poly(trimethylene terephthalate-<Emphasis Type="Italic">co</Emphasis>-trimethylene 2,6-naphthalate) copolymers

Poly(trimethylene terephthalate-co-trimethylene 2,6-naphthalate)s (P(TT-co-TN)s) with various copolymer composition were synthesized, and their chain structure, thermal property and crystalline structure were investigated by using¹H-NMR spectroscopy, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD), respectively. It was found from sequence analysis that all the P(TT-co-TN) copolymers synthesized have a statistical random distribution of TT and TN units. It was also observed from DSC thermograms that the glass transition temperature increases linearly with increasing the TN comonomer content, whereas the melting temperature of copolymer decreases with increasing the corresponding comonomer content in respective PTT- and PTN-based copolymer, showing pseudo-eutectic melting behavior. All the samples melt-crystallized isothermally except for P(TT-co-66 mol % TN) exhibit multiple melting endotherms and clear X-ray diffraction patterns. The multiple melting behavior originates from the dual lamellar population and/or the melting-recrystallization-remelting. The X-ray diffraction patterns are largely divided into two classes depending on the copolymer composition, i.e., PTT and PTNβ-form diffraction patterns, without exhibiting cocrystallization.     

Preparation and Properties of Nylon 4/6 Copolymer Nanofibers Containing Silver-Zeolite Nanoparticles

Nylon 4/6 copolymer has desirable properties, such as high affinity to water and good tensile strength. These properties originate from the characteristics of nylon 4 and nylon 6. Zeolite is a good adsorptive material that has many pores in its structure and the ability to capture metallic ions. As a multifunctional additive, silver-ion-loaded zeolite nanoparticles were used to increase the moisture regain and impart antimicrobial properties to the nylon 4/6 copolymer. A nylon 4/6 nanofiber web was prepared by electrospinning from a polymer solution containing silver zeolite nanoparticles. The moisture regain of the nylon 4/6 nanofiber web increased with increasing amount of silver zeolite added. The web showed excellent antimicrobial activity against Klebsiella pneumoniae and Staphylococcus aureus. Overall, the nylon 4/6 nanofiber web could be a good material for wound healing dressings and high functional medical filters.     

Preparation,chemical, and thermal characterization of nylon 4/6 copolymers by anionic ring opening polymerization of 2-Pyrrolidone and ε-Caprolactam

Nylon 4/6 copolymers based on 2-pyrrolidone (C4) and ε-caprolactam (C6) were synthesized and characterized as part of ongoing efforts to develop thermally stable, melt-processable 2-pyrrolidone (C4) based Nylons. Copolymers of various compositions were synthesized at between 50 and 100 °C via the anionic ring opening polymerization of C4 and C6 using a potassium tert-butoxide catalyst and a benzoyl chloride initiator. The polymers were characterized by NMR spectroscopy, DSC, TGA, GPC, intrinsic viscosity measurements, and X-ray scattering (SAXS and WAXS). Their chemical compositions and sequence distributions were obtained by ¹H- and ¹³C-NMR spectroscopies, respectively. X-ray scattering was used to investigate the lamellar morphologies and the crystal structures of solvent cast films of the copolymers. WAXS revealed the presence of α-phase crystals in the copolymers. TGA data coupled with molecular weight and sequence distribution information indicated that the polymers’ thermal stability depended on both their chemical composition and their sequence distribution.     

Synthesis and hydrophilicities of Poly(ethylene 2,6-naphthalate)/Poly(ethylene glycol) copolymers

Poly(ethylene 2,6-naphthalate) (PEN)/Poly(ethylene glycol) (PEG) copolymers were synthesized by two step reaction during the melt copolymerization process. The first step was the esterification reaction of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) and ethylene glycol (EG). The second step was the condensation polymerization of bishydroxyethylnaphthalate (BHEN) and PEG. The copolymers contained 10 mol% of PEG units with different molecular weights. Structures and thermal properties of the copolymers were studied by using¹H-NMR, DSC, TGA, etc. Especially, while the intrinsic viscosities of PEN/PEG copolymers increased with increasing molecular weights of PEG, but the glass transition temperature, the cold crystallization temperature, and the weight loss temperature of the copolymers decreased with increasing molecular weights of PEG. Consequently, the hydrophilicities by means of contact angle measurement and moisture content of the copolymer films were found to be significantly improved with increasing molecular weights of PEG.     

Kinetics on the copolymerization of acrylonitrile with itaconic acid or methyl acrylate in dimethylsulfoxide by NMR spectroscopy

The free radical solution polymerization of acrylonitrile (AN) with itaconic acid (IA) or methyl acrylate (MA) was carried out in dimethylsulfoxide (DMSO) using 2 2'-azobisisobutyronitrile (AIBN) as the initiator. Based on the monomer conversion versus time data, the copolymerization rate was retarded by IA but promoted by MA. The monomer sequence distribution was characterized by ¹³C NMR to explain the significant difference in the copolymerization kinetics of the ANIA and AN-MA copolymers. The results of the copolymer composition curves and ¹³C NMR spectral analysis illustrated that the penultimate model was suitable for describing the copolymerization behavior of AN-IA, and the terminal and penultimate models were adequate for AN-MA. The penultimate reactivity ratios, r _MA , were ~2 times higher than r _IA , indicating that the reactivity of AN-terminated radical having MA as the preceding group was higher than that with IA. Then, the corresponding content of triads sequence AN-AN-AN (AAA) in the AN-MA copolymers was higher than those in the AN-IA copolymers. The appearance of new resonance signals of the quaternary and methyl carbon indicated a higher content of IA in copolymers. The higher IA concentrations the lower viscosity-average molecular weight of the polymers. The decrease in the molecular weight was correlated to the formation of the oligomers.     

Improved compressive strength of poly(p-phenylene benzobisoxazole) copolymer fiber containing multi-functional comonomer

Multi-functional comonomer from pentaerythritol (PE) and terephthaloyl chloride (TPC) was synthesized and used for polymerization of poly(p-phenylene benzobisoxazole) (PBO) copolymer. PBO copolymer fibers were prepared from PBO copolymers using a dry-jet wet spinning. The tensile strength of PBO copolymer fibers was higher than that of PBO, and showed 42 % increase at 0.5 mol% loading of comonomer. The tensile modulus of PBO copolymer fiber at 0.5 mol% loading showed 192 % increase compared to PBO fiber. The compressive strength of PBO copolymer fiber had values between 0.46 GPa and 0.6 GPa with the comonomer content. 64-114 % increase in compressive strength of PBO copolymer fibers was observed compared to PBO fiber.     

Heat resistance,impact strength,and transparency of PET copolymer containing fluorenylidene bis(2-phenoxyethanol)

Poly(ethylene terephthalate) (PET) copolymers containing fluorenylidene bis(2-phenoxyethanol) (FBPE) were prepared. The glass transition temperature of copolymers increased continuously with the composition of FBPE. The glass transition temperature of PET/FBPE copolymer at loading of 15 mol% FBPE was 107 °C, which was 35 °C higher than that of PET. The melting temperature of PET/FBPE copolymers was decreased with the composition of FBPE, and it disappeared above 6 mol% of FBPE. The heat deflection temperature of copolymers increased from 60.7 °C for PET to 89.9 °C for the copolymer containing 15 mol% of FBPE. The values of optical transmittance of copolymers were 89-90 % at 550 nm, and no significant change was observed with the FBPE composition. The impact strength value of copolymer at loading of 10 mol% FBPE was 26 J/m, which was 20 J/m higher than that of PET.     

Synthesis and hydrophilicity of poly(trimethylene 2,6-naphthalate)/poly(ethylene glycol) copolymers

Poly(trimethylene 2,6-naphthalate) (PTN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two-step melt copolymerization process of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) with 1,3-propanediol (PD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structure, thermal property, and hydrophilicity of these copolymers were studied by proton nuclear magnetic resonance (¹H-NMR) analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and by contact angle, moisture content, and instantaneous elastic recovery measurements. The intrinsic viscosity and the instantaneous elastic recovery of the PTN/PEG copolymers increased with increasing PEG molecular weight and content, whereas the glass transition, melting, and cold crystallization temperatures, and the heat of fusion of the PTN/PEG copolymers all decreased with increasing PEG molecular weight or content. The thermal stability of the copolymers was not affected by PEG molecular weight or content. The hydrophilicity, as determined by contact angle and moisture content measurements of the copolymer films, was significantly improved with increasing PEG molecular weight and content.     

Synthesis and characterization of new copolymers from glycidyl methacrylate and tetrahydrofurfuryl acrylate: Determination of reactivity ratios

The new copolymers from different feed compositions of glycidyl methacrylate (GMA) and tetrahydrofurfuryl acrylate (THFA) were synthesized using free radical polymerization in toluene at 70±1 °C using benzoyl peroxide (BPO) as initiator. The polymers were characterized by ¹H NMR, ¹³C NMR and FTIR spectroscopic techniques. The polydispersities of the copolymers suggest a strong tendency for chain termination by disproportionation. The glass transition temperature of the copolymers increases with increase in GMA content. The thermal stability of the copolymers increases with increase in THFA content. The copolymer compositions were determined using ¹H NMR analysis. Reactivity ratios for GMA and THFA as determined by the Mao-Huglin method were r₁=0.379 and r₂=0.266. The results showed that all these copolymerizations are strictly linear systems describable by the Mayo-Lewis equation based on the terminal model and that accurate reactivity ratio data can be obtained.     

Rheological and thermal properties of acrylonitrile-acrylamide copolymers: Influence of polymerization temperature

An attempt was made to correlate the polymerization temperature and rheological and thermal properties of acrylonitrile (AN)-acrylamide (AM) copolymers. The copolymers were synthesized at different polymerization temperature. The copolymer structure was characterized by gel permeation chromatography (GPC) and Infrared spectrum (IR). The rheological and thermal properties were investigated by a viscometer and differential scanning calorimeter-thermogrametric (DSCTG) analysis, respectively. When the polymerization temperature increased from 41 °C to 65 °C, the molecular weight ([`(M)] <sub>w</sub> )(\overline M _w ) of copolymers decreased from 1,090,000 to 250,000, while its conversion increased from 18% to 63%, and the polymer composition changed slightly. To meet the requirements of carbon fibers, the rheological and thermal properties of products were also investigated. It was found that the relationship between viscosity and [`(M)] _w\overline M _w was nonlinear and the viscosity index (n) decreased from 3.13 to 2.69, when the solution temperature increased from 30 °C to 65 °C. This suggests the dependence of viscosity upon [`(M)] _w\overline M _w is higher at lower solution temperature. According to the result of activation energy, the sensivity of viscosity to solution temperature is higher for AN-AM copolymers synthesized at higher polymerization temperature. The result of thermal analysis shows that the copolymers obtained at higher polymerization temperature are easier to cyclization evidenced from lower initiation temperature. The weight loss behavior changed irregularly with polymerization temperature due to irregular change of liberation heat.     

Photo-induced living cationic polymerization of tetrahydrofuran. III. Synthesis of poly(THF-co-3-MTHF)

Poly(3-methyltetrahydrofuran)(3-MTHF) and poly(tetrahydrofuran-co-3-MTHF), having very narrow molecular weight distribution were successfully synthesized via photo-induced living cationic polymerization in the presence of diphenyliodonium hexafluorophosphate. Linear relationship between % conversion and number average molecular weight of resulting poly(3-MTHF) in the polymerization of 3-MTHF, carried out at −22°C, indicates that the 5-membered cyclic oxonium ion, being responsible for the cationic propagation is stabilized by ion pair formation with hexafluorophosphate anion, supplied from the salt. The linear relationship between two parameters, mentioned above was also observed in the copolymerization of 3-MTHF with THF, carried out at 0 and −22°C. The molecular structures including the copolymer composition and average molecular weight and its distribution is determined by reaction parameters such as monomer feed ratio and reaction temperature.     

Properties of polyurethane-poly(2,2,3,3-tetrafluoropropyl acrylate) triblock copolymer aqueous dispersion and its film cast from the dispersion

Polyurethane-poly(2,2,3,3-tetrafluoropropyl acrylate) (PU-PTFPA) triblock copolymer aqueous dispersions were synthesized by three-step polymerization. Infra-red (IR) data verify the copolymerization between PU and TFPA. The properties of copolymer aqueous dispersion and its film cast from the dispersion have been investigated by transmission electron microscopy (TEM), dynamic light scattering (DLS), and some other physical testing methods. TEM observations indicate that the morphologies of copolymer particles formed in water are almost irregular spherical shape with core-shell structure. DLS results verify that the introduction of TFPA monomer changes the average particle size of copolymer particles. The experimental data demonstrate that the factors influencing the properties of PU-PTFPA triblock copolymer aqueous dispersion and its film cast from the dispersion mainly involve PU content, DMPA content and PTFPA content.     

Synthesis and crystallization behaviors of modified PET copolymers

A series of random copolyesters having various compositions were synthesized by bulk copolymerization of bishydroxyethyl terephthalate (BHET) with 1,4-cyclohexane dimethanol (CHDM) or dimethyl isophthalate (DMI). CHDM and DMI content was less than 10 wt%. For the synthesized copolyesters, isothermal crystallization rate, melting behavior, and equilibrium temperature were investigated by calorimetry and by Avrami and Hoffman-Weeks equation. Crystalline lattice and morphology were studied by WAXD and SEM. Regardless of the composition, the value of the Avrami exponent was about 3, which indicates that crystallization mechanism of the copolyester was similar to those of PET homopolymer. Incoporation of CHDM or DMI units in PET backbone decreased the crystallization rate of the copolyesters. Surface free energy of copolyesters was evaluated using the newly proposed equation. The value of surface free energy was about 189×10⁻⁶ J²/m⁴ regardless of comonomer contents. This result is in good agreement with that of PET homopolymer.     

Radical Polymerization and Kinetics of N,N-diallyl-N,N-dimethylammonium Chloride and Vinyl Ether of Monoethanolamine

N,N-diallyl-N,N-dimethylammonium chloride (DADMAC) and vinyl ether of monoethanolamine copolymer (VEMEA) was synthesized by radical polymerization in aqueous media using ammonium persulfate as initiator. Copolymers synthesis was carried out by varying monomer composition at low conversion level. The viscosity of high molecular weight products was measured in aqueous 1 M NaCl solution and it was increased with increasing DADMAC amounts in the copolymer due to increasing positive charge. The structure of the product was identified by FTIR, ¹H, ¹³C-NMR spectroscopies and conductometric titration methods. We calculated monomer reactivity ratios with help of Finemann-Ross, Kelen-Tudos, and inverted Finemann-Ross methods. It was found that DADMAC is more reactive than VEMEA, therefore the amount of DADMAC in the copolymers always dominated regardless of the initial monomer ratio in solution and it was shown that the monomers are connected randomly in the polymer chain. The effect of various parameters such as monomer [M], initiator [I] concentrations, ratio of comonomers, etc. on polymerization was investigated systematically. So, the polymerization rate (R_p) equation was found to be R_p=k[M]^2.6[I]^0.6 where molar fractions of DADMAC and VEMEA was 90:10 and the temperature was 65 °C. Degree of polymerization was examined by using various monomers and initiator concentrations via the dilatometeric method. It was found that the polymerization rate increased directly with total monomer concentration and initiator content.     

Fabrication and characterization of dense Chitosan/polyvinyl-alcohol/poly-lactic-acid blend membranes

Dense membranes of Chitosan (CS)/Poly(vinyl alcohol) (PVA)/Poly(lactic acid) (PLA) blend were successfully fabricated using casting technique. The mechanical properties, moisture regain and water vapor permeability of polymer blend membranes were estimated by tensile test, moisture regain rate and dish method test respectively. The microstructures, morphology, chemical composition and thermal properties were also characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) respectively. Results indicated that there were interactions and good compatibility among CS, PLA and PVA. And the blend membranes have good breaking elongation and slightly decreased breaking strength, and show best moisture regain at the case of CS60 (the content of CS in the blends is 60 %). They also have excellent porous structure, which is beneficial to their air permeability and may also contribute to cell regeneration. With the adding of PVA content, the melting peaks of blend membranes reduce and gradually close to that of PVA, demonstrating that the regularity of CS molecular chain may be destroyed and hydrogen bonds of macromolecules in polymers were newly formed. As a result, solution blending of the three polymers could complement their disadvantages and significantly improve the membrane performance of a single polymer, thus promote the mechanical and biological properties of blend membrane.     

Copolymerization of benzyl methacrylate and a methacrylate bearing benzophenoxy and hydroxyl side groups: Monomer reactivity ratios,thermal studies and dielectric measurements

Statistical copolymers of 2-hydroxy-3-benzophenoxy propyl methacrylate (HBPPMA) and benzyl methacrylate (BzMA) in different feed ratios were synthesized by free radical copolymerization method at 60 °C in presence of AIBN initiator. The compositions of copolymer were estimated from ¹H-NMR technique. The monomer reactivity ratios of HBPPMA and BzMA were calculated as r₁ (r_HBPPMA)=0.51±0.076 and r₂ (r_BzMA)=1.07±0.140 for Kelen-Tüdos method, and was estimated as r₁=0.37±0.0006 and r₂=0.64±0.0485 according to Fineman Ross equation. The average values estimated from the two methods showed that monomer reactivity ratio of benzyl methacrylate was a slightly high in comparison to HBPPMA. The copolymer system showed an azeotropic point, which is equal to M _BzMA =m _BzMA =0.43. DSC measurements showed that the T_g’s of poly(HBPPMA) and poly(BzMA) were 84 °C and 73 °C, respectively. The T_g in the copolymer system decreased with increase in benzyl methacrylate content. The decomposition temperature of poly(BzMA) and poly(HBPPMA) occurs in a single stage at about 207 °C and 260 °C, respectively. Those of HBPPMA-BzMA copolymer systems are between decomposition temperatures of two homopolymers. The dielectric constant, dielectric loss factor and electrical conductivity were investigated depend on the frequency of the copolymers. The highest dielectric constants depending on all the studied frequencies were recorded for the poly(HBPPMA) and the copolymer containing the highest HBPPMA unit. The dielectric constant for P(HBPPMA) and P(BzMA) at 1 kHz are 6.56 and 3.22, respectively. Also, those of copolymer systems were estimated between these two values. Similarly, poly(HBPPMA) and copolymers, which are prepared under the same conditions show the dissipation factor and conductivity as well.     

Optimization of papain treatment for improving the hydrophilicity of polyester fabrics

The goal of this study was to establish optimal conditions for improving the hydrophilicity of polyester fabrics. The hydrolytic activity of papain was determined by measuring the number of carboxylic groups in the treatment solution. Papain treatment conditions-such as pH, temperature, treatment time, and enzyme concentration-were optimized by measuring hydrolytic activity, moisture regain, and wettability. Optimal papain treatment conditions were identified as a pH of 7.5, temperature of 30 °C, treatment time of 60 min, and papain concentration of 100 %(o.w.f.). The moisture regain for polyester fabrics treated with papain improved to 1.28±0.02 %, a 2.7-fold increase compared to that of untreated polyester fabrics. As the hydrolytic activity increased, the moisture regain and wettability of the treated fabrics improved. L-cysteine and sodium sulfite did not affect the moisture regain of papain-treated polyester fabrics.     

自由基聚合法合成天然橡胶接枝共聚物的研究综述

通过聚合物接枝改性天然橡胶(NR)是改善NR性能和扩展其应用范围的重要方法之一。目前,人们主要通过自由基聚合(freeradical polymerization,FRP)法合成NR接枝共聚物,本文就其反应机理和反应工艺进行了综述,并从接枝共聚物的结构可控性和可控/“活性”自由基聚合的角度对NR接枝共聚物的合成方法进行了展望。     

Synthesis of core-shell fluorinated acrylate copolymers and its application as finishing agent for textile

Core-shell fluorinated acrylate copolymers emulsion was thus synthesized via the core-shell emulsion polymerization with the fluorinated monomers and acrylic monomers as the main raw materials and its properties were studied. PFMA, the fluorinated acrylate monomers, was synthesized by the esterification of perfluorooctanoyl chloride (PFOC) and hydroxypropyl methacrylate (HPMA). Then the core-shell fluorinated acrylate copolymers emulsion with a poly(MMA/BA/St) core and a poly(PFMA/MMA/BA) shell was synthesized via a starved semi-continuous core-shell emulsion polymerization method by using KPS and sodium bicarbonate as the initiator/buffer system and SDS/Twain 80 as the commixture emulsifier. Lastly, the synthesized copolymers was applied as textile finishing agent for cotton textile. The results of FT-IR and NMR indicated that PFMA had been synthesized as expected and effectively combined in the emulsion copolymerization. The GPC, zeta potential, TEM and DSC showed that the particles had uniform spherical core-shell structure with a diameter of 65-150 nm, and the distribution and emulsion stability was satisfactory. As XPS, FESEM and AFM shown, a hydrophobic structure which was similar to the structure of the lotus leaf were formed and the surface hydrophobicity of the films can be improved. Based on the analysis of DSC, thermal stabilities of the films were enhanced with the increase of fluorine content. Besides, FESEM of textiles showed that the surface of treated textiles were smooth and the edges were clear and visible, indicating significant improvement of the performance on water and oil repellent.     

Glass transition behavior of corn distillers dried grains with solubles (DDGS)

Distillers dried grains with solubles (DDGS), a major co-product from the corn ethanol industry, has high feed value for its chemical composition. The ratio of wet distillers grains (WDG) and condensed distillers solubles (CDS) added during the production process determines the chemical composition of DDGS. Effect of changing this ratio and the influence of moisture content on glass transition behavior of DDGS was studied. Five prediction models were evaluated to explain the glass transition of DDGS. The mixed trends in the result indicated the complex behavior of DDGS particles and revealed that both moisture content and chemical composition impact the glass transition behavior of DDGS. Onset glass transition temperature ranged from 20 to 30 °C depending on the chemical composition. Kwei equation predictions were better than the predictions by Gordon-Taylor equation. The glass transition temperature of DDGS can be mathematically explained by combining the moisture content and chemical components protein, fiber, glycerol, and sugar percent. The artificial neural network (ANN) model gave a better prediction of onset and midpoint glass transition temperature of DDGS and this might be due to the accurate mapping of the interaction between chemical components.