Reaction of poly(vinyl alcohol) with diketene

A study has been made on the modification of poly (vinyl alcohol) with diketene using tertiary amines as catalysts. The structure of the resulting polymers was determined by means of IR, ¹H- and ¹³C-NMR spectroscopy as well as by chemical analysis. Vinyl alcohol-vinyl acetoacetate (VAL-VAA) copolymers were obtained. It has been found a linear dependence of reaction rate on polymer, diketene and pyridine concentrations, respectively. The activation energy was found to be 35.5 kJ/mol (8.5 kcal/mol). ¹³C-NMR spectroscopy was used for the determination of the sequence distribution in VAL-VAA copolymers. The obtained results show that VAA units have a little alternating tendency in the copolymer chain. Polymeric chelates between VAL-VAA copolymers and cupric ions have been prepared. It is noteworthy that not all the β-keto ester groups in the VAL-VAA copolymers participate in binding cupric ions.     

Kinetic study of the hydrolysis of vinyl alcohol-vinyl n-alkyl carbonate copolymers

A kinetic study of the hydrolysis of vinyl alcohol-vinyl n-alkyl carbonate copolymers has been made as a function of the base or acid concentration, the temperature, and the structure of the carbonate units. The homogeneous hydrolysis in alkaline medium was found to be first order with respect to both the hydroxyl ion and the carbonate; the acid hydrolysis was of first order with respect to the acid concentration. The heterogeneous hydrolysis in alkaline medium followed a pseudo-first-order kinetics with respect to the base concentration; the hydrolysis rate was affected by the carbonate content and the structure of the carbonate units. The activation energies obtained for the acid and base catalyzed homogeneous hydrolysis and the base catalyzed heterogeneous hydrolysis were 13.8, 10.0, and 10.3 kcal/mol, respectively. α-Chymotrypsin was inactive in the hydrolysis experiments carried out with these copolymers.     

Partial esterification of poly(vinyl alcohol) with acid chlorides

This work deals with some features of the reaction of organic acid chlorides with poly(vinyl alcohol). The structure of the modified polymers was determined by means of IR, UV and NMR spectroscopy as well as by chemical analysis. Vinyl alcohol-vinyl butyrate copolymers were obtained by reaction of poly(vinyl alcohol) with n-butyryl chloride without any catalyst. The reaction appeared to satisfy a second order kinetics for conversions no higher than 50%. The activation energy found was of 9.9 kcal/mol. The use of pyridine as a catalyst involved a noticeable increase of the reaction rate, but this effect was found to be independent of the acid chloride used. When triethylamine was used as a catalyst, β-keto ester groups were found to be grafted onto the polymer chain. The steric hindrance of these groups were thought to be sufficiently important for the conversion to reach a limit of about 30%. The observed swelling in water of vinyl alcohol-vinyl butyrate copolymers made it reasonable to conclude that the hydrophilic character of the copolymers decreased progressively when the ester group content increased.     

Hyperbranched polymer based on triphenylamine and pyridine: Fluorescent chemosensors for palladium ions

Two new hyperbranched fluorescent conjugated polymers containing pyridine units were synthesized via Heck coupling reaction and Sonogashira coupling reaction, respectively, and characterized by ¹H NMR, ¹³C NMR, FTIR, and GPC. The copolymers are readily soluble in common organic solvents such as chloroform, THF, and DMF. Thermal analysis revealed that the copolymers had good thermal stability. The fluorescence quenching behaviors of the hyperbranched copolymers by metal ions were studied. It was found that the fluorescence of the copolymers can be effectively quenched by Pd²⁺. Moreover, the two hyperbranched copolymers exhibited different quenching efficiency, which may be related to difference in the hindrance for the chelation of pyridine unit with metal ions of the two polymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation,Characterization and Biodegradable Characteristics of Poly(D,L-lactide-co-1,3-trimethylene carbonate)

Poly(D ,L -lactide-co-1,3-trimethylene carbonate) (PLCA) has been synthesized by ring-opening polymerization of 1,3-trimethylene carbonate (CA) and D ,L -lactide (LA) using stannous octoate as catalyst. The copolymers were characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR and differential scanning calorimetry. Water content and static contact angle of distilled water on the polymer surface were used to evaluate hydrophobicity of the polymers. It was found that the hydrophobicity increased with increasing CA fractions in the copolymers. Biodegradation experiments were conducted in vitro and in vivo. The results indicated that the biodegradation behaviour changed from surface to bulk degradation when the LA content exceeded 30mol% in the copolymers. These properties of PLCA may be useful in protein delivery systems. © of SCI.     

Graft copolymerization of 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method

An attempt has been made to graft copolymerize 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method in an aqueous medium. Polypropylene hydroperoxide has been prepared by irradiating recrystallized polypropylene beads from a Co⁶⁰ source in the presence of air. The resulting polypropylene hydroperoxide beads have been used as the backbone polymer and grafting of 4-vinyl pyridine has been studied as a function of various reaction parameters. Optimum conditions for maximum percentage of grafting have been evaluated. Rate of grafting (R_g) has been determined as a function of preirradiation dose and initial monomer concentration. Water has been found to affect percentage of grafting. The graft copolymers have been characterized by spectroscopic method and isolation of the grafted poly(4-VP) from the graft copolymer. A plausible mechanism is proposed to explain the mutual grafting of 4-vinyl pyridine onto polypropylene hydroperoxide. © 1993 John Wiley & Sons, Inc.     

Preparation,characterization and biodegradable characteristics of poly(1,3-trimethylene carbonate-co-glycolide)

Poly(1,3-trimethylene carbonate-co-glycolide) (PGCA) has been synthesized by ring-opening polymerization of 1,3-trimethylene carbonate (CA) and glycolide (GA) with stannous octoate as catalyst. The copolymers were characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR and differential scanning calorimetry. Water content and static contact angle of distilled water on the polymer surface were used to evaluate the hydrophobicity of the copolymers. There was no apparent difference in hydrophobicities of copolymers containing up to 30 mol% GA. The biodegradation of PGCA was conducted in phosphate buffer solution at 37°C and in rats. The results indicated that the degradation rates of PGCA were higher than that of PCA and depended on the GA fraction in the copolymers. Furthermore, degradation occurred in the bulk when the GA content exceeded 20 mol%. With less GA units the degradation became a surface reaction both in vitro and in vivo. These properties of PGCA may be useful in protein delivery systems.     

Dextran functionalized by 4-nitrophenyl carbonate groups. Aminolysis reactions

The modification reaction of dextran with 4-nitrophenyl chloroformate using pyridine as catalyst was studied. The structure of the resulting polymers was determined by means of IR, ¹H and ¹³C NMR spectroscopy as well as by chemical analysis. Under the used experimental conditions only acyclic carbonate groups have been detected. Preliminary experiments have shown that the reaction of 4-nitrophenyl carbonate groups with several model amines is greatly dependent on the basic character of the amine. Model amino-type drugs (phenethylamine and tyramine) were satisfactorily bound to activated dextran with 4-nitrophenyl carbonate groups. The heterogeneous hydrolysis of dextran-phenethylamine or dextran-tyramine adducts showed that no significant hydrolysis takes place under the applied conditions (pH 1 and pH 9, 37°C).     

One-pot synthesis of poly(vinyl alcohol)-based biocompatible block copolymers using a dual initiator for ROP and RAFT polymerization

Biocompatible poly(ε-caprolactone)-b-poly(vinyl alcohol) (PCL-b-PVA), poly(δ-valerolactone)-b-PVA, and poly(trimethylene carbonate)-b-PVA block copolymers were synthesized at 30 °C using a hydroxyl-functionalized xanthate reversible addition-fragmentation chain transfer (RAFT) agent, 2-hydroxyethyl 2-(ethoxycarbonothioylthio)propanoate, as a dual initiator for ring-opening polymerization (ROP) and RAFT polymerization in a one-pot procedure. The ROP of ε-caprolactone, δ-valerolactone, and trimethylene carbonate was first performed using diphenyl phosphate as the ROP catalyst followed by the RAFT polymerization of vinyl chloroacetate after quenching the ROP with 4-dimethyamino pyridine. The resulting block copolymers were aminolyzed directly to the PVA-based biocompatible block copolymers by adding hexylamine to the reaction mixture. To the best of our knowledge, this is the most convenient method for synthesizing PVA-based biocompatible block copolymers.     

Synthesis and properties of polycarbonate copolymers of trimethylene carbonate and 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate

The polycarbonate copolymers poly[trimethylene carbonate‐co‐2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate] [P(TMC‐co‐PTC)] were synthesized by the ring‐opening polymerization of trimethylene carbonate (TMC) and 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate (PTC) with tin(II) 2‐ethylhexanoate and aluminum isopropoxide as the catalysts. These copolymers were further reduced by a palladium/carbonate (Pd/C; 10%) catalyst to produce partly deprotected copolymers. These two types of copolymers were characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, UV spectroscopy, gel permeation chromatography, differential scanning calorimetry, and an automatic contact angle meter. The influences of the feed molar ratio of the monomers, the catalyst concentration, the reaction time, and the reaction temperature on the copolymerization process were also studied. The copolymerization of the TMC and PTC monomers was a nonideal copolymerization, and the copolymerization reactivity ratio of TMC was higher than that of PTC. In vitro degradation tests indicated that the partly deprotected copolymers possessed faster degradation rates and more hydrophilicity than the corresponding unreduced copolymers. Moreover, the degradation of these two type copolymers increased when the pH value of the buffer solutions decreased. In vitro drug‐release experiments showed that these two types of copolymers had steady drug‐release rates and good controlled release properties. Moreover, the partly deprotected copolymers had faster drug‐release rates than the corresponding unreduced copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of ABA‐type block copolymers of trimethylene carbonate and ϵ‐caprolactone

This paper describes the synthesis of a series of ABA‐type triblock copolymers of trimethylene carbonate and ?‐caprolactone with various molar ratios and analyses the thermal and mechanical properties of the resulting copolymers. The structures of the triblock copolymers were characterized by ¹H and ¹³C nuclear magnetic resonance spectroscopy, FT‐IR spectroscopy and gel permeation chromatography. Results obtained from the various characterization methods proves the successful synthesis of block copolymers of trimethylene carbonate and ?‐caprolactone. The thermal properties of the block copolymers were investigated by differential scanning calorimetry. The T_m and ΔH_m values of the copolymers decrease with increasing content of trimethylene carbonate units. Two T_gs were found in the copolymers. Furthermore, both of the T_g values increased with increasing content of trimethylene carbonate units. The mechanical properties of the resulting copolymers were studied by using a tensile tester. The results indicated that the mechanical properties of the block copolymers are related to the molar ratio of trimethylene carbonate and ?‐caprolactone in the copolymers, as well as the molecular weights of the resulting copolymers. The block copolymer with a molar composition of 50/50 possessed the highest tensile stress at maximum and modulus of elasticity. Block copolymers possessing different properties could be obtained by adjusting the copolymer compositions. Copyright © 2004 Society of Chemical Industry     

Modified acrylic-based superabsorbents with hydrophobic monomers: synthesis,characterization and swelling behaviors

A novel family of acrylic acid-based superabsorbent polymers (SAP-n) with controlled-absorption rate were synthesized via aqueous solution polymerization using K₂S₂O₈/NaHSO₃ as the redox initiators, N, N'-methylenebisacrylamide (NMBA) as the crosslinker, 2-methacryloyloxyethyl n-alkyl dimethyl ammonium bromide (C_nDM, n = 4, 8, 12, 16) as the hydrophobic comonomers. The structures of the copolymers were elucidated by FT-IR and ionic chromatographic (IC) analysis respectively, and the swelling properties of the copolymers were examined. It was found that the water absorbency capacity either in distilled water or in 0.9% NaCl brine decreased with increasing hydrophobe length or content, and the water absorbency rate of SAP-n was as expected lower than that of SAP without hydrophobic monomer; in addition, water retention evaluation under different temperatures revealed that this kind of copolymers could absorb and retain large amount of water at room temperature and release it at high temperature.     

Ring‐opening copolymerization and properties of polycarbonate copolymers

A series of polycarbonate copolymers were synthesized by the ring‐opening bulk polymerization of 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate (PTC) and 5,5‐dimethyl trimethylene carbonate (DTC) with tin(II) 2‐ethylhexanoate and aluminum isopropoxide as initiators. The copolymers obtained were characterized by ¹H‐NMR, Fourier transform infrared, and ultraviolet. The influence of the molar ratio of the monomers, the initiators, and their concentrations, the reaction time, and the reaction temperature on the copolymerization was also studied. The copolymerization of monomers DTC and PTC was a nonideal copolymerization, and the copolymerization reactivity ratio of the monomer DTC was higher than that of PTC in the copolymerization process. In vitro release profiles of fluorouracil from the copolymers showed that the copolymer had a steady drug‐release rate and good controlled‐release property. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Block copolymerization of carbon dioxide with cyclohexene oxide and 4-vinyl-1-cyclohexene-1,2-epoxide in based poly(propylene carbonate) by yttrium-metal coordination catalyst

The coordination system, Y(CF₃CO₂)₃ (I)-Zn(Et)₂ (II)-m-hydroxybenzoic acid (III), was found to be the most active catalyst to generate poly(propylene carbonate) (PPC) from carbon dioxide and propylene oxide (PO) in 1,3-dioxolane. A high yield and a high molecular weight could be obtained at the conditions of a II/I molar ratio of 20, a III/II molar ratio of 1.0, a temperature of 60 °C, and a pressure of 2.76 MPa. The carbonate content in the resultant PPC was found to be nearly 100%.The block copolymerization in the based PPC was carried out by in situ introducing an epoxide other than PO right after the copolymerization of carbon dioxide with PO using the same catalyst system. The IR and ¹H NMR spectra as well as the measured molecular weights verified the resulting copolymers were block copolymers. For the block copolymerization of CO₂ with cyclohexene oxide and CO₂ with 4-vinyl-1-cyclohexene-1,2-epoxide in the based PPC, the yield as well as the cyclohexene carbonate and the 4-vinyl-1-cyclohexene carbonate contents were found to increase with increasing temperature. The most appropriate temperature was around at 80 °C. The weight-average molecular weights of the block copolymers lay in a range from 2.44×10⁵ to 3.16×10⁵, the polydispersity in a range from 5.0 to 6.3, and the 10% weight loss temperature in a range from 226 to 253 °C. The thermal and mechanical properties of the resultant block copolymers lay between those of PPC, poly(cyclohexene carbonate), and poly(4-vinyl-1-cyclohexene carbonate), indicating the desired properties of a polymer can be achieved via block copolymerization.     

Radiation-initiated graft copolymerization of 4-vinylpyridine onto polyethylene and polytetrafluoroethylene films and anion-exchange membranes therefrom

Radiation-initiated graft copolymerization of 4-vinylpyridine (4VP) onto low-density polyethylene (LDPE) and polytetrafluoroethylene (PTFE) films was carried out by γ-rays from ⁶⁰Co source in nitrogen atmosphere. The direct method of multiple grafting was used, connected with posteffect taking place at irradiation doses from 1 to 35 kGy. Thus the monomer diffused into the polymer matrix together with the stepwise generation of free radicals to reduce the thickness of the nongrafted layer. The grafting proceeds in the amorphous phase of the polymers which is further amorphized by the irradiation. Copolymers with grafting degree (P) from 17 to 75% for LDPE and from 0.7 to 13% for PTFE were obtained. The dependence of the degree of grafting of 4VP on irradiation dose was established. The spectral and thermodynamic properties of the synthesized copolymers were studied. The degree of crystallinity was found to decrease and a two-stage mechanism of thermooxidative destruction was observed. The synthesized copolymers contain pyridine groups determining their anion-exchange properties. The initial pyridine groups in the grafted copolymers were quaternized. Some of the basic characteristics, such as water content and specific electric resistance of anion-exchange membranes (AEM) were studied depending on the grafting degree of 4VP. The ionomers studied possess high transport number (t_- ∼ 0.8–0.9), good diffusion characteristics (9.2 × 10⁻⁸−1.7 × 10⁻⁷ cm²/s), and suitable tensile properties. The AEM obtained, combined with the cation exchange membranes we have synthesized earlier on the same polymeric basis, can be used successfully in various electrodialysis processes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1469–1475, 1997     

Radiation‐induced graft copolymerization of 2‐vinylpyridine and styrene onto isotactic polypropylene fiber

Isotactic polypropylene fiber (IPP) was graft‐copolymerized using 2‐vinyl pyridine (2‐VP) and styrene (sty) as the monomers by the mutual irradiation method in air. The percentage of grafting was determined as a function of various reaction parameters and it was found that the maximum grafting of 2‐VP (114%) and sty (76%) was obtained at an optimum dose of 1.08 × 10⁴ and 0.64 × 10⁴ Gy using 1.8 × 10⁻² mol of 2‐VP and 4.3 × 10⁻² mol of sty, respectively. The graft copolymers were characterized by differential scanning calorimetric analysis and isolation of the grafted chains from the grafted iPP samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2959–2969, 1999     

Alkaline hydrolysis of homopolymers and copolymers of 2-hydroxypropyl methacrylate

Homopolymers of 2-hydroxypropyl methacrylate (HPMA) and copolymers with acrylic acid (AA) were prepared in 1,4-dioxane. The reactivity ratios were determined to be r_AA = 0.27 ± 0.04 and r_HPMA = 2.2 ± 0.2. The alkaline hydrolysis by sodium hydroxide of the HPMA monomer and polymers showed that while the HPMA monomer hydrolyzed readily as expected for a low-molecular-weight carboxylic ester the HPMA homopolymer and water-soluble sodium acrylate (NaA) copolymers were extremely resistant to alkaline hydrolysis. The saponification reaction followed a second-order rate equation, being first order with respect to both HPMA and hydroxide ion concentration. The Arrhenius parameters, activation energy E and frequency factor A, for the alkaline hydrolysis of HPMA monomer in water were found to be E = 10.3 Kcal/mol and A = 1.5 × 10⁸ L/mol min, and those for the NaA–HPMA copolymers in water were found to be E = 24 kcal/mol and A = 4 × 10¹² L/mol min. The NaA–HPMA copolymers had a limiting extent of hydrolysis, ranging from 9–90% ester conversion. A sharp rate decrease at low conversion was noted during the HPMA homopolymer hydrolysis in 58/42 dimethyl sulfoxide/water, allowing the calculation of two distinct reaction rates. © 1992 John Wiley & Sons, Inc.     

A new synthetic approach to asymmetric amphiphilic ABA′ block copolymers by ATRP and click reactions

Well‐defined asymmetric amphiphilic ABA′ block copolymers composed of poly(ethylene oxide) monomethylene ether (MPEO) with different molecular weights as A or A′ block and poly(styrene) (PS) as B block were synthesized by the combination of atom transfer radical polymerization (ATRP) and click reactions. First, bromine‐terminated diblock copolymer poly(ethylene oxide) monomethylene ether‐block‐poly(styrene) (MPEO‐PS‐Br) was prepared by ATRP of styrene initiated with macroinitiator MPEO‐Br, which was prepared from the esterification of MPEO and 2‐bromoisobutyryl bromide. Then, the azido‐terminated diblock copolymers MPEO‐PS‐N₃ were prepared through the bromine substitution reaction with sodium azide. Propargyl‐terminated MPEO with a different molecular weight was prepared under the basic condition from propargyl alcohol and p‐toluenesulfonyl‐terminated MPEO, which was prepared through the esterification of MPEO and p‐toluenesulfochloride using pyridine as solvent. Asymmetric amphiphilic ABA′ block copolymers, with a wide range of number–average molecular weights from 1.92 × 10⁴ to 2.47 × 10⁴ and a narrow polydispersity from 1.03 to 1.05, were synthesized via a click reaction of the azido‐terminated diblock copolymers and the propargyl‐terminated MPEO in the presence of CuBr and 1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) catalyst system. The structures of these ABA′ block copolymers and corresponding precursors were characterized by NMR, IR, and GPC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Card-type Organosiloxane Copolymers with Silaoxaphenantrene Fragments in Dimethylsiloxane Chain

Abstract

The reaction of heterofunctional condensation of 1,1-dichloro-1-sila-2-oxaphenantrene with α,ω-dihydroxydimethylsiloxane in the presence of pyridine has been investigated and card-type organosiloxane copolymers with regular arrangement of silaoxaphenantrene fragments in dimethylsiloxane chain has been obtained. It is shown, that at small length of linear dimethylsiloxane chain, besides the reaction of intermolecular condensation, intramolecular cyclization takes place with formation of bicyclic compounds. Thermogravimetric, DSC, GPC and X-ray analysis of the synthesised copolymers have been carried out.     

Novel amphiphilic polymer gel electrolytes based on (PEG‐b‐GMA)‐co‐MMA

Amphiphilic conetwork–structured copolymers containing different lengths of ethylene oxide (EO) chains as ionophilic units and methyl methacrylate (MMA) chains as ionophobic units were prepared by free radical copolymerization and characterized by FTIR and thermal analysis. Polymer gel electrolytes based on the copolymers complexed with liquid lithium electrolytes (dimethyl carbonate (DMC) : diethyl carbonate (DEC) : ethylene carbonate (EC) = 1 : 1 : 1 (W/W/W), LiPF₆ 1.0M) were characterized by differential scanning calorimetry and impedance spectroscopy. A maximum ion conductivity of 4.27 × 10^?4 S/cm at 25^oC was found for the polymer electrolyte based on (PEG2000‐b‐GMA)‐co‐MMA with long EO groups. Moreover, the effect of temperature on conductivity of the amphiphilic polymer electrolytes obeys the Arrhenius equation. The good room temperature conductivity of the polymer electrolytes is proposed to relate to the enhancement in the amorphous domain of the copolymers due to their amphiphilic conetwork structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010