Synthesis and biodegradability evaluation of 2‐methylene‐1,3‐dioxepane and styrene copolymers

Biodegradable copolymers of 2‐methylene‐1,3‐dioxepane (MDO) and styrene (ST) were synthesized by free‐radical copolymerization using di‐t‐butyl peroxide (DTBP) as the initiator. The copolymers containing ester units were characterized by Fourier transform infrared (FTIR), ¹H‐NMR, and ¹³C‐NMR spectroscopy. Their molecular weight and polydispersity index were determined by gel permeation chromatography (GPC). In vitro enzymatic degradation of poly(MDO‐co‐ST) was performed at 37°C in phosphate buffer solution (PBS, pH = 7.4) in the presence of Pseudomonas lipase or crude enzyme extracted from earthworm. The experiment showed that incorporating ester units into C? C backbone chain of polystyrene would result in a biodegradable copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1146–1151, 2007     

Synthesis of copolymer from 1,3,5‐trioxane and 1,3‐dioxolane catalyzed by Maghnite‐H+

Copolymers (polyoxymethylene) were prepared by cationic copolymerization of 1,3,5‐trioxane (TOX) with 1,3‐dioxolane (DOX) in the presence of Maghnite‐H⁺ (Mag‐H⁺) in solution. Maghnite is a Montmorillonite sheet silicate clay, with exchanged protons to produce Mag‐H⁺. Various techniques, including ¹H‐NMR, ¹³C‐NMR, FT‐IR spectroscopy, and Ubbelohde viscometer were used to elucidate structural characteristics properties of the resulting copolymers. The influence of the amount of catalyst, of dioxolane (DOX), temperature, solvent, and time of copolymerization on yield and on intrinsic viscosity of copolymers was studied. The yield of copolymerization depends on the amount of Mag‐H⁺ used and the reaction time. We also propose mechanisms involved in the synthesis of copolymer (polyoxymethylene). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of pH‐sensitive networks containing degradable poly(1,3‐dioxolane) segments

pH‐sensitive networks were obtained by radical copolymerization of telechelic poly(1,3‐dioxolane) (PDXLDA) with acrylic acid (AA). PDXLDA was synthesized by acrylation of the corresponding dihydroxylated polyacetal (polyDXL) with AA in pyridine. The copolymer networks of poly(AA‐b‐DXL) showed pH sensitivity due to —COOH groups, which are insoluble in any solvents, but can swell in water or good solvents. The swelling behavior is closely related to the solvents and is composition‐dependent. The networks containing polyDXL segments can be decrosslinked under acidic conditions due to the low ceiling temperature of polyDXL. After degradation, the linear segments of polyDXL became cycled molecules. The networks' structure, swelling behavior, and degradation were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, GC–MS analysis, and swelling data. This kind of material can be potentially used in biosystems, such as in intelligent drug‐delivery systems. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1678–1682, 2002     

Copolymerization of N‐(4‐carboxyphenyl) itaconimide or N‐(4‐carboxyphenyl) itaconamic acid with methyl methacrylate

This paper describes the synthesis and characterization of N‐(4‐carboxyphenyl) itaconamic acid (CPA) and N‐(4‐carboxyphenyl) itaconimide (CPI) obtained by reacting itaconic anhydride with p‐aminobenzoic acid. Structural and thermal characterization of CPA and CPI was done using ¹H‐NMR, FTIR, and differential scanning calorimetry (DSC). Copolymerization of CPA or CPI with methyl methacrylate (MMA) in solution was carried out at 60 °C using azobisisobutyronitrile as an initiator and dimethyl acetamide or THF as solvent. Feed compositions having varying mole fractions of CPA or CPI ranging from 0.05–0.20 or 0.1–0.5 were taken to prepare copolymers. Copolymerizations were terminated at low percentage conversion. Structural characterization of copolymers was done by ¹H‐NMR and elemental analysis. Copolymer composition was determined using percentage nitrogen content. The reactivity ratios were r₁ (MMA) = 0.68 ± 0.06 and r₂ (CPI) = 0.46 ± 0.06. The intrinsic viscosity [η] was determined using an Ubbelohde suspension level viscometer. [η] decreased with increasing mole fraction of N‐(p‐carboxyphenyl) itaconimide or N‐(p‐carboxyphenyl) itaconamic acid in copolymers. Glass transition temperature and thermal stability of the copolymers were determined using DSC and thermogravimetric analysis, respectively. The glass transition temperature (T_g) as determined from DSC scans increased with increasing amounts of CPA or CPI in copolymers. A significant improvement in the char yield was observed upon copolymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1909–1915, 2005     

Synthesis and characterization of poly[4‐(2‐thiazolylazo)phenyl methacrylate]‐co‐poly(methyl methacrylate)

A new methacrylic monomer, 4‐(2‐thiazolylazo)phenylmethacrylate (TPMA) was synthesized. Copolymerization of the monomer with methyl methacrylate (MMA) was carried out by free radical polymerization in THF solution at 70 ± 0.5°C, using azobisisobutyronitrile (AIBN) as an initiator. The monomer TPMA and the copolymer poly(TPMA‐co‐MMA) were characterized by Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance (NMR), and elemental analysis methods. The polydispersity index of the copolymer was determined using gel permeation chromatography (GPC). Thermogravimetric analysis (TGA) of the copolymer performed in nitrogen revealed that the copolymer was stable to 270°C. The glass transition temperature (T_g) of the copolymer was higher than that of PMMA. The copolymer with a pendent aromatic heterocyclic group can be dissolved in common organic solvents and shows a good film‐forming ability. Both the monomer TPMA and the copolymer poly (TPMA‐co‐MMA) have bright colors: orange and yellow, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2152–2157, 2007     

Binary copolymerization of 4‐methyl‐1,3‐pentadiene with styrene,butadiene and isoprene catalysed by a titanium [OSSO]‐type catalyst

Binary copolymerization of 4‐methyl‐1,3‐pentadiene (4MPD) with styrene, butadiene and isoprene promoted by the titanium complex dichloro{1,4‐dithiabutanediyl‐2,2′‐bis[4,6‐bis(2‐phenyl‐2‐propyl)phenoxy]}titanium activated by methylaluminoxane is reported. All the copolymers are obtained in a wide range of composition and the molecular weight distributions obtained from gel permeation chromatographic analysis of the copolymers are coherent with the materials being copolymeric in nature. The copolymer microstructure was fully elucidated by means of ¹H NMR and ¹³C NMR spectroscopy. Differential scanning calorimetry shows an increase of glass transition temperature (T_g) with the amount of 4MPD in the copolymers with butadiene and isoprene, while in the copolymers with styrene T_g is increased on increasing the amount of styrene. © 2016 Society of Chemical Industry     

Synthesis,characterizations and thermal behavior of methyl methacrylate and N‐(p‐carboxyphenyl) methacrylamide/acrylamide copolymers

The synthesis, characterization, and thermal properties of copolymers of methyl methacrylate (MMA) and N‐(p‐carboxyphenyl) methacrylamide/acrylamide (CPMA/CPA) are described. The copolymerization was carried out in solution by taking different mole fractions (0.1–0.5) of CPMA/CPA in the initial feed using azobisisobutyronitrile as an initiator and dimethylformamide as a solvent at 60°C. The copolymer composition was determined from ¹H‐NMR spectra by taking the ratio of the proton resonance signal due to the  OCH₃ of MMA (δ = 3.59 ppm) and the aromatic protons (δ = 7.6–7.8 ppm) of CPMA/CPA. The monomer reactivity ratios of MMA:CPMA and MMA:CPA were determined using the Fineman Ross and Kelen Tudos methods and were found to be 1.32 ± 0.01 [MMA], 1.11 ± 0.02 [CPMA], 2.60 ± 0.01 [MMA], and 0.20 ± 0.01 [CPA]. Incorporation of these comonomers in the MMA backbone resulted in an improvement in the glass‐transition temperature and thermal stability. The percent char also increased with the increase of CPMA/CPA content in the copolymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 259–267, 2000     

Studies on the copolymerization of methyl methacrylate with N‐(o/m/p‐chlorophenyl) itaconimides

The article describes the synthesis and characterization of N‐aryl itaconimide monomers such as: N‐(p‐chlorophenyl) itaconimide (PI)/N‐(m‐chlorophenyl) itaconimide (MI)/N‐(o‐chlorophenyl) itaconimide (OI) and its copolymerization behavior with MMA. The homopolymers and copolymers of N‐aryl itaconimides and methyl methacrylate (MMA, M₂) were synthesized by varying the mol fraction of N‐aryl itaconimides in the initial feed from 0.1 to 0.5 using azobisisobutyronitrile (AIBN) as an initiator and tetrahydrofuran (THF) as the solvent. Copolymer composition was determined using ¹H‐NMR spectroscopy [by taking the ratio of intensities of signals due to ? OCH₃ of MMA (δ = 3.59 ppm) and the aromatic proton (δ = 7.2–7.5 ppm) of N‐aryl itaconimides] and percent nitrogen content. The reactivity ratios were found to be r₁ = 1.33 and r₂ = 0.36 (PI‐MMA) r₁ = 1.15 and r₂ = 0.32 (MI‐MMA) and r₁ = 0.81 and r₂ = 0.35 (OI‐MMA). Molecular weight as determined using high‐performance liquid chromatography decreased with increasing mol fraction of itaconimides in copolymers. All the polymers had a polydisperstivity index in the range of 1.5–2.6.Thermal characterization was done using differential scanning calorimetry and dynamic thermogravimetry in nitrogen atmosphere. Incorporation of these N‐aryl itaconimides in PMMA backbone resulted in an improvement in glass transition temperature (T_g) and thermal stability. Percent char increased with the increase of PI/MI/OI content in the copolymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2078–2086, 2001     

One‐step synthesis of bis‐macromonomers of poly(1,3‐dioxolane) catalyzed by Maghnite‐H+

Telechelic poly(1,3‐dioxolane) (PDXL) bis‐macromonomers bearing methyl methacrylate end groups were prepared by cationic ring‐opening polymerization of 1,3‐dioxolane (DXL), in the presence of methacrylic anhydride, catalyzed by Maghnite‐H⁺ (Mag‐H⁺), in bulk and in solution. Maghnite is a montmorillonite sheet silicate clay, which exchanged with protons to produce Mag‐H⁺. The influence of the amount of Mag‐H⁺, monomer (DXL), and methacrylic anhydride on monomer conversion was studied. The polymerization yield and the molecular weight of α,ω‐bis‐unsaturated PDXLs prepared depend on the amount of Mag‐H⁺ used and the reaction time. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis and characterization of new polyamides derived from 1,3‐(4‐carboxy phenoxy) propane and aromatic diamines

Six new polyamides 5a‐f containing flexible trimethylene segments in the main chain were synthesized through the direct polycondensation reaction of 1,3‐(4‐carboxy phenoxy) propane 3 with six derivatives of aromatic diamines 4a‐f in a medium consisting of N‐methyl‐2‐pyrrolidone, triphenyl phosphite, calcium chloride, and pyridine. The polycondensation reaction produced a series of novel polyamides containing flexible trimethylene segments in the main chain in high yield with inherent viscosities between 0.32 and 0.68 dL/g. The resulted polymers were fully characterized by means of FTIR spectroscopy, elemental analyses, inherent viscosity, and solubility tests. Thermal properties of these polymers were investigated by using thermal gravimetric analysis (TGA) and differential thermal gravimetric (DTG). The glass‐transition temperatures of these polyamides were recorded between 165 and 190°C by differential scanning calorimetry, and the 10% weight loss temperatures were ranging from 360 to 430°C under nitrogen. 1,3‐(4‐Carboxy phenoxy) propane 3 was prepared from the reaction of 4‐hydroxy benzoic acid 1 with 1,3‐dibromo propane 2 in the presence of NaOH solution. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Controllable radical copolymerization of styrene and methyl methacrylate using 1,1,2,2‐tetraphenyl‐1,2‐bis(trimethylsilyloxy) ethane as initiator

Copolymerization of styrene (St) and methyl methacrylate (MMA) was carried out using 1,1,2,2‐tetraphenyl‐1,2‐bis (trimethylsilyloxy) ethane (TPSE) as initiator; the copolymerization proceeded via a “living” radical mechanism and the polymer molecular weight (M_w) increased with the conversion and polymerization time. The reactivity ratios for TPSE and azobisisobutyronitrile (AIBN) systems calculated by Finemann–Ross method were r_St = 0.216 ± 0.003, r_MMA= 0.403 ± 0.01 for the former and r_St= 0.52 ± 0.01, r_MMA= 0.46 ± 0.01 for the latter, respectively, and the difference between them and the effect of polymerization conditions on copolymerization are discussed. Thermal analysis proved that the copolymers obtained by TPSE system showed higher sequence regularity than that obtained by the AIBN system, and the sequence regularity increased with the content of styrene in copolymer chain segment. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1474–1482, 2001     

Synthesis and characterization of poly(1,3‐thiazol‐2‐yl‐carbomoyl) methyl methacrylate: Its metal complexes and antimicrobial activity studies

Poly(1,3‐thiazol‐2‐yl‐carbomoyl) methyl methacrylate [poly(TCMMA)] is prepared in dimethyl sulfoxide using 2,2′‐azobisisobutyronitrile as an initiator at 60°C. Poly(TCMMA) is characterized by IR and ¹H‐NMR spectroscopic techniques. Cadmium(II), copper(II), and nickel(II) chelates of poly(TCMMA) were synthesized. An elemental analysis of the polychelates suggests a metal/ligand ratio of 1:2. The polychelates are further characterized by IR and magnetic susceptibility measurements. The thermal properties of the polymer and metal chelates are also discussed. The molecular weights of the poly(TCMMA) are determined by the gel permeation chromatography technique. The antimicrobial activities of the polymer and metal chelates are tested against Staphylococcus aureus COWAN I (bacteria), Escherichia coli ATCC 25922 (bacteria), Listeria monocytogenes SCOTTA (bacteria), Bacillus subtilis LMG (bacteria), Enterobacter aeroginosa CCM 2531 (bacteria), Klebsiela pneumania FMCS (bacteria), Candida albicans CCM 314 (Mayo yeast), and Saccharamyces cerevisiae UGA 102 (Mayo yeast). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3244–3251, 2003     

Water‐soluble copolymers from functionalized monomers (sodium o‐ and p‐methacryloylaminophenylarsonate): Synthesis and characterization

Copolymers of sodium o‐methacryloylaminophenylarsonate (o‐MAPHA‐Na) 1 and p‐methacrylolylaminophenylarsonate (p‐MAPHA‐Na) 2 with sodium acrylate (AA‐Na) 3 , sodium methacrylate (AM‐Na) 4 and acrylamide (AAD) 5 were prepared by free radical polymerization in aqueous media at 70°C using potassium persulfate (K₂S₂O₈) as the initiator. The total monomer concentration was carried out at 0.5M and the feed ratio ( M₁ : M₂ ) was varied from 10 : 90 to 90 : 10 mol%. The kinetic study was carried out by dilatometric method. The copolymer compositions were calculated by arsenic content in the copolymers. The As content (ppm) was determined by atomic absorption spectrometry (AAS). The reactivity ratios (r₁, r₂) were estimated by the Kelen‐Tüdös linearization method as well as error‐in‐variables method using the computer program RREVM®. In all cases, r₁ < 1 and r₂ > 1, indicating a tendency to form random copolymers. The values suggest that the copolymers contain a larger proportion of comonomer (i.e., AA‐Na, AM‐Na, or AAD). Weight‐average molar masses (M _w) of copolymers were determined by multi‐angle light scattering. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Shape memory effect of poly(methylene‐1,3‐cyclopentane) and its copolymer with polyethylene

Poly(methylene‐1,3‐cyclopentane) (PMCP) cyclopolymerized from 1,5‐hexadiene by metallocene catalyst, rac‐(ethylenebis(1‐indenyl))Zr(N(CH₃)₂)₂ is partially crystalline and has a value of elongation at break of more than 400% in the temperature range 25–85 °C. The shape memory effect of PMCP with moderate molecular weight is enhanced by sequentially polymerized polyethylene segments, the crystalline phase of which seems to strengthen the fixed structure which memorizes the original shape. The glass transition temperature or melting temperature of PMCP can be selectively used as shape recovery temperature when an appropriate deformation temperature is chosen. © 2002 Society of Chemical Industry     

Synthesis and characterization of temperature‐responsive poly(vinyl alcohol)‐based copolymers

A poly(vinyl alcohol) (PVA)/sodium acrylate (AANa) copolymer was synthesized to improve the water solubility of PVA at the ambient temperature. Furthermore, a series of temperature‐responsive acetalyzed poly(vinyl alcohol) (APVA)‐co‐AANa samples of various chain lengths, degrees of acetalysis (DAs), and comonomer contents were prepared via an acid‐catalysis process. Fourier transform infrared and ¹H‐NMR techniques were used to analyze the compositions of the copolymers. The measurement of the turbidity change for APVA‐co‐AANa aqueous solutions at different temperatures revealed that the lower critical solution temperature (LCST) of the copolymers could be tailored through the control of the molecular weight of the starting PVA‐co‐AANa, DA, and comonomer ratios. Lower LCSTs were observed for APVA‐co‐AANa with a longer chain length, a higher DA, and fewer acrylic acid segments. In addition, the LCSTs of the APVA‐co‐AANa aqueous solutions appeared to be salt‐sensitive. The LCSTs decreased as the concentration of NaCl increased. Moreover, atomic force microscopy images of APVA‐co‐AANa around the LCST also proved the temperature sensitivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization of the luminescent lanthanide complexes with copolymer of (Z)‐4‐oxo‐4‐phenyloxyl‐2‐butenoic acid and styrene

The copolymers of (Z)‐4‐oxo‐4‐phenoxyl‐2‐butenoic acid with styrene (PSt/OPBA) and their macromolecular luminous lanthanide complexes (Ln‐PSt/OPBA) have been synthesized and characterized by means of GPC, elemental analysis, FTIR, X‐ray powder diffraction, spectral analysis, and thermal analysis. The IR studies showed that the carboxylic groups on the side chain of the polymer were coordinated to lanthanide ions by bidentate manner. However, the ethereal oxygen, instead of carbonyl, also bonded to the central lanthanide ions, which was an intriguing phenomenon for ester‐coordinated complexes. X‐ray diffraction experiments revealed that these PSt/OPBA copolymers were amorphous, but Ln‐PSt/OPBA were crystalline, in which the complex Eu‐L^c belonged to a high symmetric structure of orthorhombic quadratic system, with a = 10.59 ± 0.02 Å, c = 8.02 ± 0.01 Å; c/a = 0.763. In addition, the value δ (the number of free carboxylic groups) in Ln‐PSt/OPBA complexes increased with the decreasing mole ratio of styrene in the copolymers, while it decreased with increasing pH values of the solution. Eu³⁺ and Tb³⁺ complexes exhibited characteristic fluorescence with comparatively high brightness and good monochromaticity, and the fluorescence intensity was enhanced with increasing the content of lanthanide up to around 18 wt % without typical fluorescence concentration quenching behavior in the solid state. So using polymers as a matrix, Ln‐PSt/OPBA are likely to provide new materials that possess specific properties and desired features. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012