Extended Kelen-Tudos Methods Research Articles

Copolymerization of 4-biphenyl methacrylate with glycidyl methacrylate: Synthesis, Characterization, thermal properties and determination of monomer reactivity ratios

The methacrylic monomer, 4-biphenylmethacrylate (BPM) was synthesized by reacting 4-biphenyl phenol dissolved in ethyl methyl ketone (EMK) with methacryloyl chloride in presence of triethylamine as a catalyst. The copolymers of BPM with glycidyl methacrylate (GMA) were synthesized by free radical polymerization in EMK solution at 70±1 °C using benzoyl peroxide as a free radical initiator. The copolymerization behaviour was studied in a wide composition interval with the mole fractions of BPM ranging from 0.15 to 0.9 in the feed. The copolymers were characterized by FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. The solubility was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the polymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in BPM content. The thermogravimetric analysis of the polymers showed that the thermal stability of the copolymer increases with BPM content. The copolymer composition was determined using 1H-NMR spectra. The monomer reactivity ratios were determined by the application of conventional linearization methods such as Fineman-Ross (r1=0.392 ± 0.006, r2 = 0.358 ± 0.007, Kelen-Tudos (r1= 0.398 ± 0.004, r2= 0.365 ± 0.013) and extended Kelen-Tudos methods (r1= 0.394 ± 0.004, r2= 0.352 ± 0.006).

Co-polymerization of 4-biphenyl methacrylate with methyl methacrylate: synthesis, characterization and determination of monomer reactivity ratios

Co-polymerization of BPM with methyl methacrylate (MMA) has been carried out in methyl ethyl ketone (MEK) by free radical solution polymerization at 70 ± 1°C utilizing benzoyl peroxide (BPO) as initiator. Poly(BPM-co-MMA) co-polymers were characterized by FT-IR, 1H-NMR and 13C-NMR spectroscopy. The molecular weights (M w and M n) and polydispersity indices (M w//M n) of the polymers were determined using gel permeation chromatograph. The glass transistion temperatures (T g) of the co-polymer increases with MMA content. Thermogravimetric analysis of the polymers performed in nitrogen shows that the stability of the co-polymer increases with an increase in BPM content. The solubility of the polymers was tested in various polar and nonpolar solvents. Co-polymer compositions were determined by 1H-NMR spectroscopy by comparing the integral peak heights of well separated aromatic and aliphatic protons peaks. The monomer reactivity ratios were determined using Fineman–Ross (r 1 = 1.70 ± 0.054, r2 = 0.065 ± 0.004), Kelen–Tudos (r1 = 1.73 ± 0.035, r2 = 0.077 ± 0.008) and extended Kelen–Tudos methods (r1 = 1.866 ± 0.100, r2 = 0.069 ± 0.008).

1,4-pentadien-3-one-1-p-hydroxyphenyl-5-p-phenyl Acrylate: Crosslinking Studies and Reactivity Ratios with Glycidyl Methacrylate

1,4-pentadien-3-one-1,5-bis(p-hydroxyphenyl) (PBHP) was synthesized by reacting p-hydroxybenzaldehyde and acetone in the presence of HCl gas. 1,4-pentadien-3-one-1-p-hydroxyphenyl-5-p-phenyl acrylate (HPA) was prepared by reacting PBHP with acryloyl chloride in ethyl methyl ketone (EMK) medium at 0 °C. Copolymerization of different feed compositions of HPA with glycidyl methacrylate (GMA) was carried out using benzoyl peroxide (BPO) as initiator in EMK solvent under nitrogen atmosphere at 70±1 °C. Polymers thus synthesized were characterized by IR and NMR (1H/13C) spectroscopic techniques. Reactivity ratios of the monomers were calculated from the 1H NMR data by applying linearization methods such as Fineman–Ross, Kelen–Tudos and extended Kelen–Tudos methods. Photocrosslinking property of the polymer samples was studied using the solvent method. Thermal stability of the polymers were measured using thermogravimetric analysis. Molecular weights (Mw and Mn) and polydispersity value of the polymer were determined using gel permeation chromatographic technique.

Water-soluble Copolymers of N-vinylpyrrolidone and Vinyl Acetate: Synthesis, Characterization, and Monomer Reactivity at High Conversions

Homogeneous copolymers of N-vinylpyrrolidone (VP) and vinyl acetate (VA) which form clear aqueous solutions were prepared by free radical polymerization in a solution of isopropanol alcohol, using 2,2-azobisisobutyronitrile as an initiator. They were characterized by FTIR, 1H-NMR, and element analysis studies. The reactivity ratios of the monomer were computed by the Extended Kelen–Tudos method at high conversions, using data from both 1H-NMR and elemental analysis studies. The reactivity ratios of VP and VA in a homogenous copolymer were observed to be very different from that of a heterogeneous copolymer. Additional information was obtained by finding out the sequence length distribution for copolymers.

Fast, multi-responsive microgels based on photo-crosslinkable poly(2-(dimethylamino)ethyl methacrylate)

Multi-responsive microgels based on poly(2-( N, N-dimethylamino)ethyl methacrylate) were developed and their properties were investigated. The primary goal of this research was to speed up the stimulus-response time of the hydrogels to a level usable for actuator applications, by reducing the diffusion distance of water. The gels were prepared by a UV induced photodimerization of a copolymer of 2-(dimethylamino)ethyl methacrylate and 4-cinnamoyl-phenyl methacrylate. Patterning studies showed that these materials can be used as photo-resist materials with high resolution at short exposure times. They showed lower critical solution temperature behavior in water, as well as pH dependent solubility and swelling ratios. While 1 mm thick gels showed response times to temperature and pH-changes of several hours, Si-supported microgels of 300 nm thickness had response times in the range of only a few seconds. The copolymer was prepared by free radical copolymerization, and the reactivity ratios were determined with the extended Kelen Tudos method. Spin-coating of this copolymer on Si supports and subsequent UV-irradiation yielded microgels of variable thickness (200 nm–15 μm), which was determined by confocal scanning laser microscopy. Surface plasmon resonance spectroscopy measurements demonstrated the fast, stimuli-responsive swelling behavior, while differential scanning calorimetry gave insight into the morphology of the networks.

Synthesis, characterization, and reactivity ratios of copolymers derived from 4‐nitrophenyl acrylate and n‐butyl methacrylate

AbstractFree‐radical copolymerization of 4‐nitrophenyl acrylate (NPA) with n‐butyl methacrylate (BMA) was carried out using benzoyl peroxide as an initiator. Seven different mole ratios of NPA and BMA were chosen for this study. The copolymers were characterized by IR, 1H‐NMR, and 13C‐NMR spectral studies. The molecular weights of the copolymers were determined by gel permeation chromatography and the weight‐average (Mw) and the number‐average (Mn) molecular weights of these systems lie in the range of 4.3–5.3 × 104 and 2.6–3.0 × 104, respectively. The reactivity ratios of the monomers in the copolymer were evaluated by Fineman–Ross, Kelen–Tudos, and extended Kelen–Tudos methods. The product of r1, r2 lies in the range of 0.734–0.800, which suggests a random arrangement of monomers in the copolymer chain. Thermal decomposition of the polymers occurred in two stages in the temperature range of 165–505°C and the glass transition temperature (Tg) of one of the systems was 97.2°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1817–1824, 2003

POLYACRYLONITRILE PRECURSORS FOR CARBON FIBER WITH IMIDOCARBOX YLIC ACID UNITS: COPOLYMERIZATION OF ACRYLONITRILE WITH MALEIMIDOBENZOIC ACID

ABSTRACT 4-Maleimidobenzoic acid (MBA) was explored as a comonomer in polyacrylonitrile (PAN) precursors for carbon fiber. The copolymerization of acrylonitrile (AN) with MBA was carried out in DMF. The reactivity of MBA was considerably less than that of AN, which was manifested as a negative reactivity ratio for the former. The r MBA- values from −0.24 to −0.33 and r AN values of 1.07 were obtained by Kelen-Tudos and extended Kelen-Tudos methods. The penultimate reactivity ratios were determined by both linear and non-linear methods. The values were r 1=0.0093, r 1′=0.0132, r 2=1.063 and r 2′=1.625. The relative MBA concentration in the copolymer decreased drastically on enhancing its content in the monomer mixture. The penultimate model could satisfactorily explain the feed-copolymer composition profile for the whole composition range. MBA caused a decrease in the apparent copolymerization rate and molecular weight in agreement with the observed trends in the reactivity ratios. A statistical prediction of monomer sequences based on reactivity ratios implied that MBA existed as a lone monomer unit between the long sequences of AN units. This sequence distribution is suited for the efficiency of MBA in cyclisation reaction, which stabilizes PAN during its pyrolysis. Optimum thermal stabilization effect and char yield were observed for copolymers with around 3 mol% MBA in the chain.

Copolymers of 4-nitrophenyl methacrylate with styrene: Synthesis, characterization, and reactivity ratios

Free-radical copolymerization of 4-nitrophenyl methacrylate (NPMA) with styrene (STY) was carried out at 65°C in 2-butanone by using benzoyl peroxide (BPO) as initiator. NPMA was characterized by spectral and microelemental analysis. Homo- and copolymers were characterized by IR, 1H-, and 13C-NMR studies and their copolymer compositions were evaluated by 1H-NMR spectroscopic technique. The copolymer reactivity ratios were calculated using Fineman–Ross, Kelen–Tüdos, and extended Kelen–Tudos methods. The Q,e values for NPMA were determined by Alfrey–Price Q,e rule. Thermal properties of the homo- and copolymers were studied by thermogravimetric analysis and differential scanning calorimetry methods. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1186–1193, 1999

4-CHLOROPHENYL ACRYLATE AND GLYCIDYL METHACRYLATE COPOLYMERS: SYNTHESIS, CHARACTERIZATION, REACTIVITY RATIOS, AND APPLICATION

4-Chlorophenyl acrylate (CPA) and glycidyl methacrylate (GMA) copolymers having different copolymer compositions were synthesized in 1,4-dioxane using benzoyl peroxide as initiator at 70 ± 0.5°C. Using 1H-NMR spectroscopy, the composition of the two monomers in the copolymers were calculated by comparing the integral values of the aromatic and alifatic proton peaks. The reactivity ratios (average r1 = 0.03 ± 0.04 and r2 = 2.27 ± 0.55) were calculated by Fineman-Ross, Kelen-Tudos and extended Kelen-Tudos methods. The copolymers were characterized by 1H and proton decoupled 13C-NMR spectroscopies. Gel permeation chromatography was employed for estimating the Mw and Mn and Mw/Mn of the homo- and co-polymers. Thermal analysis showed copoly(CPA-GMA) (49:51) to be less stable (345°C) than poly(CPA) (417°C) at 50°C. DSC was utilized in determining the glass transition temperature. The 49:51 copolymer was chosen for making adhesives by curing with diethanolamine in chloroform. The cured resins were tested for the adhesion properties on leather-leather bonding at 50° and 90°C. It was found that the resin cured at 90°C exhibited a maximum peel strength of 1.1 N/mm, revealing a good adhesive behavior.

COPOLYMERIZATION OF 4-NITROPHENYL ACRYLATE (NPA) WITH METHYL METHACRYLATE (MMA): SYNTHESIS, CHARACTERIZATION AND REACTIVITY RATIOS

4-Nitrophenyl acrylate (NPA) has been synthesized from the precursor viz 4-nitrophenol, and characterized by IR, 1H and 13C NMR spectroscopic methods. Homo- and copolymerization of NPA with methyl methacrylate (MMA) has been carried out in 2-butanone by free radical polymerization using benzoyl peroxide (BPO) as initiator at 70°C. Poly(NPA) and poly(NPA-co-MMA) were characterized by IR, 1H and 13C NMR spectral studies and their copolymer compositions were evaluated by 1H NMR spectroscopy. The reactivity ratios were calculated by Fineman-Ross, Kelen-Tudos, and Extended Kelen-Tudos methods. The Q and e values for NPA has been determined by using Alfrey-Price scheme. The thermal properties of the polymers have been studied by TGA and DSC analysis. The molecular

Copolymerization of 4-chlorophenyl acrylate with methyl acrylate: synthesis, characterization, reactivity ratios, and their applications in the leather industry

4-Chlorophenyl acrylate (CPA) was prepared by reacting 4-chlorophenol and acryloyl chloride in the presence of triethylamine in ethyl acetate solution. Poly(4-chlorophenyl acrylate) and copoly(4-chlorophenyl acrylate–methyl acrylate) were synthesized by the free radical polymerization in ethyl acetate at 70°C. All the polymers were characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopic techniques. The composition of the copolymers was determined by the 1H-NMR spectroscopic technique, that is, by integrating the aromatic peaks corresponding to the 4-chlorophenyl acrylate unit against the carbomethoxy group in the methyl acrylate unit. The reactivity ratios were calculated by Fineman–Ross, Kelen–Tudos (K–T), and the extended Kelen–Tudos methods. The values of r1 and r2 obtained by these methods were in close agreement with each other; that is, r1(CPA) = 0.64 and r2(MA) = 0.13 by the K–T method. The number-average molecular weight (M̄n = 1.55 × 103), the weight-average molecular weight (M̄w = 8.39 × 103), and the polydispersity index (M̄w/M̄n = 5.42) of poly(CPA) were determined by gel permeation chromatography (GPC). Thermal properties of the polymers were studied in a nitrogen atmosphere using thermogravimetric analysis (TGA). As the CPA increases in the copolymer, thermal stability of the copolymer increases (e.g., 90% weight loss occurs at 480°C for 20 mol % CPA, whereas the same weight loss occurs at 571°C for 80 mol % CPA). Acrylic binders, based on the CPA–MA–BA terpolymer, of different glass transition temperatures were prepared for applications in leather industry as top coat and base coat materials. These acrylic emulsions were cast into thin films, and their characteristics were tested for physical properties. These acrylic emulsions were applied as a base coat on leather, and the compositions having Tg values of 1.08 and 9.25°C were found to have excellent properties as base coats for leather when compared with commercial samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1153–1160, 1999

Copolymers Derived from 4-Nitrophenyl Methacrylate (Npma) and Methyl-Methacrylate (MMA)-Synthesis, Characterization, and Reactivity Ratios

The free radical copolymerization of 4-nitrophenyl methacrylate (NPMA) with methylmethacrylate (MMA) in 2-butanone was carried out with different mole ratios of NPMA and MMA. The resulting copolymers were characterized by spectral studies. The molecular weights of the copolymers were determined by gel permeation chromatography and both number average (Mn) and weight average (Mw/ molecular weights lie in the range of 1.7–1.9 × 104 and 3.2–3.6 × 104, respectively. The copolymer composition was evaluated by 1H NMR spectroscopic technique. The reactivity ratios of the monomers in the copolymer were calculated by Fineman-Ross, Kelen-Tudos and extended Kelen-Tudos methods. The product of these values are close to each other (0.73–0.80) and suggest a random arrangement of monomers in the copolymer chain. Thermal properties of these systems investigated by TG and DSC indicate that the decomposition of all the copolymers occurs in the temperature range 175°C–535°C.

Copolymers ofN-vinylcarbazole and ethyl iodide quarternized dimethylaminoethyl methacrylate

Copolymers of N-vinylcarbazole (NVC) and the quarternary salt of N,N- dimethylaminoethyl methacrylate with ethyl iodide (DMAEMArEI) were prepared by free-radical copolymerization in dimethyl sulfoxide at 707C using a,a*-azobisisobutyro- nitrile (AIBN) as an initiator. The reactivity ratios of both monomers were determined according to the general copolymerization equation using the extended Kelen-Tudos method and found to be r1 A 0.12 ({0.04) and r2 A 0.84 ({0.08). Copolymers were characterized by viscosity measurements and thermogravimetric analysis (TGA). Co- polymers containing DMAEMArEI higher than 60 mol % were water-soluble. q 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1517-1521, 1998

Spontaneous copolymerization of maleic anhydride andN-vinylimidazole in 1,4-dioxane. I. Charge transfer complexation and kinetics of the copolymerization

Maleic anhydride (MAH) and N-vinylimidazole (NVIM) were found to form a charge transfer complex in 1,4-dioxane. The equilibrium constant, K, of the complex and its composition were calculated from the modified Benesi–Hildebrand equation by using UV spectrophotometry. Spontaneous copolymerization of MAH and NVIM has been studied in the range from 20 to 80 mol % MAH in the feed. The effects of the polymerization temperature, monomer feed composition, and total monomer concentration on the initial rate of polymerization were investigated. The values of overall activation energy, Ea, and overall order with respect to total monomer concentration were calculated. Copolymer compositions were found from the elemental analysis data. Reactivity ratios were calculated by the extended Kelen—Tudos method. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3735–3743, 1997

Copolymerization of 4-acetyl phenylacrylate with methyl methacrylate and butyl methacrylate: Synthesis, characterization and reactivity ratios

Several copolymers of methyl methacrylate (MMA) and butyl methacrylate (BMA) with 4-acetyl phenylacrylate (APA) having different copolymer compositions were synthesized in 2-butanone using benzoyl peroxide as a free radical initiator at 65 ± 0.5 °C. The composition of monomeric units in the copolymer system was calculated using 1H NMR spectroscopy by comparing the integral values of well separated aromatic and aliphatic proton peaks. The reactivity ratios were calculated by employing Fineman-Ross, Kelen-Tudos and extended Kelen-Tudos methods. The values of r 1, and r 2 obtained by the Kelen-Tudos and the Extended Kelen-Tudos methods appear to be in close agreement with each other i.e r 1 (APA) = 0.78 and r 2 (MMA): 0.575 for the copoly(APA-MMA) system; r 1(APA) = 1.465 and r 2(BMA) = 0.685 for the copoly(APA-BMA) system. The copolymers were characterized by IR, 1H and 13C NMR spectroscopic techniques. By using gel permeation chromatography, weight average ( M ̄ w ) and number average ( M ̄ n ) molecular weights and polydispersity indices of the copolymers were determined. Thermal stabilities of the homo- and co-polymers were calculated using thermogravimetric analysis, while differential scanning calorimetry was used to determine the glass transition temperature. Thermally stable copolymers were obtained by the incorporation of APA units as the initial decomposition temperature of the copolymers increased with increase in concentration of APA units.

Copolymerization of 4-nitrophenyl acrylate with glycidyl methacrylate: Synthesis, characterization, and reactivity ratios

4-Nitrophenyl acrylate (NPA) was prepared and characterized by IR and NMR spectroscopic techniques. Poly(4-nitrophenyl acrylate) [poly(NPA)] and copolymers of glycidyl methacrylate ( GMA) and NPA having various feed compositions in a 2-butanone solution using benzoyl peroxide as an initiator at 65°C ± 0.5°C were prepared. Copolymer compositions were determined by 1 H-NMR analysis. The monomer reactivity ratios were determined by Fineman-Ross, Kelen-Tudos, and extended Kelen-Tudos methods. The molecular weights of the polymers were determined by gel permeation chromatography. Thermogravimetric analysis of the polymers was performed in air and their thermal stability was studied.

5-indanyl acrylate monomer: Synthesis, characterization and copolymerization with glycidyl methacrylate

A new monomer, 5-indanyl acrylate (IdA), has been synthesized from the precursor viz., 5-indanol, and characterized by FT-IR, 1H-NMR and 13C-NMR spectroscopies. Homo- and copolymerization of IdA with glycidyl methacrylate (GMA) have been carried out in benzene by free radical polymerization at 70 °C utilizing 2,2′-azobisisobutyronitrile (AIBN). Poly(IdA) and IdA-GMA copolymers were characterized by 1H-NMR and 13C-NMR, and the copolymer compositions were evaluated by 1H-NMR spectroscopy. The reactivity ratios were estimated using Fineman-Ross, Kelen-Tudos and extended Kelen-Tudos methods. The Q and e values for IdA have been determined adopting the Alfrey-Price scheme. By TGA and DSC analyses, the thermal properties of the polymers have been studied.

Copolymerization of 4-methyl- and 4-methoxyphenyl acrylates with glycidyl methacrylate: Synthesis, characterization, reactivity ratios, and application as adhesives for the leather industry

Copolymers of 4-methyl- and 4-methoxyphenyl acrylates with glycidyl methacrylate having different copolymer compositions were synthesized in 1,4-dioxan using benzoyl peroxide as a radical initiator at 70 ± 0.5°C. The composition of the monomers in the copolymers were calculated using 1H-NMR spectroscopy by comparing the integral values of well-separated aromatic and alifatic proton peaks. The reactivity ratios were calculated by Fineman-Ross, Kelen-Tudos, and extended Kelen-Tudos methods. The copolymers were characterized by 1H-NMR and proton decoupled 13C-NMR spectroscopic techniques. Gel permeation chromatography was used for determining the and and polydispersity indexes of the copolymers. Thermal stability of the homo- and copolymers was calculated using thermogravimetric analysis, while differential scanning calorimetry was utilized in determining the glass transition temperature. Copolymers of suitable composition were chosen for curing reactions with diethanolamine in chloroform. The cured resins were tested as adhesives for leather-leather bonding at different temperatures (50, 90, 100, and 110°C). It was found that copoly(MOPA-GMA) at 50°C gave the best adhesive property over all other samples tested. © 1996 John Wiley & Sons, Inc.

Synthesis, characterization and the reactivity ratios of copolymers of cyclohexyl acrylate with styrene and N-vinyl-2-pyrrolidone

Copolymerization of cyclohexyl acrylate (CHA) with styrene (Sty) and N-vinyl-2-pyrrolidone (VPD) was carried out in benzene and dioxane at 70°C and 75°C, respectively, using benzoyl peroxide as initiator. The copolymers were characterized by i.r., 1H n.m.r., g.p.c. and viscometry. The compositions of the copolymers were determined by elemental analysis and the reactivity ratios were computed by Fineman-Ross, Kelen-Tudos and extended Kelen-Tudos methods. r CHA = 0.272 ± 0.048, r Sty = 0.913 ± 0.107 for CHA-Sty system and r CHA = 1.297 ± 0.088, r VPD = 0.122 ± 0.014 for CHA-VPD system are determined by extended Kelen-Tudos method. The Q and e values for CHA monomer were also determined.

Glycidyl methacrylate and N‐vinyl‐2‐pyrrolidone copolymers: Synthesis, characterization, and reactivity ratios

AbstractFree radical copolymerization of glycidyl methacrylate (GMA) and N‐vinyl‐2‐pyrrolidone (VPD) was carried out using 2,2′‐azobisisobutyronitrile (AIBN), in chloroform at 60°C. The polymers were characterized by IR and 13C‐NMR spectroscopic methods. The percentage composition of the copolymers were established by microelemental analysis and by 13C‐NMR spectroscopy. The copolymerization reactivity ratios were computed using the Fineman‐Ross method, the Kelen‐Tudos method, and the extended Kelen‐Tudos method. The molecular weights of the copolymers were obtained by GPC measurements. Thermal properties of the homo‐ and copolymers were also studied by thermogravimetric analysis. The copolymers were tested as adhesives for leather‐to‐leather and leather‐torubber bonding.