Preparation of polymer nanoparticles from renewable biobased furfuryl alcohol and maleic anhydride by stabilizer‐free dispersion polymerization

The spherical polymer nanoparticles of biobased renewable monomers, furfuryl alcohol (FA) and maleic anhydride (MAn), with diameters (D_n) in the range of 120 to 500 nm have been prepared by stabilizer‐free dispersion copolymerization. In acetate or its mixture, the conversion of the monomers greatly depended on the concentration of AIBN. When the molar ratio of AIBN/monomers was 3.6% (wt), the monomer conversion could be as high as 80%. The aggregations of the solvated polymer chains formed the nuclei of the polymer particles. After the nucleation stage, both the monomer conversions and particle sizes increased steadily, while the coefficient of variation of the particle size decreased. The almost linear relationship between the D_n³ and the weight of polymer suggested that there is no significant secondary nucleation. The copolymer of FA and MAn could not dissolve in common organic solvents. Elemental analyses, FTIR and ¹³CP‐MAS spectra showed that the copolymer was close to the alternative copolymer of FA and MAn irrespective to the molar ratios of FA/MAn in monomer feed. Furthermore, the two 2,5‐ and 3,4‐dihydrofuran ring configurations exist in the copolymer and the later is the major one. The reaction of copolymer particles with triethylenetetramine confirmed the reactivity of the succinic anhydride groups at the surface of copolymer particles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Radiation-induced copolymerization of methyl trifluoroacrylate with ethylene

Copolymerization of methyl trifluoroacrylate (MTFA) with ethylene in bulk was induced by γ irradiation. The copolymerization was observed to proceed in the liquid monomer mixture of MTFA and ethylene at 25°C with the dose rates ranging from 5.0 × 10⁴ to 1.0 × 10⁶ rad/hr. A wide range of the initial monomer composition gives an almost equimolar and alternating copolymer. The highest polymerization rate was observed at the equimolar monomer composition. The dose rate exponent of the polymerization rate is unity. The reactivity ratios of r₁ (MTFA) and r₂ (ethylene) were determined to be 0.034 and 0.14, respectively.     

Characterization of chloroprene and maleic anhydride copolymer by 13C-NMR spectroscopy and pyrolysis GC/MS

The radical copolymerizations of chloroprene (CP) and maleic anhydride (MAH) were carried out with AIBN in 1,4-dioxane at 60°C. The monomer reactivity ratios were estimated as r₁ (CP) = 0.38 and r₂ (MAH) = 0.07. Microstructures in the copolymer of chloroprene (CP) and maleic anhydride (MAH) were investigated by 75.4 MHz ¹³C-and 300 MHz ¹H-NMR spectroscopies. Resonances were assigned to the monomer sequence dyads CC, CM, and MC (C = chloroprene, M = maleic anhydride). Well resolved fine structure in the ¹³C-NMR spectra showed that 1,2- and 3,4-structural chloroprene units were negligible in the copolymer. The pyrolysis characterization of the copolymer was also investigated by the pyrolysis gas chromatography mass spectrometry (GC/MS). The fragments of CP and MAH monomers and CP-MAH hybrid dimer, CO, and CO₂ were identified after pyrolysis of the copolymer. © 1994 John Wiley & Sons, Inc.     

Charge transfer complex formation in in-situ maleic anhydride and N-vinyl caprolactam copolymer and copolymer/organo-montmorillonite nanoarchitectures

The binary copolymerization of maleic anhydride (MA) and N-vinyl caprolactam (VCL) or considered as acceptor (A)?donor (D) monomer systems were used (MA:VCL) 50:50 in BPO (0.5%) as an initiator at 70°C under nitrogen atmosphere. The functional copolymers, having a combination of rigid/flexible linkages and an ability of complex-formation with interlayered surface of organo-silicate, and their nanocomposites have been synthesized. Interlamellar in situ complex-radical copolymerization of intercalated monomer complexes of MA and VCL undergoes with stearyl amine surface modified montmorillonite (O-MMT) and monomer mixtures. Charge transfer complex formation was followed and identified by UV-Vis-NIR spectroscopy. Equilibrium constant (K_AD) molar absorption coefficient (?^AD)) of the complex were determined by the Benesi-Hildebrand, Scott and Ketaalar equations respectively. The results show that copolymerization of MA:VCL system was preceded via alternating copolymerization mechanism. Obtained functional alternating copolymer and copolymer/O-MMT nanostructures were characterized by XRD and TEM.     

Copolymerization of 4-methyl-1,3-dioxene-4 with maleic anhydride and terpolymerization with styrene as the third component

Copolymerization of 4-methyl-1,3-dioxene-4 with maleic anhydride was carried out. The monomer reactivity ratio was determined to be r₁ = 0.18, r₂ ～ 0 in terminal model and r₁ = 0.015, r₁′ = 0.224, r₂′ = r₂′ = 0 in the penultimate model. Calculations of run number, linkage probabilities, and number-average chain length in the terminal model and comparison of n (mole ratio of each monomer unit content in copolymer) in each model with the experimental value was made. From these results, the obtained polymer was confirmed to be alternating. Terpolymerization of 4-methyl-1,3-dioxene-4 with maleic anhydride and styrene was also carried out. The agreement of the experimental value (titration by indicator or electroconductivity) of maleic anhydride content with the theoretical value confirms that the terpolymer has a DMS triad sequence.     

Synthesis and Radical Polymerization of N‐[4‐N′‐(Phenylamino‐carbonyl)phenyl]maleimide and its Copolymerization with Methyl Methacrylate

A novel type of imide‐amide monomer, 4‐maleimidobenzanilide (MB) i.e., N‐[4‐N′‐(phenylaminocarbonyl)phenyl]maleimide was synthesized from maleic anhydride, p‐aminobenzoic acid and aniline. Radical polymerization of MB and its copolymerization with MMA (methyl methacrylate), initiated by AIBN, were performed in THF solvent at 65°C. Nine copolymer samples were prepared using different feed ratios of comonomers. All the polymer samples have been characterized by a solubility test, intrinsic viscosity measurements, FT‐IR and ¹H‐NMR spectral analysis, and thermo‐gravimetric analysis. The values of monomer reactivity ratios of MB‐MMA system (r₁, r₂) and the Alfrey‐Price parameters Q₁ and e₁ were determined.     

Radical cyclocopolymerization of divinyl ether and maleic anhydride. A 13C-NMR study of the polymer structure

The structure of the 1:2 copolymer of divinyl ether and maleic anhydride was investigated by ¹³C-NMR spectroscopy. The polymer contains the bicyclic unit composed of one molecule of each monomer and the maleic anhydride unit. The carbon chemical shift for these units was calculated on the basis of the chemical shift of many model compounds. The major peaks of the cyclopolymer prepared in chloroform were consistent with the presence of the symmetrical bicyclic unit with cis junction and the trans monocyclic anhydride unit. The carbonyl carbon spectrum for the copolymer obtained in a mixed solvent of acetone and CS₂ suggested the predominant formation of the unsymmetrical bicyclic unit. The polymerization process was discussed on the basis of these results.     

Laser-Initiated copolymerization of N-vinylpyrrolidone with maleic anhydride and maleimide

This article describes the laser-initiated copolymerization of N-vinylpyrrolidone with maleic anhydride and maleimide via charge transfer complexes. The dependence of copolymer yield on the molar ratios of the monomers in the feed and on the irradiation time is described. Based on the ultraviolet and infrared spectroscopy, and chemical analysis results, a tentative mechanism of polymerization is suggested. The rates of polymerization of several monomer systems are compared. The N-vinylpyrrolidone and maleimide system shows the highest rate of polymerization.     

Radiation-Induced Copolymerization of Thiophene with Maleic Anhydride

Radiation-induced copolymerization of thiophene with maleic anhydride has been studied. On the copolymerization in chloroform solution, the effects of dose rate, polymerization temperature, and, monomer composition and concentration on the yield and molecular weight of the copolymer were determined. The copolymerization proceeds via a radical mechanism with bimolecular termination of propagating polymer radicals, and the apparent activation energy is 5.3 kcal/mole. By NMR spectroscopy of copolymer, it was also found that these monomers copolymerize alternately to give a copolymer having structure I. In this copolymerization, the higher initial rates were obtained at an equimolar composition of monomers and by using solvents containing chlorine, such as CC1₄, CHC1₃, and C₆H₅C1.     

A polarity‐activation strategy for the high incorporation of 1‐alkenes into functional copolymers via RAFT copolymerization

A new synthetic methodology for the preparation of copolymers having high incorporation of 1‐alkene together with multifunctionalities has been developed by polarity‐activated reversible addition‐fragmentation chain transfer (RAFT) copolymerization. This approach provides well‐defined alternating poly(1‐decene‐alt‐maleic anhydride), expanding the monomer types for living copolymerizations. Although neither 1‐decene (DE) nor maleic anhydride (MAn) has significant reactivity in RAFT homopolymerization, their copolymers have been synthesized by RAFT copolymerizations. The controlled characteristics of DE‐MAn copolymerizations were verified by increased copolymer molecular weights during the copolymerization process. Ternary copolymers of DE and MAn, with high conversion of DE, could be obtained by using additive amounts (5 mol %) of vinyl acetate or styrene (ST), demonstrating further enhanced monomer reactivities and complex chain structures. When ST was selected as the third monomer, copolymers with block structures were obtained, because of fast consumption of ST in the copolymerization. Moreover, a wide variety of well‐defined multifunctional copolymers were prepared by RAFT copolymerizations of various functional 1‐alkenes with MAn. For each copolymerization, gel permeation chromatography analysis showed that the resulting copolymer had well‐controlled M_n values and fairly low polydispersities (PDI = 1.3–1.4), and ¹H and ¹³C NMR spectroscopies indicated strong alternating tendency during copolymerization with high incorporation of 1‐alkene units, up to 50 mol %. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3488–3498, 2008     

Bioengineering functional copolymers. III. Synthesis of biocompatible poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrocomplexes and their thermostabilization effect on the activity of the enzyme penicillin G acylase

Stimuli‐responsive poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrobranched macrocomplexes were synthesized by (1) the radical copolymerization of N‐isopropylacrylamide and maleic anhydride with α,α′‐azobisisobutyronitrile as an initiator in 1,4‐dioxane at 65 °C under a nitrogen atmosphere, (2) the polyesterification (grafting) of prepared poly(N‐isopropylacrylamide‐co‐maleic anhydride) containing less than 20 mol % anhydride units with α‐hydroxy‐ω‐methoxy‐poly(ethylene oxide)s having different number‐average molecular weights (M_n = 4000, 10,000, or 20,000), and (3) the incorporation of macrobranched copolymers with poly(ethylene imine) (M_n = 60,000). The composition and structure of the synthesized copolymer systems were determined by Fourier transform infrared, ¹H and ¹³C NMR spectroscopy, and chemical and elemental analyses. The important properties of the copolymer systems (e.g., the viscosity, thermal and pH sensitivities, and lower critical solution temperature behavior) changed with increases in the molecular weight, composition, and length of the macrobranched hydrophobic domains. These copolymers with reactive anhydride and carboxylic groups were used for the stabilization of penicillin G acylase (PGA). The conjugation of the enzyme with the copolymers significantly increased the thermal stability of PGA (three times at 45 °C and two times at 65 °C). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1580–1593, 2003     

Radical copolymerization behavior of a highly fluorinated cyclic olefin with vinyl ether

The copolymerization of a highly fluorinated cyclic monomer, octafluorocyclopentene (OFCPE, M₁), with ethyl vinyl ether (EVE, M₂) was investigated with a radical initiator in bulk. Despite the poor homopolymerizability of each monomer, the copolymerization proceeded successfully, and the molecular weights of the copolymers reached up to more than 10,000. Incorporation of the OFCPE units into the copolymer led to an increase in the glass‐transition point. The copolymer composition was determined from ¹H NMR spectra and elemental analysis data. The molar fraction of the OFCPE unit in the copolymer increased and approached but did not exceed 0.5. The monomer reactivity ratios were estimated by the Yamada–Itahashi–Otsu nonlinear least‐squares procedure as r_1,OFCPE = ?0.008 ± 0.010 and r_2,EVE = 0.192 ± 0.015. The reactivity ratios clearly suggest that the copolymerization proceeds alternatively in the case of an excessive feed of OFCPE. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1151–1156, 2002     

The Copolymerization of Alkenes with Maleic Anhydride

The investigations presented deal with the experimental results of the copolymerization of maleic anhydride (MAn) with alkenes. The course of the reaction is explained by the overall rate of the copolymerization (v _Br), which correlates with the solution viscosity of the copolymer, and the dependence of the v _Br maximum on the mole ratio of the monomers at constant total monomer concentration. The use of solvents with increasing donor power leads to increased complexing of the free MAn molecules and of the MAn radical chain ends. The results demonstrate that, for low 1-alkenes, the addition of the MAn chain radical is the rate-determining step of the copolymerization. As the substituents on the olefinic double bond become larger or the double bond shifts to the 1,2-position, the addition of MAn to the hydrocarbon radical becomes more and more the rate-determining step. On the other hand, an increase of the CT complexation of the MAn polymer radical by use of donor solvents decreases the alkene addition rate.     

A study of the relative reactivity of maleic anhydride and some maleimides in free radical copolymerization and terpolymerization

Composition data for the free radical copolymerization of maleic anhydride with N-phenylmaleimide in toluene at 60°C have been obtained. Relative reactivity ratios in terminal and penultimate models using nonlinear least-squares optimization routine have been determined. The standard error was found to be somewhat smaller in the penultimate model, but is still larger than the uncertainty estimated for the copolymer composition. Terpolymers of maleic anhydride and styrene with maleimide, N-butylmaleimide, N-phenylmaleimide, and N-carbamylmaleimide were obtained. On the basis of analysis of the product composition at various monomer feeds the relative reactivity of maleic anhydride and maleimides in these reactions is compared and the influence of the structure of thesemonomers on the rate of some chain growth reactions is discussed.     

Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25°C, a dose rate of 1 × 10⁶ rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene was nearly 1/2 over a wide range of the monomer compositions. The Mayo–Lewis method gave negative r₁ (FVA) and r₁ (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model.     

Polymerization of itaconic acid derivatives

The γ-ray-initiated polymerization of dimethyl itaconate was studied. Dimethyl itaconate was polymerized by γ-irradiation at temperatures where the monomer does not polymerize thermally; so long as the monomer is kept in a liquid state, even at temperatures below the melting point, the polymerization takes place. Itaconic anhydride was polymerized in the solid state with γ-irradiation or benzoyl peroxide. The molecular weight of the polymer increases with time or yield and is greater than that of polymer obtained by other methods. The kinetic study and crystallographic study indicate that the γ-ray-initiated solid-phase polymerization is a first-order reaction with respect to monomer and the rate-determining step changes as the polymerization proceeds.     

γ-Ray-induced copolymerization of ethylene and vinyl chloride in liquid carbon dioxide

The γ-ray-induced copolymerization of ethylene and vinyl chloride with the use of liquid carbon dioxide as a solvent was studied under a total pressure of 400 kg/cm², with a dose rate of 2.5 × 10⁴ rad/hr at 30°C. A rubberlike, sticky polymer is obtained when the molar concentration of vinyl chloride is less than 30% in the monomer mixture, and the polymer is a white powder at higher concentrations of vinyl chloride. Infrared, x-ray, and differential thermal analyses confirm that the polymerization products are noncrystalline, true random copolymers. The rate of copolymerization decreases markedly when a small amount of vinyl chloride is added to ethylene monomer. In the range of vinyl chloride concentration higher than 5%, however, the rate and the molecular weight of copolymer increase with increasing concentration of vinyl chloride. It has been concluded from kinetic considerations based on these results that the rate of initiation increases proportionally with the concentration of vinyl chloride. Further, the growing chain radicals are shown to be deactivated by the cross-termination reaction between the radicals with terminal unit of ethylene and vinyl chloride, and no transfer reaction occurs.     

Copolymerization of ethylene and butadiene with supported titanium catalyst

The copolymerization of ethylene and butadiene with a supported titanium catalyst (TiCl₄/MgCl₂/EB/Φ₂SiCl₂/AlEt₃) is described. The resulting products were characterized by IR, ¹³C-NMR, x-ray diffraction, differential thermal analysis, electron microscopy, and solvent extraction. It was found that the butadiene units are substantially in trans-1,4 configuration and blocked sequences. Both ethylene and butadiene blocks form crystalline phases. The presence of unsaturated bonds made it possible to graft MMA and maleic anhydride. The influences of monomer composition, temperature, Al/Ti ratio, catalyst concentration, and solvents on the copolymerization were investigated.     

Alternating polyampholytes prepared by hydrolysis of copolymer of maleic anhydride and N-vinylsuccinimide

Alternating polyampholytes (MA-VA) containing two acidic groups and one basic group were prepared by the copolymerization of maleic anhydride (M₁) and N-vinylsuccinimide (M₂) at 60°C with AIBN as the initiator, followed by acid hydrolysis with 1N hydrochloric acid at 140°C for 24 hr. The monomer reactivity ratios r₁ and r₂ are 0.025 and 0.06, respectively. The structure of polymers was discussed on the basis of the data of their elementary, infrared (IR), and thermal analyses and the binding ability of heavy metal ion. Polyampholytes were soluble in strong acidic and basic media but were precipitated in the pH range 3–4. An isoelectric point at pH 3 was determined by potentiometric titration and the turbidimetric method. By thermal treatment above 205°C the polyampholyte turned quantitatively into a cyclized lactam. This suggests that the polyampholyte MA–VA has an intramolecular hydrogen bond between the amino and γ-carboxyl groups. The binding of Cu²⁺ and Hg²⁺ by the polyelectrolyte was evaluated by equilibrium dialysis.     

Effect of dicitrato- and dimalatogermanic acids on polycondensation of maleic anhydride with ethylene glycol

The catalytic activity of citric (H₄Citr) and malic (H₃Mal) acids, their coordination compounds with germanium(IV) H₂[Ge(HCit)₂] and H₂[Ge(Mal)₂], and germanium dioxide GeO₂ in polycondensation of maleic anhydride and ethylene glycol at various temperatures was studied (catalyst: ethylene glycol molar ratio 0.01: 1). The process kinetics was evaluated and the time of its completion was determined. The copolymerization kinetics of some of the prepared oligoesters with triethylene glycol dimethacrylate was studied, and the copolymer properties were determined.