Novel AB crosslinked polymer networks from telechelic 4‐vinylbenzyl carbamate terminated polyurethanes and different vinyl monomers

Novel AB crosslinked polymer (ABCP) networks were synthesized from telechelic 4‐vinylbenzyl carbamate terminated polyurethanes and monomers such as styrene, 4‐vinylpyridine, methyl methacrylate and butyl acrylate. Telechelic 4‐vinylbenzyl carbamate terminated polyurethanes were synthesized from polypropylene glycol‐based NCO‐terminated polyurethane and vinylbenzyl alcohol. Effect of changing the molecular weight of polypropylene glycol on the static and dynamic mechanical properties of ABCP networks from polyurethane‐polymethyl methacrylate was studied in detail. Dynamic mechanical thermal analysis results show that polymethyl methacrylate and polystyrene‐based ABCPs have good damping over a broad temperature range. ABCP networks prepared from 4‐vinylbenzyl carbamate terminated polyurethane and different monomers such as methyl methacrylate, butyl acrylate and styrene exhibit single tan δ_max value which implies excellent interlocking between the two polymers present in the ABCP networks. Static mechanical studies showed that methyl methacrylate and styrene‐based ABCP networks exhibit better tensile properties compared to other ABCP networks from butyl acrylate and 4‐vinyl pyridine monomers. Thermogravimetric analysis results revealed that the ABCP networks showed an improved thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of styrene-methyl methacrylate block copolymers using germanium and tin derivatives containing a macroradical

Block copolymerization of polystyrene synthesized in the presence of catecholate complexes of Group IV nontransition elements was studied. The effect of Ge(IV) and Sn(IV) o-semiquinolate derivatives formed in the course of styrene polymerization on the formation of the macroinitiator of methyl methacrylate polymerization was examined.     

Addition–fragmentation behavior of a capto-dative group-substituted acrylic ester in free-radical polymerization and reactivity of the derived macromonomers

Ethyl-2-(2-cyano-2-ethylthio)-ethyl-propenoate (ECEP) was synthesized and examined as free-radical addition–fragmentation chain transfer agent (AFCTA) in the bulk polymerization of methyl methacrylate (MMA) and styrene at various temperatures. A better chain transfer constant (C_tr) was observed for styrene than for MMA, projecting the potentiality of the compound as a better end-functionalizing agent for the former. In both cases, copolymerization of ECEP with the monomer predominated over fragmentation, the relative proportions of which were dependent on the monomer. The ECEP-terminated radical fragmented to an extent of 26% in the presence of MMA, whereas it was only 9.5% in the case of styrene. The relative extent of fragmentation and copolymerization was in conformation to the calculated reactivity ratios and chain transfer constants. Addition–fragmentation chain transfer resulted in the formation of methacrylic-functional macromonomers. The copolymerizability of the resultant macromonomer was found to depend on the nature of the backbone and on the comonomer. On copolymerizing with MMA, the terminal monomer moiety on polystyrene (PS)-based macromonomers preferred to undergo fragmentation, whereas that of the polymethyl methacrylate (PMMA)-based one copolymerized readily with styrene because of thermodynamic and kinetic factors. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2511–2524, 1999     

Synthesis and Mechanical Properties of Polypropylene-based Polymer Hybrids via Controlled Radical Polymerization

Isotactic polypropylene-based graft copolymers linking poly(methyl methacrylate), poly(n-butyl acrylate) and polystyrene were successfully synthesized by a controlled radical polymerization with isotactic polypropylene (iPP) macroinitiator. The hydroxylated iPP, prepared by propylene/10-undecen-1-ol copolymerization with a metallocene/methyl-aluminoxane/triisobutylaluminum catalyst system, was treated with 2-bromoisobutyryl bromide to produce a Br-group containing iPP (PP-g-Br). The resulting PP-g-Br could initiate controlled radical polymerization of methyl methacrylate, n-butyl acrylate and styrene by using a copper catalyst system, leading to a variety of iPP-based graft copolymers with a different content of the corresponding polar segment. These graft copolymers demonstrated unique mechanical properties dependent upon the kind and content of the grafted polar segment.     

Emulsion copolymerization of styrene and methyl methacrylate

Chain transfer constants to monomer have been measured by an emulsion copolymerization technique at 44°C. The monomer transfer constant (ratio of transfer to propagation rate constants) is 1.9 × 10^?5 for styrene polymerization and 0.4 × 10^?5 for the methyl methacrylate reaction. Cross-transfer reactions are important in this system; the sum of the cross-transfer constants is 5.8 × 10^?5. Reactivity ratios measured in emulsion were r₁ (styrene) = 0.44, r₂ = 0.46. Those in bulk polymerizations were r₁ = 0.45, r₂ = 0.48. These sets of values are not significantly different. Monomer feed compcsition in the polymerizing particles is the same as in the monomer droplets in emulsion copolymerization, despite the higher water solubility of methyl methacrylate. The equilibrium monomer concentration in the particles in interval-2 emulsion polymerization was constant and independent of monomer feed composition for feeds containing 0.25–1.0 mole fraction styrene. Radical concentration is estimated to go through a minimum with increasing methyl methacrylate content in the feed. Rates of copolymerization can be calculated a priori when the concentrations of monomers in the polymer particles are known.     

Free-radical copolymerization of 9-vinylanthracene

Free-radical copolymerization of methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate with 9-vinylanthracene was studied, and the reactivity ratios r ₁ and r₂ were calculated. In the light of earlier data on copolymerization of 9-vinylanthracene with styrene results show that the difference in polarity of the monomers participating in the copolymerization has an insignificant influence compared with that of the steric factors involved in the reaction.     

Copolymerization of <Emphasis Type="Italic">p</Emphasis>-(2,2-dichlorocyclopropyl)styrene with Methyl methacrylate and properties of the resulting copolymers

A copolymer based on p-(2,2-dichlorocyclopropyl)styrene and methyl methacrylate was prepared by radical copolymerization. The copolymerization constants were determined, and the parameters of the Q-e scheme were calculated.     

1H-NMR study of structure and tacticity in p-t-butylstyrene/methyl methacrylate copolymers

Copolymers prepared by the bulk copolymerization of p-t-butylstyrene (S) and methyl methacrylate (M) were analyzed by ¹H-NMR. The spectra showed fine structure in the δ 2.2–3.6 region similar to that reported for styrene/methyl methacrylate copolymers. Reactivity ratios for S-M copolymers determined by classical composition measurements differed markedly from the same ratios determined by NMR when it was assumed that NMR peak-triad assignments could be made by analogy with published styrene/methyl methacrylate assignments. A new set of peak-triad assignments was proposed that reconciles this difficulty and gives good agreement between triad fractions measured by NMR and those calculated from theory.     

Synthesis of polymer particles possessing radical initiating sites on the surface by emulsion copolymerization and construction of core–shell structures by a photoinduced atom transfer radical polymerization approach

The crosslinked polystyrene particles possessing photofunctional N,N‐diethyldithiocarbamate groups on their surface were prepared by free‐radical emulsion copolymerization of a mixture of styrene, divinylbenzene and 4‐vinylbenzyl N,N‐diethyldithiocarbamate with redox system as an initiator under UV irradiation. In this copolymerization, the inimer 4‐vinylbenzyl N,N‐diethyldithiocarbamate acted the formation of hyperbranched structures by living radical photopolymerization. The particle sizes (number‐average particle diameter = 214–523 nm) were controlled by varying the feed amount of surfactant and size distributions were relatively narrow. Subsequently, core–shell particles were synthesized by photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by photofunctional polystyrene particles as a macroinitiator. Such core–shell particles were stabilized sterically by grafted chains in organic solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1771–1777, 2007     

Biodestruction of Lignins by the Basidiomycete Pleurotus ostreatus

The depolymerization, demethoxylation, and oxidation of lignin by the common oyster mushroom (Pleurotus ostreatus)is demonstrated     

Metal‐catalyzed living radical graft copolymerization of olefins initiated from the structural defects of poly(vinyl chloride)

Commercial poly(vinyl chloride) (PVC) contains allyl chloride and tertiary chloride groups as structural defects. This article reports the use of the active chloride groups from the structural defects of PVC as initiators for the metal‐catalyzed living radical graft copolymerization of PVC. The following monomers were investigated in graft copolymerization experiments: methyl methacrylate, butyl methacrylate, tert‐butyl methacrylate, butyl acrylate, methacrylonitrile, acrylonitrile, styrene, 4‐chloro‐styrene, 4‐methyl‐styrene, and isobornylmethacrylate. Cu(0)/bpy, CuCl/bpy, CuBr/bpy, Cu₂O/bpy, Cu₂S/bpy, and Cu₂Se/bpy (where bpy = 2,2′‐bipyridine) were used as catalysts. Living radical polymerizations initiated from 1‐chloro‐3‐methyl‐2‐butene, allyl bromide, and 1,4‐dichloro‐2‐butene as models for the allyl chloride structural defects and from 3‐chloro‐3‐methyl‐pentane and 1,3‐dichloro‐3‐methylbutane as models for the tertiary chloride defects were studied. Graft copolymerization experiments were accessible in solution, in a swollen state, and in bulk. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1120–1135, 2001     

Friedel-Crafts acylation reactions in copolymers of methyl methacrylate and styrene and in mixtures of the homopolymers

In the presence of SnCl₄ in 1,2-dichloroethane solution, copolymers of styrene and methyl methacrylate undergo a Friedel-Crafts acylation reaction between the ester groups and the ortho position of adjacent styrene units to form a partial ladder polymer. This has been confirmed by infrared and ultraviolet spectral analysis and by observing the influence of substituted styrenes on the rate of the reaction. A similar reaction can be induced to occur between polystyrene and poly(methyl methacrylate). Thermal analysis measurements demonstrate that the degradation properties of copolymers of styrene and methyl methacrylate are profoundly changed by this treatment.     

Multifunctional ATRP initiators: Synthesis of four‐arm star homopolymers of methyl methacrylate and graft copolymers of polystyrene and poly(t‐butyl methacrylate)

Tetrakis bromomethyl benzene was used as a tetrafunctional initiator in the synthesis of four‐armed star polymers of methyl methacrylate via atom transfer radical polymerization (ATRP) with a CuBr/2,2 bipyridine catalytic system and benzene as a solvent. Relatively low polydispersities were achieved, and the experimental molecular weights were in agreement with the theoretical ones. A combination of 2,2,6,6‐tetramethyl piperidine‐N‐oxyl‐mediated free‐radical polymerization and ATRP was used to synthesize various graft copolymers with polystyrene backbones and poly(t‐butyl methacrylate) grafts. In this case, the backbone was produced with a 2,2,6,6‐tetramethyl piperidine‐N‐oxyl‐mediated stable free‐radical polymerization process from the copolymerization of styrene and p‐(chloromethyl) styrene. This polychloromethylated polymer was used as an ATRP multifunctional initiator for t‐butyl methacrylate polymerization, giving the desired graft copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 650–655, 2001     

N‐Bromosuccinimide as a thermal iniferter for radical polymerization

N‐Bromosuccinimide (NBS) was used as a thermal iniferter for the initiation of the bulk polymerizations of methyl methacrylate, methyl acrylate, and styrene. The polymerizations showed the characteristics of a living polymerization: both the yields and the molecular weights of the resultant polymers increased linearly as the reaction time increased. The molecular weight distributions of the polymers were 1.42–1.95 under the studied conditions. The resultant polymers could be used as macroiniferters to reinitiate the polymerization of the second monomer. The copolymers poly(methyl methacrylate)‐b‐polystyrene and polystyrene‐b‐poly(methyl methacrylate) were obtained and characterized. End‐group analysis of the resultant poly(methyl methacrylate), poly(methyl acrylate), and polystyrene confirmed that NBS behaved as a thermal iniferter. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2567–2573, 2005     

Synthesis of Graft Polymers by Copolymerization of Macromonomers. II. Copolymerization Kinetics of Styrene-and Methacrylate-Terminatedpoly(2-Acetoxyethyl Methacrylate) Macromonomers

Styrene-terminated poly(2-acetoxyethyl methacrylate) macromonomer (EBA), methacrylate-terminated poly(2-acetoxyethyl methacrylate) macromonomer (MPA), and methacrylate-terminated poly(methyl methacrylate) macromonomer (MPM) were synthesized and subjected to polymerization and copolymerization by a free-radical polymerization initiator (AIBN). EBA and MPA were homopolymerized at various concentrations. EBA exhibited higher reactivity than styrene. The reactivity of MPA, however, was almost equal to that of glycidyl methacrylate. Cumulative copolymer compositions were determined by GPC analysis of copolymerization products. The reactivity ratios estimated were r_a = 0.95 and r_b , = 0.90 for EBA macromonomer (a)-methyl methacrylate (b) copolymerization. These values were not consistent with literature values for the styrene-methyl methacrylate and p-methoxy-styrene-methyl methacrylate systems. The reactivity ratios estimated for MPA and 2-bromoethyl methacrylate were r_a - 0.95 and r_b , = 0.98; equal to the glycidyl methacrylate-2-bromoethyl methacrylate system. MPA or MPM was also copolymerized with styrene, and the reactivity ratios were r_a = 0.40, r_a = 0.60 and r_a = 0.39, r_a = 0.58, respectively. These estimates were in good agreement with the reactivity ratios for glycidyl methacrylate and styrene. Thus, no effect of molecular weight was observed for both copolymerization systems.     

Synthesis and properties of cyclopropane-containing optically transparent polymers

New cyclopropane-containing optically transparent polymers were prepared by radical homopolymerization of p-(2-methoxycarbonylcyclopropyl)styrene and by its binary copolymerization with styrene and methyl methacrylate. The composition and structure of these macromolecular compounds were determined, and their main service characteristics were evaluated.     

Organometallic polymers. XVI. Copolymerization of styrenetricarbonylchromium and the reaction of polystyrene with chromium hexacarbonyl

Styrenetricarbonylchromium (IV) has been synthesized. Monomer IV did not homopolymerize with free-radical initiation but copolymerized with styrene, methyl acrylate, and vinylcymantrene. The copolymerizations were carried out in benzene solutions at 70°C with azobisisobutyronitrile as the initiator. The relative reactivity ratios were determined for the styrene and methyl acrylate copolymerizations. They were (defining M₁ as monomer IV) r₁ ? 0, r₂ ? 1.39 for styrene copolymerizations and r₁ ? 0, r₂ ? 0.75 for methyl acrylate copolymerization. Polystyrene reacted with chromium-hexacarbonyl in refluxing DME to produce a polymer in which about 32% of the benzene rings were complexed with ? Cr(CO)₃ units. The use of a polystyrene of narrow molecular weight distribution in this reaction demonstrated that no decomposition of the polystyrene chains occurred.     

Polymerization of coordinated monomers. VI. Molecular complex formation of methyl methacrylate coordinated to stannic chloride with styrene or toluene

The equilibrium constants for the complex formation between stannic chloride and methyl methacrylate were determined in n-hexane–toluene solution at 0, ?20, and ?30°C by using the absorption band at 350 nm. Continuous variation plots at ?20°C in n-hexane based on the ¹H-chemical shifts definitely show a 1:1 interaction between the coordinated methyl methacrylate and styrene or toluene. The magnitudes of the shifts for the four groups of protons in methyl methacrylate are found to be in a specific ratio in common with the 1:2 complex–styrene or -toluene system. The equilibrium constants for the ternary molecular complex formation between the 1:2 complex and styrene or toluene were determined in n-hexane in the temperature range ?50 to +20°C by use of the chemical shifts. The concentrations of the complex species in the alternating copolymerization solutions were estimated by use of the equilibrium constants. There is a linear relationship between the enthalpy and the entropy changes for the ternary molecular complex formation, which is governed by the enthalpy factor. The specificity of the interactions indicates a specific time-averaged orientation of benzene ring to the coordinated methyl methacrylate. The effects of the coordination of methyl methacrylate to stannic chloride were discussed on the basis of results of ¹³C-NMR spectroscopy.     

SYNTHESIS OF MACROMONOMER USING END FUNCTIONAL POLYSTYRENE PREPARED FROM p-METHOXYBENZYL p-TRIMETHYL-SILYLPHENYL SELENIDE AS A PHOTOINIFERTER

The end functional polystyrene having phenylseleno group at ω-chain end was prepared from radical polymerization of styrene in the presence of p-methoxybenzyl p-trimethylsilylphenyl selenide as a photoiniferter. The phenylseleno group at ω-chain end in polystyrene was eliminated by hydrogen peroxide. The resulting polystyrene was interconverted quantitatively to polystyrene having epoxy end group by the oxidation with m-chloroperbenzoic acid. The macromonomer having a meth-acryloyl end group was synthesized from polystyrene containing epoxy end group with methacrylic acid in xylene at 140°C. Copolymerization of this macromonomer with methyl methacrylate afforded effectively a graft copolymer composed of a poly-(methyl methacrylate) backbone and polystyrene branches.     

Free-radical polymerization of vinyl ferrocene

The results of quantitative studies of the rates of free-radical polymerization of vinyl ferrocene indicate that the latter has polymerization characteristics similar to those of styrene. The rates of homopolymerization of these two monomers in benzene at 70°C. were measured with the use of azobisisobutyronitrile as catalyst. The rate constants (k = R_p/[M][I]^1/2) are k_VF = (1.1 ? 1.8) × 10^?4, k_STY = 1.65 × 10^?4. Small amounts of vinyl ferrocene and styrene have similar effects on the rates of polymerizations of methyl methacrylate and ethyl acrylate and on the molecular weights of the resulting polymer. Polystyrene and poly(vinyl ferrocene) with similar molecular weights are isolated from polymerizations carried out under identical conditions. The rates of copolymerization of vinyl ferrocene—methyl methacrylate, vinyl ferrocene—styrene, and styrene—methyl methacrylate were determined by following the disappearance of monomers by means of gas chromatographic analyses. The relative reactivity for vinyl ferrocene is slightly lower than that for styrene.