Telomerization of Butyl Methacrylate and 1‐Octadecanethiol by Reactive Extrusion

Butyl methacrylate and 1‐octadecanethiol telomers were prepared by radical reactive extrusion. The main advantages of the use of this processing technique are that mass reactions can be conducted and continuous production is achieved within a reduced reaction time and a correct temperature control. Preliminary studies concerned the choice of the reactants for the telomerization reaction and the adaptation of the telomerization reaction to the reactive extrusion process. The transfer constant to C₁₈H₃₇SH was measured, and then experimental studies were conducted to verify that the hypothesis and approximations made for kinetic modeling are realistic. Particularly, it was shown that the use of relatively high chain‐transfer agent to monomer concentration ratio had no perceptible effect on the monomer conversion kinetic. These results allowed the choice of reactive extrusion conditions. Telomers were prepared using a laboratory co‐rotating twin‐screw extruder. The effect of reaction conditions (temperature, 1‐octadecanethiol to monomer concentration ratio) and of processing conditions (throughput, screw rotation speed) on the residence time distributions, molar mass and monomer conversions were examined. This study allowed the continuous synthesis of butyl methacrylate telomers having variable controlled molar masses and complete monomer conversion.

Screw profile used in reactive extrusion telomerization.     

Kinetic analysis of the imidization of poly(styrene‐co‐maleic anhydride) with aniline in the melt

On the basis of the competitive reactions of intermediate poly(styrene‐co‐N‐phenyl maleamic acid) (SNPMA) to produce either poly(styrene‐co‐maleic anhydride) (SMA) or poly(styrene‐co‐N‐phenyl maleimide) (SNPMI), the imidization kinetics of SMA with aniline in the molten state were investigated by a novel approach. The volatiles emitted during the reaction of SNPMA were monitored online with both thermogravimetric analysis and Fourier transform infrared (FTIR) integrated technology. The experimental results directly and definitely indicate that the amidization reaction from SMA to SNPMA in the melt was reversible. Moreover, the kinetic parameters of the competitive reactions of SNPMA in the melt to produce either SMA or SNPMI were determined by FTIR analysis and then compared with those parameters in solution that were obtained in our previous study. It was also implied that the forward ring‐opening reaction of SMA in the melt was nearly instantaneous and that the rates of the competitive reactions of SNPMA to produce either SMA or SNPMI were crucial for the total imidization of SMA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Bulk polymerization of methyl methacrylate initiated by high intensity ultrasonic irradiation and ESR study

High‐intensity ultrasound was used to initiate the bulk polymerization of methyl methacrylate. The polymerization rate varied with the sonication time, the intensity of the ultrasound, and the initiator concentration of poly (methyl methacrylate) in the monomer. Electron spin resonance (ESR) spectra, obtained by the spin trapping technique, testified that free radicals were produced during the sonication process, and the concentration of radicals also changed with the sonication condition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1731–1735, 2002     

反应挤出技术在高聚物本体聚合中的应用进展

反应挤出技术是高聚物加工的一种新技术，是目前国际上竞相投资的热点。在高聚物本体聚合中反应挤出技术具有广阔的发展前景。重点介绍了反应挤出技术的特点，阐述了用反应挤出技术进行本体聚合制备高聚物的优点，综述了国内外近十年来反应挤出技术在高聚物本体聚合中的应用进展。     

Co(acac)2‐Mediated Radical Polymerization of Acrylonitrile: Control Over Molecular Weights and Copolymerization With Methyl Methacrylate

The cobalt‐mediated radical polymerization of acrylonitrile in DMSO using cobalt (II) acetylacetonate [Co(acac)₂] as mediator is studied. Both the evolution of molecular weight and conversion over time under various conditions are monitored. Molecular weights increase sharply at the beginning of the reaction and subsequently grow linearly with conversion. No branching of the polymer is observed by ¹³C NMR. By a careful design of the reaction parameters, number‐average molecular weights >1.2 · 10⁵ g · mol^?1 with a PDI around 2.4 together with conversions of up to 90% within 24 h are achieved. The copolymerization parameters of acrylonitrile with methyl methacrylate in DMSO at 30 °C are determined using the Kelen‐Tüdõs approach giving r_AN = 0.33, r_MMA = 0.71.

     

Continuous polymerization of ε‐caprolactone initiated by titanium phenoxide in a twin‐screw extruder

The continuous polymerization of ε‐caprolactone initiated by titanium phenoxide was carried out in both an internal mixer and a twin‐screw extruder. The polymerization was performed under different processing conditions, including various temperatures and screw speeds. To perform a kinetic study, samples were collected along the time axis (internal mixer) and along the screw axis (extruder). Size exclusion chromatography and proton nuclear magnetic resonance were used to study the evolution of the conversion degree with mixing time and with the extruder. The rheological behavior was also characterized. Temperature had a strong effect on conversion in the internal mixer, whereas in the twin‐screw extruder, both temperature and screw speed played major roles. The specificity of the titanium phenoxide to lead to high‐molar‐mass poly(ε‐caprolactone) under these processing conditions was also confirmed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetic study of the free‐radical polymerization of vinyl acetate in the presence of deuterated chloroform by 1H‐NMR spectroscopy

The free‐radical polymerization of vinyl acetate was performed in the presence of deuterated chloroform (CDCl₃) as a chain‐transfer agent (telogen) and 2,2′‐azobisisobutyronitrile as an initiator. The effects of the initiator and solvent concentrations (or equivalent monomer concentration) and the reaction temperature on the reaction kinetics were studied by real‐time ¹H‐NMR spectroscopy. Data obtained from analysis of the ¹H‐NMR spectra were used to calculate some kinetic parameters, such as the initiator decomposition rate constant (k_d), k_p(f/k_t)^1/2 ratio (where k_p is the average rate constant for propagation, f is the initiator efficiency, and k_t is the average rate constant for termination), and transfer constant to CDCl₃ (C). The results show that k_d and k_p(f/k_t)^1/2 changed significantly with the solvent concentration and reaction temperature, whereas they remained almost constant with the initiator concentration. C changed only with the reaction temperature. Attempts were made to explain the dependence of k_p(f/k_t)^1/2 on the solvent concentration. We concluded from the solvent‐independent C values that the solvent did not have any significant effect on the k_p values. As a result, changes in the k_p(f/k_t)^1/2 values with solvent concentration were attributed to the solvent effect on the f and/or k_t values. Individual values of f and k_t were estimated, and we observed that both the f and k_t values were dependent on the solvent (or equivalent monomer) concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymerization of acrylonitrile using potassium peroxydisulfate as an initiator in the presence of a multisite phase‐transfer catalyst: A kinetic study

In this article, the kinetics and mechanism of the free‐radical polymerization of acrylonitrile (AN) using potassium peroxydisulfate (PDS) as a water‐soluble initiator in the presence of synthesized 1,4‐bis(triethyl methyl ammonium) benzene dichloride (DC‐X) as a phase‐transfer catalyst (PTC) were studied. The polymerization reactions were carried out under inert and unstirred conditions at a constant temperature of 60 ± 1°C in cyclohexane/water biphasic media. The rate of polymerization (R_p) increased with an increase in the concentrations of AN, PTC, and PDS. The order with respect to the monomer, initiator, and PTC was found to be 1.0, 0.5, and 0.5, respectively. R_p was independent of the ionic strength and pH of the medium. However, an increase in the polarity of the solvent slightly increased the R_p value. On the basis of the obtained results, a mechanism is proposed for the polymerization reaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Reverse atom transfer radical polymerization of methyl methacrylate in different solvents

The reverse atom transfer radical polymerization of methyl methacrylate was investigated in different solvents: xylene, N,N‐dimethylformamide, and pyridine. The polymerizations were uncontrolled, using 2,2′‐bipyridine as a ligand in xylene and pyridine because the catalyst (CuBr₂/2,2′‐bipyridine complex) had poor solubility in the xylene system. In the pyridine system, the solubility of the catalyst increased, but the solvent could complex with CuBr₂, which influenced the control of the polymerization. In the N,N‐dimethylformamide system, the catalyst could be dissolved in the solvent completely, but the ? N(CH₃)₂ group in N,N‐dimethylformamide could also complex with CuBr₂, so the polymerization could not be well controlled. The ligand of 4,4′‐di(5‐nonyl)‐2,2′‐bipyridine was also investigated in xylene; the introduction of the ? CH(C₄H₉)₂ group enabled the CuBr₂/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine complex to easily dissolve in xylene, and the polymerizations were well controlled. The number‐average molecular weight increased linearly with the monomer conversion from 4280 to 14,700. During the whole polymerization, the polydispersities were quite low (1.07–1.10). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Reverse atom transfer radical polymerization of acrylonitrile under microwave irradiation

Reverse atom transfer radical polymerization was first used to successfully synthesize polyacrylonitrile under microwave irradiation. FeCl₃, coordinated by isophthalic acid, was used as the catalyst, and 2,2′‐azobisisoheptonitrilewas used as the initiator. N,N‐Dimethylformamide was used as the solvent to improve the solubility of the ligand. Under the same experimental conditions, the apparent rate constant under microwave irradiation was higher than that under conventional heating. The polymerization not only showed the best control of the molecular weight and its distribution but also provided a rather rapid reaction rate with the [acrylonitrile]/[2,2′‐azobisisoheptonitrile]/[FeCl₃]/[isophthalic acid] ratio of 300 : 1 : 1 : 2. The polymers obtained were used as macroinitiators to initiate the chain extension and successfully synthesize acrylonitrile polymers with a molecular weight higher than 50,000 and a narrow polydispersity as low as 1.30. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics and Mechanism of Potassium Persulphate/L-Serine Initiated Polymerization of Methylmethacrylate

The polymerization kinetics of methyl methacrylate with K₂S₂O₈/L-serine redox system has been investigated volumetrically at 35±0.1°C under nitrogen atmosphere acidic aqueous medium in DMF/H₂O mixture (50% v/v). The rates of polymerization were measured varying concentrations of the monomer, initiator, L-serine as well as temperature; and it was found to increase with increasing of both temperature and concentrations of monomer, initiator, and L-serine. The overall energy of activation (E _a ) has been calculated to be 29.48 kJ/mol from the Arrhenius plot in temperature range 25–50°C. The molecular weight of the polymer was determined by gel permeation chromatography (GPC). Based on kinetic studies and depending on the results obtained, a suitable reaction mechanism has been suggested and the rates of polymerization found to obey the following equation: V _p [methyl methacrylate]^1.09[L-serine]^1.03[K₂S₂O₈]^0.96.     

聚合物反应挤出技术及其应用研究进展

聚合物反应挤出技术是一门将聚合反应与挤出成型结合在一起的新兴工艺,简述了聚合物反应挤出技术的原理及特点,综述了聚合物反应挤出技术在本体聚合、接枝反应、反应共混、以及可控降解等方面的应用研究新进展。     

Concentrated emulsion polymerization of methyl methacrylate/butyl acrylate initiated by a redox system

Stable concentrated emulsions of methyl methacrylate/butyl acrylate were prepared with sodium dodecyl sulfate and cetyl alcohol as the compound surfactant and poly(vinyl alcohol) as the major reinforcer of the liquid film. With a redox system based on benzoyl peroxide/N,N′‐dimethyl phenylamine introduced into the concentrated emulsions, polymer particles with different shapes and sizes were obtained by initiation of the polymerization at low temperatures. We investigated the kinetic behaviors of concentrated emulsion polymerization and drew linear regression diagrams of its time–conversion curves in a constant rate phase (conversions ranged from 20 to 70%), and the experimental results show that the variation of the concentrations of the compound surfactant and initiator, the categories of reinforcers of the liquid film, the temperatures, and so on were responsible for the polymerization stability and the polymerization rate. Finally, the kinetics equation and activation energy of the initiator were obtained. The particle size and distribution of particle diameters of latex particles were determined by photon correlation spectroscopy. The determination results reveal that concentrations of the compound surfactant, polymerization temperatures, and so on affected the shape and size of the polymer particles greatly. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1695–1701, 2005     

A new general approach to determine more accurate comonomer reactivity ratios in controlled/living radical copolymerization systems

In controlled/living radical copolymerization (atom transfer radical copolymerization in this study) and in any other living chain‐growth copolymerization, the possible preferential addition of one of the comonomers onto the (macro)initiator‐derived (macro)radical can affect the copolymer composition, especially at low conversion; this results in inaccurate comonomer reactivity ratio estimation by the classic approach. A new general approach is introduced in this article, which allowed us to exclude the influence of the possible preferential addition of one of the comonomers onto the (macro)initiator‐derived (macro)radical on the copolymer composition at any conversion. According to this approach, copolymer chain grown during time t (t ≠ 0) is considered to be, in fact, the macroinitiator terminated with one of the comonomers under study, which will further grow during the time interval Δt′ = t′ ? t [where any reaction time t′ is considered to be grater than reaction time t, i.e. t′ > t] from a comonomer mixture with composition of f(t) [where f(t) is the molar ratio of comonomer i to comonomer j in the comonomer mixture] at time t. In such a situation, it is possible to obtain individual comonomer conversions [x_i(Δt′) and x_j(Δt′)], the overall comonomer conversion [x_ov(Δt′)], and the cumulative average copolymer composition for the copolymer formed during Δt′, from which more accurate comonomer reactivity ratios can be calculated by the various low‐ or high‐conversion methods, depending on the overall comonomer conversion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Bulk polymerization of styrene in the presence of organomodified montmorillonite

The effect of montmorillonite (Cloisite 6A) on the bulk polymerization of styrene initiated by benzoyl peroxide (BPO) was studied by the dilatometric determination of the polymerization rates. The bulk polymerization rates increased as the montmorillonite input quantity increased. The effect became greater when the BPO concentration decreased. Under the assumption that clay participated in the radical initiation reaction of the chains, the reaction orders for clay and BPO were determined to be approximately 1.0 and 0.5, respectively. X‐ray diffraction and thermogravimetric analysis studies showed that the structure and properties of the obtained polystyrene (PS)/montmorillonite nanocomposites were greatly affected by the BPO concentration. With lower BPO concentrations, a larger interlayer distance and a higher extent of delamination for the clay were observed in the obtained PS/montmorillonite nanocomposites. The nanocomposites prepared with lower BPO concentrations also showed higher heat‐decomposition‐resistance temperatures. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1146–1152, 2005     

Effect of the carboxylic acid monomer type on the emulsifier‐free emulsion copolymerization of styrene and butadiene

Carboxylated styrene–butadiene rubber latexes were prepared through the emulsifier‐free emulsion copolymerization of styrene and butadiene with various carboxylic acid monomers. The effects of various carboxylic acid monomers on the particle formation process were investigated. The type of carboxylic acid monomer strongly affected the particle nucleation. The number of particles and thus the polymerization rate increased with the increasing hydrophobicity of the carboxylic acid monomers. There was a significant difference in the polymerization rate per particle. The results showed that particle nucleation and growth were dependent on the hydrophilic nature of the carboxylic acid monomers. The average particle diameter of the carboxylated styrene–butadiene rubber latexes in the dry state was obtained through some calculations using direct measurements of the average particle diameter in the monomer‐swollen state by a dynamic light scattering technique. Several parameters, such as the polymerization rate, number of latex particles per unit of volume of the aqueous phase, and polymerization rate per particle, were calculated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Reactivity ratios and monomer partitioning in the microemulsion copolymerization of vinyl acetate and butyl acrylate

The true monomer reactivity ratios for the vinyl acetate/butyl acrylate system were determined with experimental data from the cumulative copolymer composition at low, intermediate, and high conversions and with the monomer partitioning among the aqueous, microemulsion droplet, and polymer particle phases taken into account. A mixture of sodium dodecyl sulfate and poly(ethylene oxide) (23) dodecyl ether (Brij‐35; 3 : 1 w/w) was used as a stabilizer. Potassium persulfate was used as an initiator. The true values of the monomer reactivity ratios were 0.028 ± 3.2 × 10^?3 for vinyl acetate and 6.219 ± 3.1 × 10^?1 for butyl acrylate, and these were in agreement with those reported in the literature for bulk copolymerizations but differed from values reported for other compartmentalized copolymerizations. Thus, these results indicate that the monomer partitioning and cumulative copolymer composition throughout the reaction have to be duly accounted for in the determination of monomer reactivity ratios in heterogeneous polymerizations. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Styrene/tetradecyl methyl acrylate/3‐methacryloxylpropyl trimethoxyl silane triblock copolymers: Atom transfer radical polymerization synthesis and effects on the glass‐fiber/polypropylene interphase properties as a macromolecular coupling agent

Styrene/tetradecyl methyl acrylate/3‐methacryloxylpropyl trimethoxyl silane triblock copolymers (PSTKs), with well‐defined structures and narrow molecular weight distributions, were synthesized by atom transfer radical polymerization. They were investigated as macromolecular coupling agents for the surface treatment of glass fibers. The reaction kinetics for the triblock copolymers were studied. The contact angles of the copolymers with water and diiodomethane showed that a modified‐glass‐fiber surface treated with a PSTK solution had strong hydrophobicity and that the impregnation of polypropylene on glass fibers was improved dramatically. In comparison with a film of 3‐methacryloxylpropyl trimethoxyl silane, the polarity of the surface free energy of a PSTK film decreased, whereas the dispersion increased greatly. The critical concentration of the macromolecular coupling agents was obtained, and the monolayer saturated adsorptive capacity was calculated with the Gibbs absorption isotherm equation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1661–1670, 2007     

塑料光纤成型技术及应用前景展望

简要描述了塑料光纤的种类和材料,着重阐述其主要成型技术：棒拉法和挤出法,并对塑料光纤的应用前景进行了展望。