Polymerization in a magnetic field. XV Some azo‐initiators behavior in a high magnetic field

The effect of a high magnetic field of 7 T on styrene polymerization reactions was taken under study. The intervened magnetokinetic modifications are correlated to the system of radical initiation, respectively: benzoyl peroxide, 2, 2′‐azobis(2‐methylpropionitrile), 4, 4′‐azobis(4‐cyanopentanoic acid), and 1,1′‐azobis (cyclohexan‐1‐carbonitrile). The reaction products are also characterized from the viewpoint of their molecular weights correlated with the reaction conditions, as well as their thermal stability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1025–1031, 2005     

Polymerization in a magnetic field,part 17: Styrene copolymerization with 2,3‐epoxypropyl methacrylate

The article presents a comparative study regarding the magnetic field influence intervened during styrene copolymerization with 2,3‐epoxypropyl methacrylate using a radical emulsion polymerization procedure. The registered magnetokinetic effects were evidenced for different reaction compositions and temperatures. The field effect influenced the conversion, the polymerization rate, and activation energy of polymerization process. An efficiency of magnetic field from the kinetic parameters has been established. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Aspects regarding the grafting of some lignosulfonates with acrylamide under a magnetic field

The kinetics of the graft polymerization of acrylamide onto some lignosulfonate products in a continuous external magnetic field was studied. The registered magnetokinetic effects were correlated and associated with the conditions of the classic reaction. The grafting process of acrylamide onto the macromolecular chains depending on the cation (Ca²⁺, Cr²⁺, Fe²⁺, Fe³⁺ and NH₄⁺) present in the lignosulfonate structure and the magnetic field influence were corroborated and explained through the radical pairs mechanism. The augmentation of the graft polymerization rate in magnetic field and conversion was ascribed to the singlet-triplet transitions in the radical pairs as a result of the presence of the magnetic field.     

Kinetic study of radical polymerization. III. Solution polymerization of acrylamide by 1H‐NMR

Solution and radical polymerization of acrylamide in the presence of potassium persulfate in D₂O was investigated up to high conversion by high‐field ¹H‐NMR spectroscopy. The kinetics of reaction was studied according to the data obtained from the corresponding spectra at various times during the polymerization reaction progress. Processing of the data led us to derive the rate equation of this polymerization reaction and determine the reaction order of each component in the rate equation. The order, with respect to initiator, was consistent with the classical kinetic rate equation (0.45), whereas the order with respect to monomer was greater than unity (1.49). The effect of temperature on the polymerization rate was also investigated and the activation energy of 48.4 kJ mol^?1 was obtained over the temperature range of 60–75°C. Also some mechanistic studies were discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2007–2013, 2004     

Polymerization in magnetic field: XVIII. Influence of surfactant nature on the synthesis and thermal properties of poly(methyl methacrylate) and poly[(methyl methacrylate)‐co‐(epoxypropyl methacrylate)]

BACKGROUND: The possibility to use β‐cyclodextrin as biodegradable tensioactive and an electromagnetic field in order to improve the kinetic parameters of radical emulsion polymerization is of interest. Thus, the influence of different surfactants—sodium lauryl sulfate (SLS) and β‐cyclodextrin (CD)—on the pathway of emulsion polymerization of methyl methacrylate (MMA) and emulsion copolymerization of MMA with 2,3‐epoxypropyl methacrylate (GMA) performed with or without the presence of a continuous electromagnetic field (MF) was studied. RESULTS: The presence of the MF leads to a considerable increase of the conversion during the first part of the reaction if the classic surfactant (SLS) is used. The reactions performed without MF and with CD exhibit a decrease of the conversion and of the polymerization rate as compared with the variants using SLS. The swelling rate and the maximum degree of swelling vary with the surfactant nature and with the reaction conditions and MF presence. Data from thermogravimetry and differential scanning calorimetry evidence the dependences between the polymer characteristics and the preparation conditions. CONCLUSION: This research underlines the coupling possibilities of the influence of a MF—growth of the reaction rate and conversion explained through radical pairs mechanism—with a combination of the ‘cage’ effect and ‘conformational control’ afforded by CD. The presence of MF and CD during the syntheses leads to an increase of T_g and an increase of PMMA and P(MMA‐co‐GMA) thermal stability. Copyright © 2007 Society of Chemical Industry     

Kinetic study of radical polymerization. II. Solid‐state bulk polymerization of sodium methacrylate by differential scanning calorimetry

The solid‐state radical polymerization of sodium methacrylate was investigated. It was initiated by azobisisobutyronitrile, which was used as a radical initiator. Differential scanning calorimetry (DSC) was used to observe the endothermic and exothermic transitions during the polymerization reaction. Structural studies were performed with the DSC thermograms and Fourier transform infrared and ultraviolet–visible spectra, and all of the results confirmed the progress of the reaction. The obtained data revealed that the polymerization reaction proceeded completely with a 100% conversion. ΔH of this reaction was calculated with various amounts of the initiator, and the peak temperatures were determined at different heating rates. The activation energy (19.7 kcal mol^?1) was also obtained by the Kissinger method for this type of solid polymerization reaction. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1648–1654, 2003     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

Reverse atom transfer radical polymerization of n‐butyl methacrylate in an aqueous dispersed system

Reverse atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) was conducted in an aqueous dispersed system. The influence of the surfactant, catalyst, reaction time and temperature on the colloidal stability and the control of polymerization was investigated. As a result, using an azo initiator (AIBN), a non‐ionic surfactant (Brij 35) and a hydrophobic ligand (dNbpy) to complex a copper halide, polymers with predetermined molecular weight and low polydispersity were obtained as stable latexes. Copyright © 2004 Society of Chemical Industry     

Characterization of poly(butyl acrylate) diols prepared via atom transfer radical polymerization and subsequent modification

We used atom transfer radical polymerization to synthesize poly(butyl acrylate) (PBA) and then substituted the bromo end group with N-ethanol methyl amine to obtain the hydroxyl (OH) end-capped poly(butyl acrylate). A compound of PBA with Mn of about 500 was first synthesized and used as a model compound to investigate the substitution reaction conditions of bromo end group with N-ethanol methyl amine. The OH functionality over 0.8 was obtained when the model compound was reacted with N-ethanol methyl amine under the reaction temperature of 90°C for about 24 h. A poly(butyl acrylate) diol of Mn 2000 with OH functionality of about 1.76 was obtained and characterized by infrared spectrum (IR), hydrogen nuclear magnetic resonance (HNMR) spectra, gel permeation chromatography (GPC) and thermo gravimetric analysis (TGA).     

Visible‐light‐induced controlled/living radical polymerization of styrene with a phenyl seleno group at one terminal chain end: 1‐(Phenylseleno)ethyl benzene as a photoiniferter

The photopolymerization of styrene with a well‐defined molecular architecture and a low polydispersity index and with methyl and phenylseleno (? SePh) groups at α‐ and ω‐chain ends, respectively, was performed via a controlled/living radical polymerization with a new initiating system, 1‐(phenylseleno)ethyl benzene/tert‐butyl diphenyl (phenylseleno) silane, through the absorption of visible light at room temperature. A novel initiating living radical polymerization was examined. The yield and number‐average molecular weight (M_n) of the resulting polymer increased with the reaction time. Furthermore, a linear relationship was found in a plot of M_n versus the polymer yield. These results indicated that this polymerization proceeded through a living radical mechanism. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 348–355, 2004     

Synthesis and characterization of diblock,triblock, and multiblock copolymers containing poly(3‐hydroxy butyrate) units

A poly[(R,S)‐3‐hydroxybutyrate] macroinitiator (PHB‐MI) was obtained through the condensation reaction of poly[(R,S)‐3‐hydroxybutyrate] (PHB) oligomers containing dihydroxyl end functionalities with 4,4′‐azobis(4‐cyanopentanoyl chloride). The PHB‐MI obtained in this way had hydroxyl groups at two end of the polymer chain and an internal azo group. The synthesis of ABA‐type PHB‐b‐PMMA block copolymers [where A is poly(methyl methacrylate) (PMMA) and B is PHB] via PHB‐MI was accomplished in two steps. First, multiblock active copolymers with azo groups (PMMA‐PHB‐MI) were prepared through the redox free‐radical polymerization of methyl methacrylate (MMA) with a PHB‐MI/Ce(IV) redox system in aqueous nitric acid at 40°C. Second, PMMA‐PHB‐MI was used in the thermal polymerization of MMA at 60°C to obtain PHB‐b‐PMMA. When styrene (S) was used instead of MMA in the second step, ABCBA‐type PMMA‐b‐PHB‐b‐PS multiblock copolymers [where C is polystyrene (PS)] were obtained. In addition, the direct thermal polymerization of the monomers (MMA or S) via PHB‐MI provided AB‐type diblocks copolymers with MMA and BCB‐type triblock copolymers with S. The macroinitiators and block copolymers were characterized with ultraviolet–visible spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, cryoscopic measurements, and thermogravimetric analysis. The increases in the intrinsic viscosity and fractional precipitation confirmed that a block copolymer had been obtained. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1789–1796, 2004     

Synthesis and characterization of novel hydrophobically modified polybetaines as pour point depressants

A novel hydrophobic monomer was synthesized from the acetoacetic ester and dodecylamine by condensation reaction in mild conditions. The modification by the dodecyl groups monomer was involved in the Michael addition reaction with acrylic (or methacrylic) acid followed by radical polymerization. Both linear and crosslinked novel betaine‐type polyampholytes bearing hydrophobic “tail” and hydrophilic “head” were obtained. The linear polymer was characterized by viscometry, FTIR, and Raman spectroscopy. Swelling–shrinking behavior of linear and crosslinked samples was studied in water–DMF and water–DMSO mixtures. The applicability of hydrophobically modified polybetaines as pour point depressants (fluidity improvers) was also demonstrated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1042–1048, 2004     

Bulk and suspension polymerization of styrene in the presence of n-pentane. An evaluation of monofunctional and bifunctional initiation

The plasticizing effect of n-pentane on the rate of bulk free radical polymerization of styrene and molecular weight distribution development has been modeled on the basis of the free volume theory for both monofunctional and bifunctional initiation. A strong decrease in the reaction rate in the late stages of the polymerization, due to the displacement of the onset of the gel effect, has been observed for both types of initiation. This decrease in the polymerization rate limited the terminal conversion to values well below 100% for mono-functional initiation. However, in bifunctionally initiated polymerization, terminal conversions close to 100% were obtained in spite of the decrease in reaction rate. Contrary to what was expected, the molecular weight distribution obtained at terminal conversion was almost completely insensitive to these changes in polymerization rate. This phenomenon is explained in terms of limited transfer to monomer reactions when n-pentane is present in the system. In suspension polymerization, the limiting conversion and plasticizing effects of n-pentane in monofunctionally initiated systems, caused enhanced coalescence leading to suspension set-up. In bifunctionally initiated systems this enhanced coalescence was completely overcome by the short duration of the particle growth stage, owing to high polymerization rates, and stable suspensions were achieved. For these systems the particle size distributions obtained were similar to that of suspension polystyrene without n-pentane. © 1993 John Wiley & Sons, Inc.     

Spatially resolved studies on the photopolymerization of dimethacrylate monomers

The photopolymerization of four dimethacrylate monomers under different irradiating conditions was followed in situ by ¹H stray-field magnetic resonance imaging (¹H STRAFI-MRI). This technique is capable of discriminating local changes at a spatial resolution of tens of micron and is suitable for studying larger samples than infrared spectroscopy and photocalorimetry. The evolution of proton magnetization with irradiation time and intensity was recorded and correlated with volumetric polymerization shrinkage, extent of reaction and spatially resolved reaction rates.     

Kinetics and reaction mechanism of template polymerization investigated by conductimetric measurements. Part 3. Radical polymerization of acrylic acid in the presence of poly(N‐vinylpyrrolidone)

Conductimetry was used for monitoring the radical polymerization of a weak electrolyte (acrylic acid) in aqueous solution and for determination of the kinetic parameters of the reaction (reaction order with respect to monomer, activation energy). The results obtained were consistent with those determined by other techniques (such as dilatometry) or expected from theory. Dilatometric and conductimetric measurements were also used to study the template polymerization of acrylic acid onto poly(N‐vinylpyrrolidone). Results indicate that the reaction proceeds according to a pick‐up mechanism. Complexes between poly(acrylic acid) and poly(N‐vinylpyrrolidone) were always isolated in equimolar composition of the two polymers, regardless of the polymerization mixture composition. Spectroscopic evidence of the existence of strong interaction and intimate mixing of the two polymers in the complexes was found. An influence of the template molecular weight on the chain length of the forming poly(acrylic acid) was detected by means of viscometry. © 2000 Society of Chemical Industry     

Toward a better understanding of the emulsion polymerization of butadiene. I. Continuous conductivity measurements

Continuous conductivity measurements were performed during the batch emulsion polymerization of butadiene along with kinetic and particle size measurements. The critical monomer conversion was obtained around 55% and the rate of polymerization was correlated to the surfactant concentration with an exponent of 0.35 which was not in agreement with the exponent offered by Smith and Ewart. In addition, the evolution of some particle‐related quantities such as particle size and number of particles during the three intervals of the emulsion polymerization and their agreements with Smith‐Ewart mechanism were investigated. The behavior of conductivity in the emulsion polymerization of butadiene normally containing a buffering agent was found to be completely different from the unbuffered one. Comparison of the conductivity profiles with the kinetic and particle‐related quantities represented that the conductivity of the reaction mixture is very sensitive to the changes in the particle size so that any small change in the forms of nucleation, growth, and coagulation is clearly observed in the conductivity profiles. Furthermore, the conductimetric data are capable of determining some important points during the polymerization such as the beginning of the reaction that can be important from the industrial process control point of view. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45262.     

Synthesis and characterization of the novel block copolymer poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine) by the combination of coordination and controlled free‐radical polymerizations

A novel block copolymer, poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine), was synthesized with a bifunctional initiator strategy. Poly(ε‐caprolactone) prepolymer with a 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) end group (PCL_T) was first obtained by coordination polymerization, which showed a controlled mechanism in the process. By means of ultraviolet spectroscopy and electron spin resonance spectroscopy, the TEMPO moiety was determined to be intact in the polymerization. The copolymers were then obtained by the controlled radical polymerization of 4‐vinyl pyridine in the presence of PCL_T. The desired block copolymers were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, and NMR spectroscopy in detail. Also, the effects of the molecular weight and concentration of PCL_T on the copolymerization were investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2280–2285, 2004     

Novel 6-bromo-3-ethyl-2-styrylbenzothiazolium <Emphasis Type="Italic">n</Emphasis>-butyl-triphenylborates as photoinitiators of trimethylolopropane triacrylate (TMPTA) polymerization

Summary The series of 6-bromo-3-ethyl-2-styrylbenzothiazolium n-butyltriphenylborates was synthesized and evaluated as photoinitiators of free radical polymerization. The dyes were obtained by the condensation reaction of the 6-bromo-3-ethyl-2-methylbenzothiazolium salts with different alkylaminobenzaldehydes. The resulting styrylbenzothiazole dyes (hemicyanine dyes) paired with n-butyltriphenylborate anion (SBrB2), are shown to be efficient photoinitiators for free radical polymerization of trimethylolpropane triacrylate (TMPTA) induced with the visible emission of an argon-ion laser. The photochemistry of the novel hemicyanine borates was compared to the photochemistry of identical series of the dyes that do not possess the bromo substituent at benzothiazolium residue. The comparison has shown that the introduction of the bromine into benzothiazolium residue causes a small red shift of the electronic absorption maxima, changes the reduction potential of the dye and, finally, increases a photoinitiation ability of the dye.     

The Cation Radical Chain Cycloaddition Polymerization of N,3‐Bis(trans‐1‐2)carbazole: The Critical Importance of Intramolecular Hole Transfer in Cation Radical Cycloaddition Polymerization

The synthesis and polymerization of N,3‐[bis(trans‐1‐2)]carbazole ( 1 ) is reported. Using either the stable cation radical salt tris(4‐2)aminium hexachloroantimonate ( 2 ^+. ) or anodic oxidation to initiate the reaction, novel cycloaddition polymers are obtained in which the intermonomer linkages are of the cyclobutane, and to some extent of the Diels−Alder, type. A novel cation radical chain mechanism is proposed for the reaction, and extensive support for this mechanism is presented. The greatly enhanced reactivity of difunctional, as opposed to monofunctional, substrates in cation radical cycloadditions is dramatically highlighted by a comparison of the cycloaddition reactivity (rapid polymerization) of 1 versus N‐propenylcarbazole (inefficient cyclodimerization) under electrochemical oxidation conditions. The sharply enhanced reactivity of 1 is attributed to the availability of intramolecular hole transfer in the bifunctional but not the monofunctional case.     

Grafting of polyacrylonitrile onto guar gum under microwave irradiation

Using microwave (MW) irradiation grafting of polyacrylonitrile (PAN) onto guar gum in water was done without using any radical initiator or catalyst within a very short reaction time. The extent of grafting could be adjusted by controlling the reaction conditions and maximum percentage grafting (%G) of about 188% was obtained under optimum conditions in 1.66 min. The average molecular weight of the grafted PAN chains and water‐retention power of the alkali hydrolyzed MW‐grafted gums were also determined and compared with those of the conventionally synthesized (cs) graft copolymer. A representative MW‐grafted copolymer, guar‐g‐polyacrylonitrile was characterized by IR, NMR, XRD, TGA, and elemental analysis. A plausible mechanism for the grafting under MW was proposed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1569–1575, 2004