Kinetics of the batch cationic emulsion polymerization of styrene: A comparative study with the anionic case

An in‐depth study on the kinetics of the cationic emulsion polymerization of styrene in a batch reactor is presented. This study is focused on the effect of the amount of the cationic surfactant dodecyltrimethylammonium bromide (DTAB), using two different cationic initiators: 2,2′‐azobisisobutyramidine dihydrochloride (AIBA), 2,2′‐azobis (N,N′‐dimethyleneisobutyramidine) dihydrochloride (ADIBA), on kinetics and colloidal features such as conversion, number of particles, number average of radicals per particle, mean particle diameter, and particle size distribution (PSD) of the polystyrene latices obtained by emulsion polymerization in a batch reactor. Furthermore, the results of the cationic emulsion polymerization were compared with its homologous anionic case. Using DTAB as cationic surfactant an expected increase in the total rate of polymerization was observed when the DTAB concentration increased. However, the total number of particles increased much more than in the anionic system. On the other hand, a dependence on the particle size of the rate of polymerization per particle together with the average number of radicals per particle was found. These differences between cationic and anionic emulsion polymerizations were explained taking into account the limited particle coagulation observed with cationic surfactants, and the high rate of radical formation of cationic initiators. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4461–4478, 2006     

A High Performance Flocculating Agent and Viscosifiers Based On Cationic Guar Gum

The anionic, cationic and nonionic polymeric flocculants endowed with several distinguished characteristics are being increasingly applied for the treatment of industrial effluents, municipal and wastewater. For the treatment of highly negatively charged particle suspensions, cationic flocculants are more efficient. A new route to guar gum derivatives bearing cationic groups has been developed. A series of cationic guar gums (Cat GG) have been developed by incorporating a cationic moiety N- (3- Chloro-2- hydroxypropyl) trimethyl ammonium chloride (CHPTAC) onto the backbone of guar gum in presence of NaOH. The various grades of cationic guar gum have been characterized by elemental analysis, FTIR spectroscopy and intrinsic viscosity measurement. The flocculation characteristics of these cationic guar gums have been evaluated in silica suspension by jar test. It has been found that among the various grades of cationic guar gums, the one with longer CHPTAC chains shows better performance. The flocculation characteristics of this best performing cationic guar are compared with those of various commercially available flocculants in silica suspension. Their rheological investigations have also been undertaken.     

Aftertreatment of Conventional Direct Dyeings of Cotton with a Bis-reactive Cationic Fixing Agent

A bis-reactive cationic fixing agent, ethylenebis[N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride] has been used as an aftertreatment reagent to improve the wash fastness of direct dyes on cotton. The effects of different pH conditions and concentrations on the effectiveness of this cationic fixing agent have been investigated. The results showed that aftertreatment at pH 11 produced dyeings with higher colour strength and better wash fastness than that at pH 7. In addition, the cationic agent at a low concentration was found to be more effective under both neutral and alkaline conditions.     

Photoinitiated Cationic Polymerization of 3-Ethyl-3-(phenoxymethyl)-oxetane in Nitrogen Atmosphere

Abstract

The photoinitiated cationic polymerizations of 3-ethyl-3-(phenoxymethyl)-oxetane (PhO) and phenyl glycidyl ether (PhE) with diphenyl-4-thiophenoxyphenyl sulfonium hexafluoroantimonate as the cationic photoinitiator were carried out in air and nitrogen atmospheres. A real time FT-IR method was used to estimate the polymerization rates. The number-average molecular weight (M _n) of the resulting polymers were measured by gel permeation chromatography. In nitrogen, the photopolymerization rate of PhO was more than four times greater than in air, while there was no essential difference for PhE. The M _n of the PhO polymer increased from 13,900 (in air) to 61,200 (in nitrogen) at the peak top. The fast polymerization mechanism in nitrogen was postulated to be the radical-assisted decomposition of the sulfonium salt.     

Semicontinuous seeded cationic emulsion polymerization of styrene: The effects of the concentration and type of cationic surfactant

The objective of this work was to analyze the effects of the concentration and type of cationic surfactant on the kinetic features (instantaneous and overall conversions) and colloidal characteristics [mean particle diameter, particle size distribution (PSD), and surface charge density] in the semicontinuous seeded cationic emulsion polymerization of styrene. 2,2′‐Azobis(N,N′‐dimethyleneisobutyramidine)dihydrochloride was used as an initiator. The surfactants were dodecyltrimethylammonium bromide (DTAB) and hexadecyltrimethylammonium bromide (HDTAB). So that the evolution of some polymeric and colloidal characteristics of the synthesized latices could be followed, the overall and instantaneous conversions were defined and determined gravimetrically. The PSDs and average particle diameters were determined by transmission electron microscopy and photon correlation spectroscopy. The surface charge density was determined by conductimetric titration. The evolution of the instantaneous conversions, the total number of particles, and the PSDs of the different reactions were related to the nucleation, growth, and coagulation processes taking place in the semicontinuous seeded emulsion polymerizations. The PSDs obtained from the reactions carried out with the emulsifier DTAB, at a concentration equal to its critical micelle concentration (cmc) and at a concentration twice its cmc, presented more and smaller particles than those obtained by the addition of HDTAB to the polymerization recipe. At lower emulsifier concentrations equal to half of the cmc, the system had lower colloidal stability with DTAB. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2322–2334, 2003     

Indefinitely active aqueous cationic polymerizations,part I: Low cost,recyclable initiator systems

This article describes the first example of an aqueous cationic polymerization that utilizes a low cost, safe, and highly recyclable initiator system (phosphotungstic acid) that retains its activity indefinitely. Quantitative yields of low to medium molecular weight polymers of p-methoxystyrene and N-vinylcarbazole are obtained within minutes to hours. Polymerization is first order in both monomer and phosphotungstic acid. Negatively charged surfactants suppress polymerization; whereas, nonionic soaps increase the reaction rate and reduce both polymer molecular weight and polydispersity index. Herein, the discovery of a new form of aqueous cationic polymerization involving the condensation of the alcoholic derivative of p-methoxystyrene, 1-(4-methoxyphenyl)ethanol, is also disclosed.     

Redox initiated cationic polymerization: Silane‐N‐aryl heteroaromatic onium salt redox couples

In this article, a new route for the synthesis of N‐aryl heteroaromatic onium salts by the direct copper catalyzed arylation of pyridine, substituted pyridines, isoquinoline, and acridine with diaryliodonium salts is described. It was demonstrated that these N‐aryl heteroaromatic onium salts undergo facile platinum or rhodium‐catalyzed reduction by silanes bearing Si? H groups. The reduction of N‐aryl heteroaromatic onium salts generates Brønsted acids. When this redox reaction was carried out in situ in the presence of an appropriate monomer, cationic polymerization was observed. Using this approach, the cationic polymerizations of epoxides, oxetanes, 1,3,5‐trioxane, styrene, and vinyl ethers were carried out. The use of optical pyrometry to monitor the redox initiated cationic polymerizations of some representative multifunctional monomers is described. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Photoinitiated cationic polymerization using o-phthaldehyde and pyridinium salt

The cationic polymerization of cyclohexene oxide (CHO), n-butyl vinylether (BVE), N-vinylcarbazole (NVC), and 4-vinyl cyclohexenedioxide (4-VCHD) is initiated upon UV irradiation (Λ_inc. = 350 nm) of dichloromethane solution containing N-ethoxy-2-methyl-pyridinium hexafluorophosphate (EMP⁺PF₆) and o-phthaldehyde. A feasible initiation mechanism involves formation of biradical by intramolecular hydrogen abstraction of triplet o-phthaldehyde. Oxidation of these radicals by EMP⁺ ions yields protons capable of initiating the cationic polymerization. © 1995 John Wiley & Sons, Inc.     

Dual Reactivity of Magnesium Compounds as Initiators for Anionic and Cationic Polymerization

Organomagnesium compounds are well known initiators of anionic polymerization of polar monomers. However, we have found recently that in the presence of compounds with labile halogen atoms, e.g., benzyl chloride, they are also active initiators of cationic polymerization of isobutylene and styrene in hydrocarbon media. The tentative scheme of cationic initiation is suggested assuming the formation of benzyl cation connected with Mg₂Cl₅⁻ counter-ion. The scheme is confirmed by quantum-chemical calculations and ¹H NMR analysis of polyisobutylene. On addition of a polar monomer, N,N-dimethylacrylamide or 2-vinylpyridine, to Bu₂Mg-BzCl-isobutylene polymerizing mixture, the former readily polymerizes. The mixture of homopolymers rather than block copolymers is formed in this case, however, this fact proves the co-existence of anionic and cationic centers in the system.     

Novel N‐methylbenzothiazolium salts as hardeners for epoxy and acrylate monomers

Novel N‐methylbenzothiazolium salts [N‐methyl‐2‐benzylthiobenzothiazolium, N‐methyl‐2‐(4‐nitrobenzylthio)benzothiazolium, N‐methyl‐2‐(1‐ethoxycarbonylethylthio)benzothiazolium, and N‐methyl‐2‐methylthiobenzothiazolium hexafluoroantimonates] were synthesized by the reaction of the corresponding 2‐substituted benzothiazole with dimethylsulfate, followed by anion exchange with KSbF₆. These benzothiazolium salts cationically polymerized an epoxy monomer by photoirradiation. They also polymerized an acrylate monomer via a photoradical process. The use of aromatic compounds such as 2‐ethyl‐9,10‐dimethoxyanthracene as photosensitizers was effective in enhancing the polymerization. These benzothiazolium salts also served as thermal cationic initiators. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3828–3837, 2003     

Novel pyridinium salts as cationic thermal and photoinitiators and their photosensitization properties

Novel pyridinium salts [N‐(α‐phenylbenzyl)‐, N‐(1‐naphthylmethyl)‐, or N‐cinnamyl p‐ or o‐cyanopyridinium hexafluoroantimonates] were synthesized by the reaction of p‐ or o‐cyanopyridine and the corresponding bromides followed by anion exchange with KSbF₆. These pyridinium salts polymerized epoxy monomers at lower temperatures than previously reported for N‐benzyl‐2‐cyanopyridinium hexafluoroantimonate. The o‐substituted pyridinium salts showed higher activity than the p‐substituted ones, and the crosslinked epoxy polymers cured with these initiators showed higher glass‐transition temperatures. These pyridinium salts photoinitiated radical polymerization as well as cationic polymerization. The photopolymerization was accelerated by the addition of aromatic ketones as photosensitizers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1037–1046, 2002     

Water‐soluble acrylamide copolymers. IX. Preparation and characterization of the cationic derivatives of poly(acrylamide‐co‐n,n‐dimethylacrylamide), poly(acrylamide‐co‐methacrylamide), and poly(acrylamide‐co‐n‐t‐butylacrylamide)

This article extends the preparative details of a series of nonionic copolymers of acrylamide with N,N‐dimethylacrylamide, methacrylamide, and N‐t‐butylacrylamide to the synthesis of cationic derivatives of these new copolymers. The described procedures gave products with cationicities of 14–26 mol %. We measured the mean squared radii of gyration and intrinsic viscosities of aqueous solutions of these products at several different pHs and NaCl concentrations to compare these values with those determined for the nonionic precursors and related commercial cationic polymers. Because the molecular weights of the examples measured varied widely, it was difficult to establish definite trends. However, the large values obtained for the mean squared radii of gyration and intrinsic viscosities, relative to the nonionic precursors of these polymers, demonstrated that the charged groups had a qualitatively greater effect on polymer extension than the nonpolar bulky groups. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2525–2535, 2001     

Antifungal Imidazole‐Decorated Cationic Amphiphiles with Markedly Low Hemolytic Activity

Herein we report that an imidazole‐decorated cationic amphiphile derived from the pseudo‐disaccharide nebramine has potent antifungal activity against strains of Candida glabrata pathogens. In combination with the natural bis‐benzylisoquinoline alkaloid tetrandrine the reported antifungal cationic amphiphile demonstrated synergistic antifungal activity against Candida albicans pathogens. This unique membrane disruptor caused no detectible mammalian red blood cell hemolysis at concentrations up to more than two orders of magnitude greater than its minimal inhibitory concentrations against the tested C. glabrata strains. We provide evidence that potency against C. glabrata may be associated with differences between the drug efflux pumps of C. albicans and C. glabrata. Imidazole decorated‐cationic amphiphiles show promise for the development of less toxic membrane‐disrupting antifungal drugs and drug combinations.     

Synthesis and polymerization of tail-type cationic polymerizable surfactants and hydrophobic counter-anion induced association of polyelectrolytes

A series of tail-type cationic surface-active monomers with the cationic charge at the -end (1; ST-C_m-AB, m=5, 7, and 9, where ST is a styrenic group, C_m the alkylene chain at the 4-position of styrene, and AB is alkyltrimethylammonium bromide) have been synthesized as a novel cationic polymerizable surfactant. Their fundamental physicochemical properties such as critical micelle concentration (cmc) and weight-average aggregation number of the micelle (N_w(agg)) have been characterized in water at 25 °C by static light-scattering measurements. The cmc values determined for the tail-type surfactant monomers are two-orders of magnitude smaller than those of the corresponding head-type cationic surfactant monomers (2; ST-C₁-AC-C_m). The N_w(agg) of ST-C_m-AB is 68 for m=5, 156 for m=7, and 413 for m=9. Free-radical homopolymerization of ST-C₇-AB proceeds very rapidly in water as a result of organization in the micelle to afford the corresponding amphiphilic cationic polyelectrolyte with M_w=3.63×10⁶ and 23 nm hydrodynamic radius at 25 °C. Emulsion copolymerization of styrene with ST-C_m-AB also proceeds rapidly to afford very stable cationic polystyrene latex particles of 30–60 nm diameter. The amphiphilic cationic polyelectrolyte of poly(ST-C₇-AB) is likely to assume a compact conformation with high segment density in 0.1 mol L^–1 NaCl in water. Addition of hydrophobic aromatic counter-anions with an weak acid group, for example potassium hydrogen phthalate (PHK) and sodium salicylate, to a salt-free aqueous solution of poly(ST-C₇-AB) induces intermolecular aggregation and increases the solution viscosity substantially, often producing gels and precipitation at high polymer concentration.     

Synthesis of cationic ether lipids of alkyl type with short-chain substituents at the 2-position of the glycerol backbone

A series of cationic ether lipids with short-chain substituents at the 2-position and various cationic groups attached directly or through a spacer group to the glycerol backbone was synthesized.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1826–1830, October, 1994.This work was supported by the Russian Foundation for Basic Research (Project No. 94-03-08-166).     

Structural characterization of polybutadiene synthesized via cationic mechanism

The microstructure of polybutadiene synthesized via cationic polymerization using TiCl₄‐based initiating systems has been investigated using 1D (¹Н, ²Н, and ¹³С) and 2D (HSQC and HMBC) NMR spectroscopy. It was found that trans‐1,4‐unit is predominant structure of unsaturated part of polymer chain. Besides, the small amount of 1,2‐structures was also detected, while cis‐1,4‐units were totally absent. The signals of carbon atoms of three types of head groups (trans‐1,4‐, 1,2‐, and tert‐butyl) and two types of end groups (trans‐1,4‐Cl and 1,2‐Cl) were identified for the first time in macromolecules of cationic polybutadiene. It was showed that tert‐butyl head groups were formed due to the presence in monomer of admixtures of isobutylene. The new methodology for calculation of the content of different structural units in polybutadiene chain as well as the head and end groups was proposed. It was established that main part of 1,2‐units distributed randomly along the polybutadiene chain as separate units between trans‐1,4‐structures. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 387–398     

D‐π‐a‐type oxime sulfonate photoacid generators for cationic polymerization under UV–visible LED irradiation

Four D‐π‐A‐type nonionic oxime sulfonate photoacid generators (PAGs) have been designed and synthesized for use in light‐emitting diode (LED) excitable cationic photoinitiators, in which N,N‐diphenylamino was used as electron donor with trifluoroacetophenone‐based oxime sulfonates (trifluoromethanoesulfonate and p‐toluenesulfonate) as electron acceptor and substituted fluorene and biphenyl groups as the π‐conjugated systems. PAG‐Ben‐Tol (with biphenyl and p‐toluenesulfonate) and PAG‐Flu‐Tol (with fluorene and p‐toluenesulfonate) showed high quantum yields of photoacid generation (0.33–0.50) and very good thermal stability (over 250 °C). The absorbance spectra of these PAGs were consistent with the emission spectra of commercially gained UV–visible LED light sources. The potential of these PAGs for cationic photoinitiators was tested in two cationic monomer systems. These PAGs needed low light intensity and low concentration for photopolymerization with high conversions of monomer, for example, over 80%, gained at 3.0 mW cm⁻² from 365 to 470 nm LEDs. The photochemical mechanisms of these PAGs are comprehensively investigated and discussed in detail. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1146–1154     

Synthesis and activity of aryl benzyl methyl sulfonium salts as cationic initiators: Effect of substituent on aryl group

Benzyl o-, m-, and p-substituted phenyl methyl sulfonium salts ( 2b – 2g ) were synthesized and their activities as cationic initiators were evaluated in the bulk polymerization of phenyl glycidyl ether (PGE). Especially, their activities were estimated with respect to the effect of substituents on the aryl groups. In the polymerizations of PGE with a series of benzyl p-substituted phenyl methyl sulfonium salts, the order of their activities was found to be 2c (CH₃OCOO) > 2b (CH₃COO) > 2d (CH₃O) ～ 2a (HO). In particular, 2c was the most active initiator of all, capable of initiating the polymerization of PGE even at room temperature. In the polymerizations with 2a, 2e (m-Cl), 2f (o-CH₃), and 2g (m-CH₃), the activity of 2e was the highest of all while those of 2a, 2f , and 2g were almost the same. These results strongly suggested that the electron-withdrawing group placed on the aryl group undoubtedly enhanced the activity of the sulfonium salts as the cationic initiators.     

Dark‐cure studies of cationic photopolymerizations of epoxides: Characterization of the active center lifetime and kinetic rate constants

We have characterized the effective rate constants for termination/trapping (k_t/t) and propagation (k_p) for solvent‐free cationic photopolymerizations of phenyl glycidyl ether for conversions up to 50%. We have performed dark‐cure experiments in which active centers are produced photochemically for a specified period of time until the initiating light is shuttered off, and then the polymerization rate is monitored in the dark. This method is especially well suited for characterizing cationic polymerizations because of the long active center lifetimes. Our analysis provides profiles of the instantaneous kinetic rate constants as functions of conversion (or time). For photopolymerizations of phenyl glycidyl ether initiated with iodonium photoinitiators, k_t/t and k_p remain essentially invariant for conversions up to 50%. For the photoinitiator (tolycumyl) iodonium tetrakis (pentafluorophenyl) borate (IPB), the values of k_t/t at 50 and 60 °C are 0.027 and 0.033 min^?1, respectively. The corresponding values of k_t/t for diaryliodonium hexafluoroantimonate (IHA) are 0.041 and 0.068 min^?1. The values of k_p at 50 °C for IPB and IHA are 0.6 and 0.4 L mol^?1 s^?1, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2064–2072, 2003     

Synthesis and characterization of cationic copolymers of butylacrylate and [3‐(methacryloylamino)‐propyl]trimethylammonium chloride

Cationic copolymers of butylacrylate (BA) and [3‐(methacryloylamino)‐propyl]trimethylammonium chloride (MAPTAC) were synthesized by free‐radical‐solution polymerization in methanol and ethanol. An FT‐Raman Spectrometer and NMR were used to monitor the polymerization process. The copolymers were characterized by light scattering, NMR, DSC, and thermogravimetric analysis. It was found that random copolymers could be prepared, and the molar fractions of BA and cationic monomers in the copolymers were close to the feed ratios. The copolymer prepared in methanol had a higher molecular weight than that prepared in ethanol. As the cationic monomer content increased, the glass‐transition temperature (T_g) of the copolymer also increased, whereas the thermal stability decreased. The reactivity ratios for the monomers were evaluated. The copolymerization of BA (M₁) with MAPTAC (M₂) gave reactivity ratios such as r₁ = 0.92 and r₂ = 2.61 in ethanol as well as r₁ = 0.79 and r₂ = 0.90 in methanol. This study indicated that a random copolymer containing a hydrophobic monomer (BA) and a cationic hydrophilic monomer (MAPTAC) could be prepared in a proper polar solvent such as methanol or ethanol. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1031–1039, 2001