The role of cationic monomers in emulsion polymerization

[2-(methacryloyloxy)ethyl] trimethylammonium chloride (MATMAC), and vinylbenzyl trimethyl ammonium chloride (VBTMAC) were chosen to be used as ionic comonomers in the emulsion polymerization of styrene. The cationic nature of the two comonomers is the same (quaternary ammonium salts), however the styrene derivate (VBTMAC) is more hydrophobic than the methacrylic one (MATMAC). With the more hydrophobic cationic comonomer (VBTMAC) higher conversions were obtained due to the in situ creation of an amphiphilic copolymer with styrene and faster rates of polymerization were observed by increasing the cationic comonomer concentration. The same behavior was observed with the more hydrophilic cationic comonomer (MATMAC) at concentrations up to 0.012 M. At higher concentrations the ionic strength controls the colloidal stability of the system and coagulation occurs.     

Which are the mechanisms governing in cationic emulsion polymerization?

The cationic emulsion polymerization of styrene in a batch reactor using different concentrations of dodecyltrimethylammonium bromide (DTAB) and hexadecyltrimethyl-ammonium bromide (HDTAB) as cationic surfactants, and 2,2′-azobisisobutyramidine dihydrochloride (AIBA), and 2,2′-azobis (N,N′-dimethyleneisobutyramidine) dihydrochloride (ADIBA) as cationic initiators has been studied. In the preliminary study, the best conditions to obtain stable cationic latexes at high conversions were identified. When the surfactant concentration was above its cmc, latexes with high conversions were achieved for the two cationic surfactants studied (DTAB and HDTAB). Cationic latexes with less coagulum were obtained using ADIBA as cationic initiator due to its superior resistance to hydrolysis. AIBA is hydrolyzed to amide at basic pHs and in this way, the concentration of radicals formed in the aqueous phase decreases. On the other hand, a stronger effect of the particle size on the kinetics of the cationic emulsion polymerization of styrene using HDTAB as cationic surfactant was observed than using DTAB. Furthermore, different kinetic behaviors were observed with the two cationic initiators (ADIBA and AIBA) using HDTAB as cationic surfactant, due to the lower stabilizing effect of the cationic radicals provided by AIBA.     

Synthesis of polyaniline/multiwall carbon nanotube composite via inverse emulsion polymerization

The composite of polyaniline (PANI) and multiwall carbon nanotube carboxylated through acid treatment (c‐MWCNT) was synthesized by chemical oxidative polymerization in an inverse emulsion system. The resultant composites were compared with products from aqueous emulsion polymerization to observe the improvements in electrical conductivity, structural properties, and thermal stability obtained by this synthetic method. Prior to the inverse emulsion polymerization, MWCNT was treated with a strong acid mixture to be functionalized with carboxylic acid groups. Carboxylic acid groups on surfaces induced selective dispersibility between polar and nonpolar solvents because of the increase of hydrophilicity. As the content of c‐MWCNT was increased, the electrical conductivity was increased by a charge transport function from the intrinsic electrical conductivity of MWCNT and the formation of a highly ordered dense structure of PANI molecules on the surface of c‐MWCNT. The images observed with electron spectroscopy showed the capping of c‐MWCNT with PANI. The growth of additional ordered structures of PANI/c‐MWCNT composite, which was observed through wide‐angle X‐ray diffraction patterns, supported the capping by PANI. It was observed that the doping of the composite had a significant relationship with the concentration of dodecylbenzenesulfonic acid (DBSA). The thermal stability of PANI composite was improved by the addition of c‐MWCNT; this was thought to be related with structure ordering by inverse emulsion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2255–2266, 2008     

The inverse emulsion polymerization of acrylamide using polystyrene-graft-polyoxyethylene as the stabilizer

Inverse emulsion polymerization of aqueous solution of acrylamide (AM) in toluene is carried out using polystyrene-graft-polyoxyethylene (PSt-g-PEO) as an emulsifier. The kinetics of polymerization, morphology of the particle, and particle size of the inverse emulsion have been investigated. The rates of polymerization are found to be proportional to the initiator concentration, the monomer concentration, and the emulsifier concentration. The morphology of the particle shows a spherical structure. The effects of amphipathic graft copolymer structure on the average molecular weight of polyacrylamide are studied. The mechanism of the inverse emulsion polymerization using amphipathic graft copolymer as emulsifier is proposed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2719–2725, 1999     

Ammonium persulfate-initiated polymerization of cationic starch-grafted-cationic polyacrylamide flocculant for the enhanced flocculation of oil sludge suspension

In this study, a novel, highly efficient and environmentally friendly flocculant, namely, cationic starch-grafted-cationic polyacrylamide (CS-g-CPAM), was synthesized by initiation polymerization of ammonium persulfate. First, CS-g-CPAM was polymerized with cationic starch(CS), acrylamide(AM) and diallyl dimethyl ammonium chloride (DMDAAC), and then the influence factors of graft polymerization were investigated, including total monomer concentration, initiator dosage, the monomer mass ratio of m_AM: m_CS: m_DMDAAC, post-polymerization temperature and post-polymerization time. And the intrinsic viscosity of the CS-g-CPAM was measured by the one point method accurately. The chemical structures and morphology of the samples were characterized by Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermo-gravimetric and differential scanning calorimetry (TG-DSC), and scanning electron microscope (SEM). The CS-g-CPAM was utilized to flocculate the oil sludge suspension, the effects of CS-g-CPAM dosage, temperature and pH value on the flocculation performance were investigated. The results show that CS-g-CPAM has outstanding flocculation effect.     

Photoinitiated,inverse emulsion polymerization of acrylamide: Some mechanistic and kinetic aspects

The kinetics of photoinitiated, inverse emulsion polymerization of acrylamide with 2,2‐dimethoxy‐2‐phenylacetophenone (DMPA) as a photoinitiator was investigated under three different cases. First, in a quartz reactor transparent to full UV light, the polymerization rate (R_p) increased and then decreased with the change of initiator order from 0.27 to a negative value when the DMPA concentration was increased, and it was particularly unusual that monomer orders at different DMPA concentrations were lower than the first. Second, for polymerization without DMPA in a quartz reactor, the dependence of R_p on monomer concentration was similar to that of R_p on initiator concentration in the aforementioned case. Third, when polymerization was carried out in a Pyrex reactor where the far UV light was filtered, a peak rate was also observed, and initiator orders varied from 0.24 to a negative value; however, under this case monomer orders at different initiator concentrations were greater than the first. These results indicated that the effect of absorbance often observed in bulk or solution photopolymerization also existed in this system, and the self‐initiation of monomer had some influence on polymerization, and the role of primary radical termination could not be neglected, as evidenced by kinetic analysis. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 846–852, 2004     

Synthesis of polytetrafluoroethylene/polyacrylate core-shell nanoparticles via emulsifier-free seeded emulsion polymerization

Polytetrafluoroethylene (PTFE)/polyacrylate core-shell nanoparticles were produced via the emulsifier-free seeded emulsion polymerization of acrylate monomers with PTFE latex as seed. The monomer conversions under different synthesis parameters were monitored by a gravimetric method. The polymerization conditions for preparing PTFE/polyacrylate core-shell nanoparticles were surveyed and optimized. The chemical component of the PTFE/polyacrylate particles was confirmed by comparing the Fourier-transform infrared spectra of PTFE and PTFE/polyacrylate particles. The core-shell structure of the resulting PTFE/polyacrylate nanocomposite particles was investigated by transmission electron microscopy. The water contact angles of the films prepared from PTFE/polyacrylate nanocomposite particles showed that the films were hydrophilic, which confirmed that polyacrylate covered the surface of the PTFE particles. This kind of PTFE/polyacrylate core-shell nanoparticles might advance the compatibility of PTFE with other materials due to the covering of the polyacrylate shell on the surface of PTFE, which would make them promising in various fields.     

Synthesis of a novel series of polymerizable surfactants and application in emulsion polymerization

A series of polymerization surfactants (surfmers) was synthesized, whose structures combined the characteristics of polyoxyethylene as nonionic group and quaternary ammonium a as cationic group. The structures of the product were confirmed by MS, and the content of cationic‐activity matter was determined by two‐phase titration. The surfmers were then used with constant addition profiles in semicontinuous polymerization of vinyl acetate–butyl acrylate–Veova 10–hexafluorobutyl methacrylate, and the polydispersity indexes (PDI) were lower than 0.1. The particle size, amount of coagulum, and stability against electrolyte and freeze/thaw were evaluated. As a reference, an unreactive surfactant cetyl trimethyl ammonium bromide (CTAB) was also used for the polymerization. Compared to CTAB, the surfmers behaved much better. Not only stabilities to electrolyte and water resistance were improved, but also freeze/thaw stability got a superior performance. Copyright © 2008 John Wiley & Sons, Ltd.     

聚[2-(丙烯酰氧基)乙基]三甲基氯化铵-乙二醇二甲基丙烯酸酯整体柱固相萃取结合高效液相色谱法测定尿液中3种苯二氮（卄卓）类药物

以[2-（丙烯酰氧基）乙基]三甲基氯化铵（DAC）为单体,乙二醇二甲基丙烯酸酯（EDMA）为交联剂在注射器中制备聚合物整体柱,用其固相萃取尿液中溴西泮（BRZ）、劳拉西泮（LRZ）和地西泮（DZP）3种苯二氮（卄卓）类药物（BZDs）,并采用高效液相色谱法（HPLC）分析。实验考察了整体柱聚合时间及固相萃取条件（淋洗溶液、洗脱溶剂种类和体积）对BZDs萃取效率的影响。结果表明,仅聚合4 h得到的整体柱对BZDs吸附效率为100%。取尿液样品4 mL上样,用4 mL H₂O冲洗,1 mL乙酸乙酯洗脱,采用高效液相色谱分析。在最优条件下,3种BZDs在4.0~1000 ng/mL范围内线性关系良好（r=0.999）,检出限（S/N=3）和定量限（S/N=10）分别为1.0~1.2 ng/mL和3.3~4.0 ng/mL;在10、25和50 ng/mL加标水平下回收率为81.4%~102%,日内（n=3）和日间（n=3）相对标准偏差分别为1.2%~4.5%和2.5%~8.3%。该整体柱可对尿液中3种BZDs有效净化,且富集达12~15倍。方法构筑的聚合物整体柱制备简单,萃取高效,可成功用于尿液中3种BZDs的分析。     

Water-tolerant catalyst systems for the bulk cationic polymerization of para-methylstyrene and indene

Water-tolerant catalyst systems have been investigated for the cationic oligomerization of technical-grade p-methylstyrene and indene, for the production of industrially relevant aromatic resins. Systems based on 1-p-tolylethanol and 1-indanol (ROH) as initiators, in association with Cu(OTf)₂, Bi(OTf)₃ (OTf = triflate) and B(C₆F₅)₃ as co-initiators/catalysts, show interesting productivities at 60 °C under air, with as low as 0.2-1.0 mol% catalyst loading. Most of the reactions are not controlled in terms of molecular weights of the products, except for indene oligomerization by the borane catalyst where experimental M_n values match well the theoretical values, as determined by the amount of added initiator over a 5-fold range (with 2-10 mol% vs. monomer). The ROH/tris(pentafluorophenyl)borane system offers the best compromise in terms of productivity and control over the molecular weights of the oligomers, which can be manipulated by the amount of initiator and reaction temperature.     

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     

Graft polymerization of polysilsesquioxane containing chloromethylphenyl groups by atom transfer radical polymerization

Polysilsesquioxane with phenyl and chloromethylphenyl groups (PCPSQ) was prepared readily from phenyltrimethoxysilane and [2‐(chloromethylphenyl)ethyl]trimethoxysilane under acidic conditions. Polymerization with chloromethylphenyl groups on PCPSQ with methyl methacrylate (MMA) was conducted in the presence of a catalytic amount of copper(I) bromide and (−)‐sparteine. Atom transfer radical polymerization yielded a graft polymer (PCPSQ‐g‐MMA) efficiently, and no gelation was observed. The process was also applied to the preparation of graft block copolymers on PCPSQ with several methacrylate monomers. An advantage of the graft hybrid polymers was shown in improved thermal behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4212–4221, 2004     

Quaternary ammonium salts as alkylating agents in the synthesis of tertiary phosphine oxides

A procedure was developed for the synthesis of tertiary phosphine oxides by alkylation of secondary phosphine oxides with quaternary ammonium salts. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 390–392, February, 1999     

2-vinyloxy ethyl phthalimide polymerization initiated by 1-(isobutoxy) ethyl acetate in the presence of ethyl aluminum dichloride and either ethyl acetate or ethyl benzoate

2-Vinyloxy ethyl phthalimide (ImVE) was polymerized using 1-(isobutoxy) ethyl acetate as the initiator in the presence of ethyl aluminum dichloride and either ethyl acetate or ethyl benzoate. The resulting polymers have a narrow molecular weight distribution, and their molecular weight can be controlled within a narrow range by varying the monomer and initiator concentrations. Diblock copolymers with n-butyl vinyl ether can also be formed. The behavior of the polymerization is consistent with a living cationic mechanism. A brief comparison of the title system with other initiating systems is also presented. © 1996 John Wiley & Sons, Inc.     

Reversible addition–fragmentation chain transfer polymerization of methyl methacrylate in emulsion

Theoretical simulations showed that for controlled/living radical polymerization in an emulsion system, some of the earliest born particles could be superswollen to a size close to 1 μm. We hypothesized that the superswelling of these particles would lead to colloidal instability. Under the guidance of the simulation results, reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of methyl methacrylate (MMA) was carried out. Experimental results showed that increasing the initiation rate, surfactant level, and targeted molecular weight could improve the colloidal stability of the RAFT polymerization of MMA in an emulsion. The experimental results were in full accord with the theoretical predictions. The poor control of the molecular weight and polydispersity index was found to have a close relationship with the colloidal instability. For the first time, we demonstrated that RAFT polymerization could successfully be implemented with little coagulum, good control of the molecular weight, and a low polydispersity index with the same process used for traditional emulsion polymerization but with higher surfactant levels and initiation rates. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:2837–2847, 2006     

氧阴离子引发甲基丙烯酸-2-(N,N-二甲氨基)乙酯聚合制备Y型大分子单体

氧阴离子聚合(Oxyanion－initiated Polymerization)是一类新型的聚合方法[‘,’‘．利用个乙烯基苦醇钾作为功能性引发剂,引发甲基丙烯酸－2－(NJ－二乙氨基)乙酯聚合,形成末端带可聚合官能团的大分子单体‘”“．氧阴离子引发剂通常难以引发甲基丙烯酸烷基酯单体聚合,但却能引发甲基丙烯酸氨基酯类单体发生聚合．由于氨基乙酯基7位上氮原子的供电子性,它能与钾离子形成螫合物,使氧阴离子的亲核性增加,从而更具有活性,引发单体聚合．氧阴离子聚合具有速度快、活性高、反应温度接近室温和产物的单分散性好等特点．尽管目前还不清楚这种反…     

阳离子光固化活性单体氧杂环丁烷的合成及表征

以3-乙基-3-羟甲基氧杂环丁烷为原料，与甲基磺酰氯磺酰化，得到3-乙基-3-甲磺酰基甲基氧杂环丁烷；在碱性条件下，以PEG600作相转移催化剂，用3-乙基-3-甲磺酰基甲基氧杂环丁烷与乙二醇醚化得到2-[（3-乙基-3-氧杂环丁基）甲氧基]乙醇；然后与甲基丙烯酸甲酯进行酯交换得到目的产物2-[（3-乙基-3-氧杂环丁烷）甲氧基]甲基丙烯酸乙酯。3-乙基-3-羟甲基氧杂环丁烷与3-溴丙烯反应，生成3-乙基-3-[（2-丙烯-1-基氧基）甲基]氧杂环丁烷，然后在氯铂酸的催化下，与三乙氧基硅烷反应得到3-乙基-3-[[3-（三乙氧基硅）丙氧基]甲基]氧杂环丁烷。产物经红外光谱和核磁共振谱表征得到确证。     

A degradable atom transfer radical polymerization inimer: Synthesis,polymerization, and cleavage of the resulting polymer products

A novel degradable inimer for atom transfer radical polymerization (ATRP), 2‐(6‐(2‐((2‐bromo‐2‐methylpropanoyl)oxy)ethyl)pyridin‐2‐yl)ethyl methacrylate (PyDEBrMΑ), was synthesized by the two‐step esterification of 2,6‐pyridinediethanol, first with α‐bromoisobutyryl bromide in order to introduce the initiator moiety, and then with methacryloyl chloride in order to introduce the monomer moiety. PyDEBrMA was subsequently used to initiate the self‐condensing ATRP of methyl methacrylate (MMA) to obtain a hyperbranched MMA homopolymer which could be cleaved at the PyDEBrMA residue either by treatment under mildly alkaline hydrolysis conditions (sodium deuteroxide in d₆‐DMSO at room temperature) or thermolysis at 150 °C. The lability of the PyDEBrMA residue arises from the presence in its structure of two 2‐(pyridin‐2‐yl)ethyl ester moieties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2831–2839     

Synthesis of P(AA‐SA)/ZnO composite latex particles via inverse miniemulsion polymerization and its application in pH regulation and UV shielding

Poly(acrylic acid‐co‐sodium acrylate)/zinc oxide, P(AA‐SA)/ZnO, composite latex particles were synthesized by inverse miniemulsion polymerization. The ZnO nanoparticles were prepared by hydrothermal synthesis and undergone oleic acid (OA) surface treatment. The X‐ray diffraction pattern and FT‐IR spectra characterized the crystal structure and functional groups of OA‐ZnO nanoparticles. An appropriate formulation in preparing P(AA‐SA) latex particles, ensuring the dominant in situ particle nucleation and growth, was developed in our experiment first. Sodium hydroxide was chosen as a costabilizer, because of its ability to increase the deprotonation of acylic acid and enhance the hydrophilicity of monomer, acrylic acid besides providing osmotic pressure. The growth mechanism of P(AA‐SA)/ZnO composite particles was proposed. The OA‐ZnO nanoparticles were adsorbed on or around the surface of P(AA‐SA) latex particles by hydrophobic interaction, thus enhanced the interfacial tension over latex particles. The P(AA‐SA)/ZnO composite latex particles owned better thermal stability than pure latex particles. The pH regulation capacity was excellent for both ZnO and P(AA‐SA) particles. Combining P(AA‐SA) and ZnO nanoparticles into composite particles, the performance in pH regulation and UV shielding was discussed from our experimental results. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8081–8090, 2008