Polymerization of surface-active monomers. I. Micellization and polymerization of higher alkyl salts of dimethylaminoethyl methacrylate

Micellization of cationic salts of dimethylaminoethyl methacrylate (DMAEMA) quaternized with n-alkyl bromides such as octyl, lauryl, myristyl, and stearyl bromide and their polymerizations were investigated. The critical micelle concentration (cmc) in water at 25°C was determined by electrical conductivity and dye(azobenzene) solubilization methods and the relation log(cmc) = 1.46–0.31N was obtained, where cmc is in mmol L^?1 and N corresponds to carbon number of alkyl bromides used for the monomer preparations. All of these monomeric salts exhibited a high radical polymerizability in water and benzene. The polymerizations in water appeared to proceed with a higher rate with increasing a chain length of the alkyl moiety of the monomers and those in benzene gave the polymers with a remarkably high viscosity. The rate of polymerization of lauryl bromide salt in anisotropic solutions (in water and benzene) was exceedingly fast as compared with that in isotropic solution(in acetonitrile). All of the polymers obtained here were insoluble in water. Solubility characteristics of these monomers and polymers in other solvents were also presented. The reduced viscosity, in dimethylformamide and methanol, of poly(lauryl bromide salt) prepared in water increased with dilution but that for the polymer obtained in benzene exhibited an inverse concentration dependence. Some discussions were made on the peculiarities of the polymerizations of these monomers and the resulting polymers.     

Preparation of functional polymers by living anionic polymerization: Polymerization of allyl methacrylate

The anionic polymerization of allyl methacrylate was carried out in tetrahydrofuran, both in the presence and in the absence of LiCl, with a variety of initiators, at various temperatures. It was found that (1,1-diphenylhexyl)lithium and the living oligomers of methyl methacrylate and tert-butyl methacrylate are suitable initiators for the anionic polymerization of this monomer. The temperature should be below −30°C, even in the presence of LiCl, for the living polymerization to occur. When the polymerization proceeded at −60°C, in the presence of LiCl, with (1,1-diphenylhexyl)-lithium as initiator, the number-average molecular weight of the polymer was directly proportional to the monomer conversion and monodisperse poly(allyl methacrylate)s with high molecular weights were obtained. ¹H-NMR and FT-IR indicated that the α CC double bond of the monomer was selectively polymerized and that the allyl group remained unreacted. The prepared poly(allyl methacrylate) is a functional polymer since it contains a reactive CC double bond on each repeating unit. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2901–2906, 1997     

Tacticity control in the radical polymerization of 2,2,2-trifluoroethyl methacrylate with fluoroalcohol

The free-radical polymerization of 2,2,2-trifluoroethyl methacrylate (TEMA) was carried out in fluoroalcohols to achieve stereoregulation. The polymerization reactivity at low temperature and syndiotactic specificity were enhanced by the use of fluoroalcohol as a solvent. The polymer having triad syndiotacticity (rr) of 70% was obtained in perfluoro-t-butyl alcohol. It was noted that the stereochemistry was nearly independent of reaction temperature. The stereoeffect of fluoroalcohols seemed to be due to the hydrogen-bonding interaction between the alcohol and the monomer or growing species. The hydrogen-bonding formation was determined by FTIR. The copolymerization of TEMA with methyl methacrylate (MMA) in hexafluoroisopropanol afforded a copolymer with syndiotactic specificity. By this method, a cladding material for an optical fiber based on poly(methyl methacrylate) (PMMA) with high mechanical strength and low refractive index could be obtained.     

Polymerization in magnetic field. XVI. Kinetic aspects regarding methyl methacrylate polymerization in high magnetic field

The effect of a high magnetic field of 7 T in the reaction of methyl methacrylate polymerization is emphasized. The intervening magnetokinetic modifications are correlated with the system of radical initiation with benzoyl peroxide, 2,2′‐azobis(2‐methylpropionitrile), 4,4′‐azobis(4‐cyanopentanoic acid), and 1,1′‐azobis(cyclohexane‐1‐carbonitrile). The characterization of the synthesized polymers is correlated with the reaction conditions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5678–5686, 2004     

Synthesis of 4-arm methyl methacrylate star polymer by atom transfer radical polymerization

The synthesis of 4-arm methyl methacrylate star polymer had been achieved successfully by atom transfer radical polymerization using CuCl as catalyst, 2, 2′-bipyridyl as ligand and pentaerythritol tetrakis (2-bromoisobutyrate) as the initiator. The star polymer was characterized by ¹H-NMR and GPC, by which the precise 4-arm structure of the PMMA was confirmed. __________ Translated from Journal of Shaanxi Normal University (Natural Science Edition), 2008, 36(2) (in Chinese)     

甲基丙烯酸甲酯原子转移自由基聚合等规度研究

在0～100℃温度范围内,由原子转移自由基聚合方法,采用助催化和非助催化体系,引发甲基丙烯酸甲酯聚合,利用¹³CNMR测定聚甲基丙烯酸甲酯的等规度.发现原子转移自由基聚合仍以间同立构为主,随着聚合温度的升高间同立构等规度降低,与通常自由基聚合对有规立构控制特征相似.助催化剂异丙醇铝和活性端羰基配位,对聚合物的立构规整性有一定的影响.     

Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers

Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80 °C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (r_MMA = 0.62 ± 0.04; r_HEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, M_n = 475 g mol⁻¹) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (r_MMA = 0.75 ± 0.07; r_PEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr₂(PPh₃)₂) were observed by ¹H NMR spectroscopy.     

Self-initiated atom transfer radical polymerization of methyl methacrylate in cyclohexanone

The self-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in cyclohexanone (CHO) in the presence of CuCl₂/N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) is reported. The linear semilogarithmic plot of ln([M]₀/[M]) vs time, the linear increase of number-average molecular weight (M_n) with conversion, and rather narrow molecular weight distributions (MWDs) have been observed, which are in agreement of the characteristics of living/controlled polymerization. The NMR spectrum revealed the existence of terminal chlorine. The chain extension further proved the living characteristic. The polymerization can only be successful using CHO as the solvent, and is well controlled at the temperature as low as 50 °C. The effects of ligand, solvent, temperature and monomer to catalyst ratio are all discussed.     

Recent progress in controlled radical polymerization of N-vinyl monomers

This review summarizes recent advances in the controlled radical polymerization of N-vinyl monomers, such as N-vinylcarbazole, N-vinylindole derivatives, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetoamide derivatives, N-vinyl(na)phthalimides, N-vinylimidazolium salts, and N-vinyltriazoles. Recent significant progress of controlled radical polymerization of these N-vinyl monomers has allowed for the synthesis of well-defined functional polymers having various architectures, including block copolymers, branched polymers (stars, star block copolymers, miktoarm star copolymers, and graft copolymers), and hybrids. Characteristic properties, assembled structures, and three-dimensional architectures of these functional polymers derived from N-vinyl monomers are briefly introduced.     

Polymerization of free secondary amine bearing monomers by RAFT polymerization and other controlled radical techniques

This work describes the polymerization of the free secondary amine bearing monomer 2,2,6,6‐tetramethylpiperidin‐4‐yl methacrylate (TMPMA) by means of different controlled radical polymerization techniques (ATRP, RAFT, NMP). In particular, reversible addition‐fragmentation chain transfer (RAFT) polymerization enabled a good control at high conversions and a polydispersity index below 1.3, thereby enabling the preparation of well‐defined polymers. Remarkably, the polymerization of the secondary amine bearing methacrylate monomer was not hindered by the presence of the free amine that commonly induces degradation of the RAFT reagent. Subsequent oxidation of the polymer yielded the polyradical poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl methacrylate), which represents a valuable material used in catalysis as well as for modern batteries. The obtained polymers having a molar mass (M_n) of 10,000–20,000 g/mol were used to fabricate well‐defined, radical‐bearing polymer films by inkjet‐ printing. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ruthenium carborane complexes in the controlled radical polymerization of methyl methacrylate

New initiators based on closo-and exo-nido-ruthenacarboranes with phosphine and diphosphine ligands were proposed as chain growth regulators. They allow conducting the controlled synthesis of poly(methyl methacrylate) under radical initiation conditions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 85–89, January, 2006.     

Synthesis of linear and starlike polymers from poly(propylene glycol) methacrylate using controlled radical polymerization

The copper‐catalyzed atom transfer radical polymerization (ATRP) of poly(propylene glycol) methacrylate (PPGM) in solution to produce linear and starlike polymers is reported, using methylethyl ketone as the solvent and a temperature of 80 °C. The ATRP system used was efficient for polymerization of the functionalized monomer without protecting hydroxyl end groups of monomer. The polymerizations were consistent with “living” or controlled processes, as revealed by the linear evolution of molecular weight with conversion. Increasing the [M]₀:[I]₀ ratio resulted in increasing molecular weights, whereas the polydispersity indices remained low (M_w/M_n < 1.4) even at high conversion. Decreasing the [CuBr]₀:[I]₀ ratio resulted in lower conversions, slightly larger polydispersities, and decreased molecular weights, likely resulting from a lower initiation efficiency. Polymers were characterized by ¹H and ¹³C NMR; molecular weights of polymers with low degrees of polymerization were estimated by end‐group analysis from ¹³C NMR spectra obtained using distortionless enhancement by polarization transfer and the gated decoupling techniques. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 334–343, 2002     

Dispersion polymerization of MMA in supercritical CO2 stabilized by random copolymers of 1H,1H–perfluorooctyl methacrylate and 2‐(dimethylaminoethyl methacrylate)

A series of random copolymers, composed of 1H,1H‐perfluorooctyl methacrylate (FOMA) and 2‐dimethylaminoethyl methacrylate (DMAEMA) were prepared as stabilizers for the dispersion polymerization of methyl methacrylate in supercritical CO₂ (scCO₂). Free‐flowing, spherical poly(methyl methacrylate) (PMMA) particles were produced in high yield by the effective stabilization of poly(FOMA‐co‐DMAEMA) containing 34–67 w/w % (15–41 m/m %) FOMA structural units. Less stabilized but micron‐sized discrete particles could be obtained even with 25 w/w % (10 m/m %) FOMA stabilizer. The result showed that the composition of copolymeric stabilizers had a dramatic effect on the size and morphology of PMMA. The particle size was controllable with the surfactant concentration. The effect of the monomer concentration and the initial pressure on the polymerization was also investigated. The dry polymer powder obtained from dispersion polymerization could be redispersed to form stable aqueous latexes in an acidic buffered solution (pH = 2.1) by an electrostatic stabilization mechanism due to the ionization of DMAEMA units in the stabilizer. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1365–1375, 2008     

Activity of the furfuryl ring in the free radical polymerization of acrylic monomers

The effect and the participation of the furfuryl ring, in particular the hydrogen at position C-5 in the free radical polymerization are analyzed following the polymerization of furfuryl acrylate (FA) and furfuryl methacrylate (FM) initiated by AIBN under photochemical activation. The results obtained indicate that the polymerization of FA deviates from the classical free radical kinetic scheme, giving rise to crosslinked polymers even at a degree of conversion lower than 7%. This behavior is well explained taking into consideration the participation of the furfuryl ring which acts as a degradative transfer agent. This was demonstrated by the kinetic analysis of the free radical polymerization of MMA initiated by the thermal decomposition of AIBN in the presence of different concentrations of furfuryl acetate. © 1996 John Wiley & Sons, Inc.     

Spacer effect of novel bifunctional organophosphorus monomers in metal-imprinted polymers prepared by surface template polymerization

The interfacial activity and the molecular structure of functional monomers are critical factors that determine the success of synthesizing metal-imprinted polymers by surface template polymerization. From this point of view, first we prepared three distinct novel bifunctional organophosphorus monomers that are interspaced, in each case, by an alkyl spacer having a specific length. Each monomer carries two phosphonic acid groups and two aromatic groups in its molecular structures. Further, by using the synthesized bifunctional monomers, we prepared highly selective Zn(II)-imprinted polymers by the surface template polymerization initiated from a water-in-oil emulsion. To evaluate the template effect, we conducted diagnostic adsorption studies on Zn(II)-imprinted and unimprinted polymers with zinc ions. A high interfacial activity was found to be required for the functional monomers to create the predominant template effect. It became clear that Zn(II)-imprinted polymers having bifuctional monomers with 12-length alkyl chains (1,12-dodecanediol-O, O′-diphenyl phosphonic acid: DDDPA) yielded the best results. Moreover, analysis results of adsorption behavior supported a high-performance of the Zn(II)-imprinted polymers with DDDPA. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2727–2734, 1998     

Living radical graft polymerization of methyl methacrylate to polyethylene film with typical and reverse atom transfer radical polymerization

Nickel‐mediated atom transfer radical polymerization (ATRP) and iron‐mediated reverse ATRP were applied to the living radical graft polymerization of methyl methacrylate onto solid high‐density polyethylene (HDPE) films modified with 2,2,2‐tribromoethanol and benzophenone, respectively. The number‐average molecular weight (M_n) of the free poly(methyl methacrylate) (PMMA) produced simultaneously during grafting grew with the monomer conversion. The weight‐average molecular weight/number‐average molecular weight ratio (M_w/M_n) was small (<1.4), indicating a controlled polymerization. The grafting ratio showed a linear relation with M_n of the free PMMA for both reaction systems. With the same characteristics assumed for both free and graft PMMA, the grafting was controlled, and the increase in grafting ratio was ascribed to the growing chain length of the graft PMMA. In fact, M_n and M_w/M_n of the grafted PMMA chains cleaved from the polyethylene substrate were only slightly larger than those of the free PMMA chains, and this was confirmed in the system of nickel‐mediated ATRP. An appropriate period of UV preirradiation controlled the amount of initiation groups introduced to the HDPE film modified with benzophenone. The grafting ratio increased linearly with the preirradiation time. The graft polymerizations for both reaction systems proceeded in a controlled fashion. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3350–3359, 2002     

Synthesis and radical polymerization of acrylate and methacrylate bearing an isocyanurate core with adamantyl bisurethane moieties

In this article, we report the synthesis of acrylate and methacrylate bearing an isocyanurate core with two adamantyl urethane moieties and their radical homo- and copolymerization with n-butyl methacrylate (BMA). The synthesized polyacrylate exhibits higher 5% weight loss and glass transition temperatures (T_d5 and T_g) than those of the comparative polyacrylate, synthesized from the isocyanurate-based acrylate with two hexyl urethane moieties, suggesting that the rigid adamantane core incorporated in the side chains of polymer largely contributes to increase in thermal stability of polymer. Similarly, the obtained copolymers show higher T_g values than that of homopolymer derived from BMA, leading to the synthesized monomers are useful as a comonomer to enhance thermal property of polymer.     

Atom transfer radical polymerization of functional monomers employing Cu‐based catalysts at low concentration: Polymerization of glycidyl methacrylate

Initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) of an epoxide‐containing monomer, glycidyl methacrylate (GMA), was successfully carried out using low concentration of catalyst (ca. 105 ppm) at 60 °C in anisole. The copper complex of tris(2‐pyridylmethyl)amine was used as the catalyst, diethyl 2‐bromo‐2‐methylmalonate as the initiator, and 2,2′‐azobisisobutyronitrile as the reducing agent. When moderate degrees of polymerization were targeted (up to 200), special purification of the monomer, other than removal of the polymerization inhibitor, was not required to achieve good control. To synthesize well‐defined polymers with higher degrees of polymerization (600), it was essential to use very pure monomer, and polymers of molecular weights exceeding 50,000 g mol^?1 and M_w/M_n = 1.10 were prepared. The developed procedures were used to chain‐extend bromine‐terminated poly(methyl methacrylate) macroinitiator prepared by activators regenerated by electron transfer (ARGET) ATRP. The Sn^II‐mediated ARGET ATRP technique was not suitable for the polymerization of GMA and resulted in polymers with multimodal molecular weight distributions. This was due to the occurrence of epoxide ring‐opening reactions, catalyzed by Sn^II and Sn^IV. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011