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Copolymerization of methyl methacrylate with lauryl methacrylate using group transfer polymerization
Abstract
The syntheses of random and block copolymers (using sequential monomer addition) of methyl methacrylate (MMA) and lauryl methacrylate (LMA) have been investigated by group transfer polymerization (GTP) over a wide composition range using tetrabutylammonium bibenzoate (TBABB) as catalyst and 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene (MTS) as initiator in tetrahydrofuran (THF) at room temperature. The absolute molecular weight of the copolymers were determined by SEC-MALLS. The observed molecular weights were generally higher than the calculated molecular weights. However, the molecular weight distributions were very narrow (1.02–1.1). Use of trimethylsilyl benzoate as a “livingness enhancer” improved the livingness of the first block (PLMA) and block copolymers with no detectable contamination of homopolymer. Statistical copolymers of MMA and LMA were prepared, and the reactivity ratios of the two monomers under the defined conditions were determined. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1999–2007, 1997
... ppm (C-4) assigned to long chain alkyl group (-CH 2 -) and 14.36 ppm (C-5) assigned to methyl carbon (-CH 3 ). The 13 C NMR spectra were also approved with some relevant reports [69][70][71]. ...
The current research focuses on tailoring silica nanoparticles (SiO2NPs) with comb-like poly(dodecyl methacrylate) (PDMA) brushes and tuning coating parameters based on roller coating process for confining surface morphology towards hydrophobic and superhydrophobic including water-repellent surface. Electron beam (EB) induced a simultaneous “graft-from” polymerization of DMA monomer onto vinyl modified SiO2NPs (SiO2NPs-V) was established in an inventive castor oil/ethanol mixed solvent. Functional surface chemistry of SiO2NPs and nanorough surface topography controlled by NPs content and coating thickness mainly influences the hydrophobic/superhydrophobic, water-repellent, and water absorption properties including gloss values, whiteness and yellowness index of coated papers. The papers coated with SiO2NPs-V-PDMA/PVA of 6–10 wt% with the thickness of ~10–14 μm exhibited matt surface and provided superhydrophobic and water-repellent properties. The coated paper has a desirable and stable water contact angle of 152°, low droplet adhesion with lower dynamic tilting angle (<5°), and 5.3-folds reduced water absorption. Our investigation provides compelling evidence that the SiO2NPs-V-PDMA obtained from EB modification and the developed coating formula for roller-based coating process are realistic approaches for hydrophobic/superhydrophobic coatings and printing inks for paper-based industries.
... This difference was caused by the different reactivity ratios of LMA and MMA in the copolymerization process as reported in the study of random copolymerization of MMA with LMA via group transfer polymerization. In this paper, the molar ratio of LMA/MMA in copolymer was also reported to be 42/58 when the LMA/MMA in feed is 40/60 (Sannigrahi et al., 1997). However, the molar ratio of LMA/MMA in DA-g-P(LMA-co-MMA)2 and P(LMA-co-MMA)4 were 41/59 and 43/57, which were probably caused by the inevitable errors of integration area obtained from 1 H NMR spectra. ...
Rosin is an important renewable resource. However, preparation of rosin-based polymers with good performance is still challenging. In this work, a series of rosin-based polymers were prepared via “grafting from” atom transfer radical polymerization (ATRP) using dehydroabietic acid (DA, extracted from pine trees) derived ATRP initiator (2-BriBEDA, (2-bromoisobutyric) hydroxyethyl ester of dehydroabietic acid). The graft polymerization behavior of polar monomer methyl methacrylate (MMA), nonpolar monomer lauryl methacrylate (LMA) from DA were investigated. The kinetic studies showed that the ATRP processes of MMA, LMA as well as MMA-co-LMA were all living and controlled, which indicated that 2-BriBEDA was a good ATRP initiator. With the introduction of DA, all rosin-based copolymers showed improved thermal stability, UV-blocking performance, hydrophobicity and mechanical properties. In addition, DA-g-P(MMA-co-LMA) polymers showed good mechanical and elastic properties with highest tensile strength of 5.10 ± 0.87 MPa and strain of 513 ± 32 % and elastic strain recovery above 70 % which was comparable with other reported sustainable thermoplastic elastomers (TPEs) polymers. This work demonstrates an alternative avenue for rosin-based polymer design to achieve the improvement in thermal, UV-blocking and mechanical performance.
... Few researchers described the homopolymerization and/or copolymerization of LMA in homogeneous conditions employing organic solvents to avoid the problems associated with the hydrophobicity of LMA (Xu et al., 2003;Demetriou and Krasia-Christoforou, 2008;Qiu et al., 2009;Chatterjee and Mandal, 2006;Beers and Matyiaszewski, 2001;Mishra et al., 2001;Sannigrahi et al., 1997). Recently, we proposed that emulsion copolymerization of LMA is possible in water-ethanol dispersion media using water soluble initiator (Ahmad et al., 2011;Shabnam et al., 2013). ...
Industrial application of hydrophobic materials is numerous particularly as adsorption beads to remove organic pollutants. In this research combined effect of hydrophobicity and reactive epoxide group on the adsorption behavior of dye molecules by composite polymer particles was investigated. Lauryl methacrylate (LMA) a poor water soluble long chain vinyl monomer is commercially available. Polystyrene/poly(LMA-divinyl benzene) or PS/P(LMA-DVB) composite seed particles were first prepared by slightly modified activated swelling of micron-sized PS seed particles utilizing either water or water-ethanol dispersion medium. The influence of poly(vinyl alcohol) (PVA) as steric stabilizer on the size and size distribution was evaluated. The poor solubility of LMA in the continuous phase hindered the homogeneous swelling of PS particles even in presence of ethanol (5% w/w) and resulted in fairly polydispersed PS/P(LMA-DVB) composite seed particles. The composite seed particles were then functionalized with epoxide group by seeded polymerization of glycidyl methacryate (GMA) to produce PS/P(LMA-DVB)/PGMA composite polymer particles. The epoxide functionalized PS/P(LMA-DVB)/PGMA composite polymer particles were used to adsorb two kinds of azo dyes, congo red (CR) and direct red-75 (DR-75). The effects of initial dye concentration at 303 and 323K on adsorption behavior were investigated and the adsorption was explained by adsorption isotherms. Temperature dependent adsorption measurements were also carried out at identical initial dye concentration. The adsorption results showed that inclusion of reactive epoxide group on/near the surface of hydrophobic PS/P(LMA-DVB) composite seed particles improved the adsorption capacity of dye molecules.
Reversible addition-fragmentation chain transfer (RAFT) polymerization of lauryl meth-acrylate (LMA) in the presence of S-methoxycarbonyl phenylmethyl dithiobenzoate (MCPDB) as a RAFT chain transfer agent (CTA) and subsequent RAFT polymerization of poly(ethylene oxide) monomethyl ether methacrylate (PEO 5MEMA or PEO 45MEMA) was done with the aim to prepare amphiphilic diblock copolymer brushes of controlled structure. Te molecular weight of PLMA and PLMA-b-PPEO 5MEMA copolymers was evaluated by several methods including SEC calibrated using polystyrene standards, and end-group analysis by 1H NMR and UV-Vis. Te kinetics of LMA polymerization was followed by 1H NMR spectroscopy by comparing the signals attributed to the monomer and corresponding monomeric units in PLMA. RAFT polymerization of LMA at the ratio [MCPDP] : [AIBN] = 4 demonstrated the "living" character enabling to synthesize PLMA with a low polydispersity (M w/M n = 1.08-1.19) and a relatively high molecular weight (M n up to 60 000, degree of polymerization DP up to 260). Several diblock copolymers PLMA-b-PPEO 5MEMA with various lengths of the blocks and a high molecular weight (M n up to 300 000) were prepared and characterized. RAFT polymerization of PEO 45MEMA from PLMA as a macro-CTA failed.
This chapter is divided into three parts. First, seminal and recent developments in the synthesis of star structures by the most important polymerization techniques, such as anionic, cationic, controlled radical, ring opening, ring-opening metathesis, group transfer, and their combinations, are presented. The synthesis of star polymers by step-growth polycondensation, metal template-assisted as well as 'electrostatic self-assembly and covalent fixation' methods is also described. In addition, the significant contribution of 'click' chemistry for the synthesis of these stars is discussed.Second, the properties of star polymers, both in solution and in bulk, are discussed. Emphasis is given to the examination of the size of the star compared to linear chains, the aggregation phenomena of telechelic stars, the micellization behavior in selective solvents, and the phase separation in star-block and miktoarm stars, as well as the dynamic behavior and the rheological properties in solution and melt. Third, almost all commercial and a few potential high-tech applications are given. Finally, a brief paragraph concluding the chapter is provided.
This contribution reports the precipitation copolymerization of lauryl methacrylate–divinylbenzene (LMA–DVB) in stable isolated droplets dispersed in water. The droplets contain either n-hexadecane (HD) or HD–toluene (HD–T) or toluene as a nonsolvent for the resulting P(LMA–DVB) copolymer. The polymerization proceeds smoothly with an appreciably high content of DVB without the formation of coagulum and thus proves the quite high stability of the droplet reactors. The differences in the interaction between the nonsolvent–copolymer combinations allow the variation of the internal morphology of the particles between core and shell type, highly porous, and solid sphere. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41881.
The application potential of hydrophobic polymer is numerous. Lauryl methacrylate (LMA) having long alkyl chain is a commercially available hydrophobic monomer. In this investigation, poly‐LMA (PLMA) latex particles were prepared by suspension polymerization in aqueous media using 2,2′‐azobis(isobutyronitrile) (AIBN) in presence of poly(vinyl alcohol) (PVA) as steric stabilizer. The preparation kinetics was studied in detail in terms of percentage yield and particle size variation. Low glass transition temperature (∼ −65°C) associated with high flexibility did not allow electron micrographic observation though 1H‐NMR and particle size measurement confirmed the formation of PLMA latex. To improve the glass transition temperature, aqueous emulsion copolymerization of LMA with methyl methacrylate (MMA) was carried out. The solubility of LMA was improved by adding ethanol to the aqueous phase. Two types of polymeric stabilizers, PVA and poly(vinyl pyrrolidone) (PVP) were used to stabilize the colloidal particles. The nature of the stabilizer affected both morphology and final rate of polymerization. The hydrophobic P(LMA‐MMA) copolymer particles were subsequently modified by nanosized magnetic (Fe3O4) particles by two different methods. The in situ formation of Fe3O4 particles in presence of P(LMA‐MMA) was found to be suitable for the preparation of magnetic latex particles. Scanning electron microscope (SEM), FTIR, transmission electron microscope (TEM), X‐ray diffraction (XRD) and energy‐dispersive X‐ray spectroscopy (EDX) were used for the characterization of magnetically doped particles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012
13C NMR spectra (75.5 MHz) of methyl methacrylate (M)-lauryl methacrylate (L) copolymers prepared by group transfer polymerization (GTP) were analyzed for sequence distribution and relative stereochemical configuration of monomer units along the macromolecular chains. The concentrations of M- and L-centered triads, determined experimentally from α-CH3 and C=O resonance signals, were in good agreement with those calculated statistically, taking into consideration the terminal copolymerization model and Bernoullian distribution of stereoregularity, with the statistical parameters Pij determined from the reactivity ratios rM=1.38±0.11 and rL=0.68±0.10 and the coisotacticity parameters σMM=0.24, σLL=0.27, σML=σLM=σ*=0.30.
The triblock copolymer poly(methyl methacrylate-b-lauryl methacrylate-b-methyl methacrylate) {P(MMA-b-LMA-b-MMA)} has been synthesized by a two stage atom transfer radical polymerization in bulk at near room temperature (ca. 35 °C) using CuCl/pentamethyldiethylenetriamine (PMDETA)/tricaprylylmethylammonium chloride (Aliquat®336) complex as the catalyst and 1,2-bis (bromoisobutyryloxy)ethane (BIBE) as the initiator for the polymerization of LMA in the first stage. The same catalyst was also used for the polymerization of MMA in the second stage. The dynamic mechanical thermal analysis of a sample with the middle block Mn = 82000 and each end block Mn = 14500 showed typical features of a thermoplastic elastomer.
Atom transfer radical polymerization of lauryl methacrylate (LMA) was carried out in the presence of various ligands using ethyl-2-bromoisobutyrate as initiator and CuBr as catalyst in toluene at 95 °C. The ligands used were 2,2′-bipyridyl,4,4′-dimethyl-2,2′-bipyridyl, N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) and N-(n-propyl)-2-pyridylmethanimine (PPMI). Controlled polymerization was observed with PMDETA and PPMI ligands and poly(LMA)s with narrow molecular weight distribution (MWD) (Mw/Mn≤1.2) were obtained. The first-order time-conversion plot showed the presence of termination in the presence of PMDETA. A linear first-order time-conversion plot with a small induction period (∼10 min) was observed in the presence of PPMI ligand. Di-block copolymers of LMA and methylmethacrylate with controlled molecular weight and narrow MWDs were synthesized via sequential monomer addition.
Anionic polymerization of lauryl methacrylate (LMA) with 1,1-diphenylhexyl lithium in tetrahydrofuran (THF) at −40 °C resulted in a multimodal and broad molecular weight distribution (MWD) with poor initiator efficiency. In the presence of additives such as dilithium salt of triethylene glycol (G3Li2), LiCl, and LiClO4, the polymerization resulted in polymers with a narrow MWD (≤ 1.10). Diblock copolymers of methyl methacrylate (MMA) and LMA were synthesized by anionic polymerization using DPHLi as initiator in THF at −40 °C with the sequential addition of monomers. The molecular weight distribution of the polymers was narrow and without homopolymer contamination when LMA was added to living PMMA chain ends. Diblock copolymers with broad/bimodal MWD were obtained with a reverse-sequence monomer addition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 875–882, 2004
The atom transfer radical polymerization (ATRP) of lauryl methacrylate (LMA) with an ethyl 2-bromobutyrate/CuCl/N,N,N′,N″,N″-pentamethyldiethylenetriamine initiation system was successfully carried out in toluene, and poly(lauryl methacrylate) with a low polydispersity (1.2 < weight-average molecular weight/number-average molecular weight < 1.5) was obtained. Plots of ln ([M])0/([M]) versus time and plots of the molecular weight versus conversion showed a linear dependence, indicating a constant number of propagating species throughout the polymerization. The rate of polymerization was 0.56-order with respect to the concentration of the initiator and 1.30-order with respect to the concentration of the Cu(I) catalyst. In addition, the effect of the solvent on the polymerization was investigated, and the thermodynamic data and activation parameters for the solution ATRP of LMA were reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1117–1125, 2003
Four well-defined diblock copolymers and one statistical copolymer based on lauryl methacrylate (LauMA) and 2-(acetoacetoxy)ethyl methacrylate (AEMA) were prepared using reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were characterized in terms of molecular weights, polydispersity indices (ranging between 1.12 and 1.23) and compositions by size exclusion chromatography and 1H NMR spectroscopy, respectively. The preparation of the block copolymers was accomplished following a two-step methodology: First, well-defined LauMA homopolymers were prepared by RAFT using cumyl dithiobenzoate as the chain transfer agent (CTA). Kinetic studies revealed that the polymerization of LauMA followed first-order kinetics demonstrating the “livingness” of the RAFT process. The pLauMAs were subsequently used as macro-CTA for the polymerization of AEMA. The glass transition (Tg) and decomposition temperatures (ranging between 200 and 300 °C) of the copolymers were determined using differential scanning calorimetry and thermal gravimetric analysis, respectively. The Tgs of the LauMA homopolymers were found to be around −53 °C. Block copolymers exhibited two Tgs suggesting microphase separation in the bulk whereas the statistical copolymer presented a single Tg as expected. Furthermore, the micellization behavior of pLauMA-b-pAEMA block copolymers was investigated in n-hexane, a selective solvent for the LauMA block, using dynamic light scattering. pLauMA-b-pAEMA block copolymers formed spherical micelles in dilute hexane solutions with hydrodynamic diameters ranging between 30 and 50 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5442–5451, 2008
The reliable estimation of monomer reactivity ratios is a key problem in the development of process models, and, thus, is an important issue in both process design and control. Copolymers of isobutyl methacrylate (i‐BMA), and lauryl methacrylate (LMA) were prepared by free radical bulk copolymerization at 70 °C using 2,2′–azobisisobutyronitrile (AIBN) as initiator. The monomer reactivity ratios as well as the 95% confidence intervals were calculated from Fineman‐Ross, Ezrielev‐Brokhina‐Roskin, Kelen & Tudos, extended Kelen & Tudos and a linear iterative method proposed by Mao and Huglin. The estimation process was performed by applying nonlinear techniques based on Marquardt optimization, “ordinary least square” (OLS) and “generalized least square” (GLS) approaches and the results were compared with each other. The novel GLS estimator program developed during this study was employed to ascertain the shape of the copolymer composition curve and good agreement between experimental and calculated copolymer composition was obtained. Also, both real and simulated data was presented, which show GLS method is a statistically valid technique for estimating reactivity ratios by accounting response error structure. This new estimation method handles regression models with error terms that are heteroskedastic or serially correlated, or both.
95% joint confidence interval for reactivity ratios from “NLLS” analysis.
magnified image 95% joint confidence interval for reactivity ratios from “NLLS” analysis.
Copper-mediated atom transfer radical polymerization (ATRP) of lauryl methacrylate (LMA) and other long-chain methacrylates was investigated in bulk at 35 °C by using CuCl/N,N,N′,N′,N′′-pentamethyldiethylenetriamine (PMDETA)/tricaprylylmethylammonium chloride (Aliquat®336) as the catalyst system and ethyl 2-bromoisobutyrate (EBIB) as the initiator. The investigated monomers can be derived from fatty alcohols and are therefore an important renewable resource for a sustainable development of our future. The amounts of ligand, Aliquat®336 and CuCl were optimized and the effect of their concentrations on the control of the polymerization and the observed conversions were investigated. It was found that a molar ratio of EBIB/CuCl/Ligand/Aliquat®336 of 1 : 1 : 3 : 1 provided the highest conversions of LMA and the best controlled polymerizations. These optimized conditions allowed for the synthesis of poly(lauryl methcarylate)s with different targeted DP (25, 50, 75, 100, 120, 240, and 500), including high-molecular-weight polymers with narrow molecular weight distributions. In addition, methacrylate monomers were prepared from fatty alcohols (capric, myristic, palmitic, stearic) and polymerized using the developed procedure to obtain polymers with the same DP and different chain lengths (C10, C12, C14, C16, and C18) of pending alkyl groups. Finally, the thermal properties of these polymers were examined by differential scanning calorimetry and thermogravimetric analysis.
The utilization of plant oil renewable resources as raw materials for monomers and polymers is discussed and reviewed. In an age of increasing oil prices, global warming and other environmental problems (e.g. waste) the change from fossil feedstock to renewable resources can considerably contribute to a sustainable development in the future. Especially plant derived fats and oils bear a large potential for the substitution of currently used petrochemicals, since monomers, fine chemicals and polymers can be derived from these resources in a straightforward fashion. The synthesis of monomers as well as polymers from plant fats and oils has already found some industrial application and recent developments in this field offer promising new opportunities, as is shown within this contribution. (138 references.)
Copolymers of methyl methacrylate (MMA) and lauryl methacrylate (LMA) were prepared to obtain injectable ductile materials to be used in restoring vertebra height in kyphoplasty. Copolymers with M(w) in the range of 130,000 and polydispersity of 1.8 were obtained. Several aspects of the effect of adding LMA monomers were examined including intrinsic viscosity, thermal properties, mechanical properties, and the ability to be injected under high pressure. By increasing the amount of LMA, the ductility of the polymer was increased, accompanied by a decrease in Young's modulus and strength. The copolymer with monomers ratio (MMA:LMA) 1:1 v/v possessed the most suitable mechanical properties and injectability, which may have potential clinical use in orthopedics.
The kinetics, mechanism, tacticity, and mol. wt. distribution in group-transfer polymn. of Me methacrylate (I) and tert-Bu methacrylate (II) in the presence of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene as initiator and tris(dimethylamino)sulfonium difluoride (III), tris(dimethylamino)sulfonium benzoate, and tetrabutylammonium dibenzoate as catalysts were studied. In the polymn. of I catalyzed by III, an induction period was obsd. and the propagation reaction was first order with respect to both I and II concns. and zeroth order with respect to the initiator concn. The group-transfer polymn. of II was similar to that of I except being slower by a factor of .apprx.2.