Synthesis and characterization of poly(catechol) catalyzed by porphyrin and enzyme

Catalytic polymerization of catechol was performed employing the cationic porphyrin and horseradish peroxidase (HRP) as catalysts. The obtained results demonstrate that the cationic metalloporphyrin is a more-efficient catalyst than the HRP in the catechol polymerization. The oxidative polymerization was carried out in the presence of polystyrene sulfonate (PSS) as a template. According to TGA data, poly(catechol) that is synthesized by porphyrin catalyst exhibits more thermal stability than the enzymatic catalyzed product. The GPC indicate higher molecular weight of polymer synthesized by porphyrin as a catalyst. Cyclic voltammetry measurements show that the synthesized polymers have convenient electroactivity. The poly(catechol) and its methyl and methoxy derivatives that are synthesized by porphyrin catalyst show low electrical conductivity.     

Poly‐2‐[(4‐methylbenzylidene)amino]phenol: Investigation of thermal degradation and antimicrobial properties

A new polyphenol (poly‐2‐[(4‐methylbenzylidene)amino]phenol) (P(2‐MBAP)) containing an azomethine group was synthesized by oxidative polycondensation reaction of 2‐[(4‐methylbenzylidene)amino]phenol (2‐MBAP) with NaOCl, H₂O₂, and O₂ oxidants in an aqueous alkaline medium. The structures of 2‐MBAP and P(2‐MBAP) were characterized by UV‐vis, FT‐IR, and ¹H NMR spectra. While the monomer decomposed completely up to 350°C and 57.2% of the polymer decomposed up to 1000°C. The thermal degradation of P(2‐MBAP) was also supported by the Thermo‐IR spectra recorded in the temperature range of 25–800°C. Electrical conductivity of the polymer was observed to increase 10⁸ fold after doping with I₂. Antimicrobial activities of the P(2‐MBAP) and 2‐MBAP against Sarcina lutea, Enterobacter aerogenes, Escherichia coli, Enterococcus feacalis, Klebsiella pneumoniae, Bacillus subtilis, Candida albicans, and Saccharomyces cerevisiae were also investigated. The number average molecular weight (M_n), weight average molecular weight (M_w) and polydispersity index (PDI) of the polymers were determined by gel permeation chromatography (GPC). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41758.     

Synthesis,structure, and properties of syndiotactic polystyrene catalyzed by Cp*Ti(OBz)3/MAO/TIBA

The synthesis of syndiotactic polystyrene (sPS) catalyzed with Cp*Ti(OBz)₃/MAO/TIBA and toluene as the solvent and the effects of polymerization temperature and the external addition of TIBA on polymerization behavior were investigated. The study revealed that catalytic activity increased with polymerization temperature. The greatest activity, 619 kg sPS mol^?1 Ti h^?1, was exhibited up to 90°C. TIBA also improved catalytic activity. The molecular weight of the polymer obtained decreased with polymerization temperature and the amount of TIBA. The structure and properties of syndiotactic polystyrene were characterized by ¹³C‐NMR, FTIR, DSC, and GPC methods. It was confirmed that the sPS obtained featured all‐trans planar zigzag conformation and higher syndiotacticity, molecular weight, and melting point. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 501–505, 2007     

Initiator‐fragment incorporation radical polymerization of ethylene glycol dimethacrylate in the presence of 1,1‐diphenylethylene: synthesis and characterization of soluble hyperbranched polymer nanoparticles

The polymerization of ethylene glycol dimethacrylate (EGDMA) as crosslinker was carried out at 70 and 80 °C in benzene using dimethyl 2,2′‐azobisisobutyrate (MAIB) as initiator at concentrations as high as 0.50–0.70 mol l^?1 in the presence of 1,1‐diphenylethylene (DPE), where the concentrations of EGDMA and DPE were 0.50–0.70 and 0.25–0.50 mol l^?1, respectively. The polymerization proceeded homogeneously, without gelation, to give soluble polymers. The yield and molecular weight of the resulting polymers increased with time. The homogeneous polymerization system involved ESR‐observable DPE‐derived radicals of considerably high concentration (3.6–5.3 × 10^?5 mol l^?1). The methoxycarbonylpropyl groups as MAIB‐fragments were incorporated as a main constituent (35–50 mol%) into the polymers (initiator‐fragment incorporation radical polymerization). The polymers also contained DPE units (15 mol%) and EGDMA units with double bonds (10–25 mol%) and without double bonds (20 mol%). Results from gel permeation chromatography (GPC)–multiangle laser light scattering (MALLS), transmission electron microscopy (TEM) and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched nanoparticles. Copyright © 2004 Society of Chemical Industry     

Polystyrene with half-titanocene/MAO catalysts: Influence of 2,6-diisopropylphenol

Styrene polymerization was carried out by a simple half-titanocene complex [cyclopentadienyltitanium trichloride] (CpTiCl₃) and pentamethyl [cyclopentadienyltitanium trichloride] (Cp*TiCl₃) combined with methylaluminoxane (MAO) as a cocatalyst. The effects of addition of 2,6-diisopropylphenol on the catalytic activity of the above catalytic systems and the microstructure of the resulting polymer were investigated. The results of the above experiments showed that the addition of the 2,6-diisopropylphenol changed the catalytic performance of the above catalytic systems, in terms of catalytic activity of the metal complexes and microstructure, molecular weight and molecular weight distribution of polystyrene synthesized. The yields of polystyrene of the above polymerization reactions indicated that the 2,6-diisopropylphenol enhanced the catalytic activity of both the CpTiCl₃/MAO and Cp*TiCl₃/MAO catalyst systems. Further Soxhlet extraction of the polymer was conducted by boiling acetone for 6 h to get pure syndiotactic polystyrene. The microstructure of polystyrene obtained by the above polymerization reactions was investigated by ¹³C NMR, GPC and DSC. Results indicated the formation of syndiotactic polystyrene in the absence of phenol and in low concentration of phenol. On the other hand, in the presence of excess phenol, the polystyrene produced was found to be completely atactic in nature. The appearance of monomodal peaks and narrow polydispersity in the GPC results of polystyrenes obtained in all the above polymerizations indicated that the polymerization was only coordination in nature.     

Synthesis and characterization of soluble hyperbranched polymer via initiator‐fragment incorporation radical polymerization of divinylbenzene with dimethyl 2,2′‐azobisisobutyrate

The homopolymerization of divinylbenzene (DVB) as an excellent crosslinker (0.20 mol/L) with dimethyl 2,2′‐azobisisobutyrate (MAIB) proceeded homogeneously without any gelation at 80°C in benzene when the MAIB concentrations as high as 0.30–0.50 mol/L were used, yielding soluble polymers. In the polymerization at the concentrations of [DVB] = 0.20 mol/L and [MAIB] = 0.50 mol/L, the polymer yield increased with time and leveled off over 90 min. The molecular weight and molecular weight distribution increased with polymer yield. The vinyl groups of DVB were observed to be almost completely consumed in about 80 min, by FT near‐IR spectroscopic analysis. The homogeneous polymerization system involved ESR‐observable polymer radical, the concentration of which increased with time up to 3.4 × 10^?5 mol/L. The polymer formed in the polymerization for 2 h consisted of 46 mol % of DVB unit and 54 mol % of the methoxycarbonylpropyl group as MAIB fragment, indicating that an initiator‐fragment incorporation radical polymerization proceeds in the present polymerization. The polymer was soluble in benzene, tetrahydrofuran, ethyl acetate, chloroform, acetone, and N,N‐dimethylformamide, while it was insoluble in n‐hexane, acetonitrile, dimethyl sulfoxide, methanol, and water. The results of the multiangle laser light scattering and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched polymer nanoparticles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 664–670, 2006     

Fate of horseradish peroxidase during oxidation of monobrominated phenols

BACKGROUND: Peroxidase‐catalyzed polymerization of phenols is accompanied by substantial enzyme precipitation with reaction products. The enzyme fate during the polymerization of monobromophenols by horseradish peroxidase (HRP) was studied. Enzyme fate was simultaneously monitored by protein, total nitrogen mass balance and gel electrophoresis (SDS‐PAGE) analysis of both soluble and precipitate fractions. RESULTS: SDS‐PAGE analysis revealed that molecular weight bands of protein in the precipitate shifted upwards toward higher molecular weights, compared with protein control. When co‐polymerization was practiced higher HRP precipitation occurred compared with polymerization of a single substrate, regardless of substrate combination applied. Addition of polyethylene glycol (PEG) to the reaction mixture decreased the extent of HRP precipitation. At 2 mmol L^?1 H₂O₂, corresponding to the stoichiometric equivalent concentration, 50% precipitation occurred after 1 h (～70% after 24 h) compared with 97–98% (～100% after 24 h) without PEG. Nevertheless, further increase of H₂O₂ increased HRP precipitation regardless of PEG (85% at 4 mmol L^?1 and 95% at 5 mmol L^?1). The lowest degree of enzyme inactivation was observed for metabromophenol, which displayed the lowest transformation yield, compared to the other congeners. CONCLUSIONS: Results from SDS‐PAGE indicate that an interaction stronger than hydrophobic, resisting the denaturative conditions, may take place between HRP and the reaction products, suggesting the occurrence of a covalent link between them. Oxidation was enhanced by inclusion of PEG, which partially suppressed product‐dependent inactivation. The extent of enzyme inactivation depends on the substrate used, while highest inactivation occurred when co‐polymerization was practiced. Copyright © 2009 Society of Chemical Industry     

Composition and long‐term stability of polyglycidol prepared by cationic ring‐opening polymerization

Polyglycidol synthesized by cationic ring‐opening polymerization of glycidol (boron trifluoride initiation in dichloromethane) was purified of low molecular weight contaminants by centrifugal filtration. The high and low molecular weight fractions were characterized by NMR, GPC, osmometry, viscometry, DSC, and FTIR. The ¹³C‐NMR spectrum of this polymer was completely annotated by proposing a new step in the reaction mechanism. The four thermal dimers of glycidol were also isolated and identified as 2,5‐bis(hydroxymethyl)‐1,4‐dioxane and 2,6‐bis(hydroxymethyl)‐1,4‐dioxane, each of which can exist in cis and trans configurations. Polyglycidol was found to be hygroscopic, picking up about 5% by weight of atmospheric moisture. It was also found that, over time (ca. 1–2 years), polyglycidol crosslinks into a rubbery, insoluble mass. It is therefore recommended that this polymer be stored dry and used within a few months of synthesis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1344–1351, 2004     

A new polymerization method and kinetics for acrylamide: Aqueous two‐phase polymerization

The concept of aqueous two‐phase polymerization and a new polymerization method for the preparation of water‐soluble polymers are presented. The phase diagram of poly(acrylamide) (PAAm)‐poly (ethylene glycol) (PEG)‐water two‐phase system was measured by the gel permeation chromatography (GPC). The aqueous two‐phase of PAAm‐PEG‐water system can be easily formed. The critical concentration of phase separation was affected by the molecular weight of PEG. The aqueous two‐phase polymerization of acrylamide (AAm) has been successfully carried out in the presence of PEG by using ammonium persulfate (APS) as the initiator. The polymerization behaviors with varying concentration of AAm, initiator and PEG, the polymerization temperature, the molecular weight of PEG, and emulsifier types were investigated. The activation energy of aqueous two‐phase polymerization of AAm was 132.3 kJ/mol. The relationship of initial polymerization rate (R_p0) with APS and AAm concentrations was R_p0 ∝ [APS]^0.72 [AAm]^1.28. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of temperature‐sensitive block copolymers from poly(N‐isopropylacrylamide) and 4‐methyl‐ε‐caprolactone or 4‐phenyl‐ε‐caprolactone

This study synthesizes thermally sensitive block copolymers poly(N‐isopropylacrylamide)‐b‐poly(4‐methyl‐ε‐caprolactone) (PNIPA‐b‐PMCL) and poly(N‐isopropylacrylamide)‐b‐poly(4‐phenyl‐ε‐caprolactone) (PNIPA‐b‐PBCL) by ring‐opening polymerization of 4‐methyl‐ε‐caprolactone (MCL) or 4‐phenyl‐ε‐caprolactone (BCL) initiated from hydroxy‐terminated poly(N‐isopropylacrylamide) (PNIPA) as the macroinitiator in the presence of SnOct₂ as the catalyst. This research prepares a PNIPA bearing a single terminal hydroxyl group by telomerization using 2‐hydroxyethanethiol (ME) as a chain‐transfer agent. These copolymers are characterized by differential scanning calorimetry (DSC), ¹H‐NMR, FTIR, and gel permeation chromatography (GPC). The thermal properties (T_g) of diblock copolymers depend on polymer compositions. Incorporating larger amount of MCL or BCL into the macromolecular backbone decreases T_g. Their solutions show transparent below a lower critical solution temperature (LCST) and opaque above the LCST. LCST values for the PNIPA‐b‐PMCL aqueous solution were observed to shift to lower temperature than that for PNIPA homopolymers. This work investigates their micellar characteristics in the aqueous phase by fluorescence spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS). The block copolymers formed micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 0.29–2.74 mg L^?1, depending on polymer compositions, which dramatically affect micelle shape. Drug entrapment efficiency and drug loading content of micelles depend on block polymer compositions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of unsaturated polyphosphoester as a potential injectable tissue engineering scaffold materials

Polyphosphoester is a kind of biodegradable polymer with excellent biocompatibility and have been used in drug delivery, tissue engineering, and other bioapplications. A novel unsaturated polyphosphoester (UPPE) based on bis(1,2‐propylene glycol) fumarate (BPGF) and ethyl dichlorophosphate was synthesized by polycondensation reaction, and crosslinkable double bonds was introduced into the resulting polymer through the fumarate groups. NMR results indicate that there are three possible bonding models in polyphosphoester because of three isomers of BPGF. The GPC results express that increase in polymerization time leads to high molecular weight of polyphosphester and narrow distribution of molecular weight. After 18 h of polymerization reaction, the molecular weight reached to 5956 g mol^?1 and the polydispersity index was 1.12. The UPPE was soluble in N‐vinyl pyrrolidone and easily crosslinked by free‐radical polymerization. At the constant temperature (37°C), the maximum temperature due to heat release during crosslinking reaction varied from 41.1°C to 82.30°C and the setting time was between 1.95 and 10.28 min, according to different formulas. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3095–3101, 2006     

2,2,6,6‐Tetramethylpiperidine‐1‐oxyl‐mediated living mini‐emulsion polymerization of styrene under ambient pressure in a semi‐batch process: effect of ascorbic acid

2,2,6,6‐Tetramethylpiperidine‐1‐oxyl (TEMPO)‐mediated living mini‐emulsion polymerization of styrene with feeding of an ascorbic acid aqueous solution throughout the polymerization was performed at 90 °C under ambient pressure. The concentrations of sodium dodecylbenzenesulfonate (SDBS) and ascorbic acid were varied to study the shell polymerization mechanism of latex particles and evolution of growing chains. Interactions between SDBS and ascorbic acid and incompatibility between ascorbic acid and styrene were evident from UV‐visible analyses. High hydrophilicity of ascorbic acid in the aqueous phase was proved using a gravimetric method. Accordingly, the formation of a surface barrier on particles was proposed because of the interactions between SDBS and ascorbic acid. For higher SDBS concentration, the surface barrier on the particles was denser. Therefore, the polymerization rate decreased with increasing SDBS concentration. However, the polymerization rate increased with increasing ascorbic acid concentration. This was due to a higher consumption rate of TEMPO by ascorbic acid. Free TEMPO tended to reside in surface zones of the particles because of the surface activity between the aqueous and oil phases. The surface zones were thus the main loci where TEMPO was consumed by ascorbic acid. The estimated number‐average molecular weight (M_n) of growing chains increased in a linear fashion with conversion. This indicated that the growing chains were produced via living mini‐emulsion polymerization. For these growing chains, the estimated M_n and final polydispersity increased with increasing SDBS concentration. This was caused by a decrease in TEMPO concentration in the surface zones of particles with increasing SDBS concentration. The ‘livingness’ of polystyrene was identified by conducting bulk polymerization of chain extension. Based on the results obtained, a shell polymerization mechanism of latex particles was proposed, and living mini‐emulsion polymerization was limited to the surface zones of particles. Copyright © 2010 Society of Chemical Industry     

Studies on the preparation of branched polymers from styrene and divinylbenzene

The self‐condensing vinyl polymerization of styrene and an inimer formed in situ by atom transfer radical addition from divinylbenzene and 2‐bromoisobutyl‐tert‐butyrate using atom transfer radical polymerization technique was studied. To study the polymerization mechanism and achieve high molecular weight polymer in a high polymer yield, the polymerization was carried out in bulk at 80°C. Proton nuclear magnetic resonance (¹H‐NMR) spectroscopy and gel permeation chromatography (GPC) coupled with multiangle laser light scattering (MALLS) were used to monitor the polymerization process and characterize the solid polymers. It is proved that the polymerization shows a “living” polymerization behavior and the crosslinking reaction has been restrained effectively due to the introduction of styrene. Polymers with high molecular weight (M_w.MALLS > 10⁵) can be prepared in high yield (near 80%). Comparison of the apparent molecular weights measured by GPC with the absolute values measured by MALLS indicates the existence of branched structures in the prepared polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Design,synthesis, and photosensitive performance of polymethacrylate‐positive photoresist‐bearing o‐nitrobenzyl group

Novel polymethacrylate‐positive photoresist‐bearing o‐nitrobenzyl group was described herein. The matrix polymer (PCHIBNB) was synthesized by copolymerization of cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBMA), and o‐nitrobenzyl methacrylate (NBMA) via reversible addition fragmentation chain transfer (RAFT) polymerization method. After UV irradiation, the o‐nitrobenzyl groups of PCHIBNB were photocleaved and the resulting carboxyl groups were highly alkali‐soluble, so that the matrix polymer could be etched by mild alkali solution with no requirements of photosensitizers or photoacid generators. PCHIBNB was characterized by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H‐NMR) spectroscopy, and gel permeation chromatography (GPC). The photocleavable behaviors of PCHIBNB were determined by FTIR, ¹H‐NMR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) analysis. The resist formulated with this polymer and cast in tetrahydrofuran (THF) solution showed 10 μm × 10 μm square pattern using a mercury–xenon lamp in a contact printing mode and tetramethyl‐ammonium hydroxide aqueous solution as a developer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41733.     

Electroinitiated polymerization of 2-allylphenol

Summary Redox behaviour of 2-allylphenol (2APhOH) was studied by using cyclic voltammetry (CV) and electroinitiated polymerization was conducted at the measured peak potentials. Constant potential electrolysis (CPE) of the monomer was carried out in acetonitrile-sodium perchlorate, solvent-electrolyte couple, at room temperature. Polymerization of the monomer yielded insoluble polymer films on the surface of the electrode together with the low molecular weight polymers in the bulk of the solution. The structural analysis of the polymers were carried by ¹H-NMR and FTIR spectroscopy. Molecular weight of the soluble polymer was determined by GPC. Thermal properties of the polymer film and soluble polymer were studied by DSC. The course of electroinitiated polymerization was monitored by in-situ UV-VIS spectroscopy. Received: 10 April 2000/Revised version: 21 June 2000/Accepted: 5 July 2000     

Synthesis and characterization of a novel hyperbranched polyether

A hyperbranched polyether has been synthesized by a single‐step nucleophilic displacement polymerization technique between cyanuric chloride and the sodium salt of bisphenol‐A. The effects of various reaction parameters on the yield, and molecular weight, as measured by the intrinsic viscosity of the polymer, have been studied. The synthesized polymer has been characterized by FT‐IR, UV and ¹H NMR spectroscopies, elemental analysis, solubility and viscosity measurements. The polymer is soluble in highly polar solvents such as N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide, partially soluble in dilute aqueous NaOH solution, methanol, ethanol, chloroform, etc., but insoluble in water and non‐polar hydrocarbon solvents. The solubility parameter of the hyperbranched polymer has also been measured experimentally. Copyright © 2004 Society of Chemical Industry     

Inverse emulsion free‐radical polymerization of acrylamide terpolymer for enhanced oil recovery application in harsh reservoir conditions

A free‐radical inverse emulsion polymerization formulation has been developed for preparation of acrylamide (AAm)/sodium 2‐acrylamido‐2‐methylpropanesulfonate (AMPSNa)/N‐vinylpyrrolidone (VP) terpolymers. An aqueous solution of a blend of monomers is emulsified in n‐decane using Tween 85 (Tw85). Ammonium persulfate (APS) and dicumyl peroxide (DCP) were used as initiators for water and oil phases, respectively. The reactions were catalyzed by temperature and by a redox pair; the former is achieved at 60°C and the latter by adding tetramethylethylenediamine (TEMED) and sodium bisulphite (BisNa) to activate the initiator in water and oil phase, respectively. The emulsion type, stability, conversion, and rate of polymerization were analyzed. The obtained terpolymer was characterized by elemental analysis, infrared spectroscopy (FTIR), ¹³C nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology. Thermal catalyzed emulsion polymerization initiated with DCP showed the best performance as viscosity control agent and as polymeric precursor for in situ gel forming, for water mobility control and flow diversification, respectively. Both application for enhanced oil recovery purposes in harsh oil reservoir conditions are presented. POLYM. ENG. SCI., 57:1214–1223, 2017. © 2017 Society of Plastics Engineers     

Synthesis of well‐defined comblike hydroxy‐functionalized atactic polystyrene promoted by metallocene/tin/poly(phenyl glycidyl ether)‐co‐formaldehyde

Well‐defined comblike atactic polystyrene functionalized with hydroxyl groups was synthesized via living/controlling radical polymerization promoted by metallocene complexes in the presence of poly(phenyl glycidyl ether)‐co‐formaldehyde as the initiator and Sn as a reducing agent. The effect of the polymerization conditions, such as the ratio of initiator to monomer, temperature, and polymerization time, and the structure of the metallocene complex on the polymerization process were investigated. The resulting polymers were characterized by gel permeation chromatography, multiangle laser light scattering, ¹H‐NMR, and ¹³C‐NMR. The results show that the polymer had a narrow molecular weight distribution in the range 1.1–1.4 and the number‐average molecular weight of the polymer linearly depended on the monomer conversion within the polymerization timescale, which confirmed that living radical polymerization characteristics prevailed in the polymerization process. Both the number of arms and the number of hydroxyl groups in each polymer molecule were about four, which suggested that they arose from the epoxy functional groups of the initiator. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Catalytic polymerization of maleic anhydride

This study examined the polymerizations of maleic anhydride in solution and in the bulk phase catalyzed by nanocrystalline titania or sodium acetate. Through IR and ¹H‐NMR, the monomer and polymer were characterized, and the structure of the polymer was confirmed. Moreover, the polymer molecular weight was measured to be 400–800 in solution and 2000–3000 in the bulk phase. The mechanism of the catalytic polymerization was also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2868–2874, 2003     

Effects of mesoporous silica particles on the emulsion polymerization of methyl methacrylate

Rod‐like and spherical mesoporous SBA‐15 silica particles were synthesized as pure silicas and surface modified by organosilane coupling agents firstly, and then the effects of these mesoporous materials on the critical micelle concentration (CMC) of sodium dodecylsulfate (SDS), the stabilities of batch and semi‐continuous MMA emulsion polymerizations, and the molecular weights and molecular weight distributions of the polymer products were studied. The incorporation of both unmodified and silane‐modified forms of the mesoporous silica particles in the polymerization reaction increased the CMC of SDS. The presence of the unmodified mesoporous silica in the polymerization process led to instability in the batch emulsion polymerization process, as indicated by the formation of increased amounts of coagulum, and a decrease in the molecular weight of the polymer product. However, in comparison to the polymer formed in the absence of particle additives the molecular weight of the PMMA polymer increased with the amount of emulsifier and the addition of silane‐modified SBA‐15 particles, suggesting the growth of the polymer chains is facilitated at least in part by reaction in the pores of the particles. The improvement in molecular weight indicates that semi‐continuous MMA emulsion polymerization is best suited for the preparation of PMMA–mesoporous silica composites. POLYM. ENG. SCI., 54:2746–2752, 2014. © 2013 Society of Plastics Engineers