Deposition conditions influence the postdeposition oxidation of methyl methacrylate plasma polymer films

Plasma polymer films were deposited from methyl methacrylate (MMA) vapor under various plasma conditions and XPS and FTIR used to study the changes to the compositions of the films as they were stored in air for longer than 1 year. The plasma power input per monomer mass unit (W/FM) markedly affected the composition of the freshly deposited MMA plasma polymers. A low value of W/FM led to a high degree of retention of the original monomer structure, whereas a high value of W/FM resulted in substantial monomer fragmentation and the formation of a partially unsaturated material considerably different to conventional PMMA. As the MMA plasma coatings were stored in ambient air after fabrication, all showed spontaneous oxidative changes to their composition, but the extents and reaction products differed substantially. Deposition at low W/FM led to moderate oxidative changes, whereas high power led to a pronounced increase in the oxygen content over time and resulted in a wide range of carbon–oxygen functionalities in the aged material. As the initial compositions/plasma deposition conditions thus influenced the oxidative postdeposition reactions, MMA plasma polymers deposited under different conditions not only varied in their initial composition but then became even more diverse as they aged. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 985–1000, 1998     

Dimethylketene: Plasma-generated gas-phase precursor of photoluminescence chromophores in plasma polymerized films of methyl methacrylate and tetramethyl-1,3-cyclobutanedione

Gas-phase chemistry of tetramethyl-1,3-cyclobutanedione (TMCB) and formaldehyde plasmas have been studied within situ Fourier Transform Infrared (FTIR) Spectroscopy. Our previous work indicated that methyl methacrylate (MMA) dissociates to intermediate species of dimethylketene (DMK) and formaldehyde in MMA plasmas. This investigation of DMK dimer (TMCB) and formaldehyde plasmas is a continuation of our effort to understand the plasma polymerization chemistry of MMA. FTIR spectra confirmed the presence of DMK in TMCB plasmas and a polymeric thin film was deposited. Formaldehyde plasmas did not deposit any film for our experimental condition. Furthermore, plasma polymerized TMCB (PPTMCB) films exhibit UV photoluminescence similar to that of PPMMA films. Therefore, DMK is proposed to be the gas-phase precursor of photoluminescence chromophores in both PPMMA and PPTMCB films. Paper based on the results presented during the workshop of the Engineering Research Center for Plasma-Aided Manufacturing held in Madison, Wisconsin, in Spring 1996.     

Grafting of polymer matrix to exfoliated montmorillonite nanoplatelets in nanocomposite film cast from soap‐free emulsion polymerized latex and its fortified mechanical properties

Poly(methyl acrylate‐co‐methyl methacrylate) [P(MA‐co‐MMA)] nanocomposite film containing 1 wt % of montmorillonite (MMT) exhibited unusual higher ductility, higher strain recovery ratio after creep, and higher modulus and strength compared to neat P(MA‐co‐MMA) as they were cast from their individual latices fabricated by soap‐free emulsion polymerization. The fortified mechanical properties were attributed to the MgO components of exfoliated MMT nanoplatelets being grafted by P(MA‐co‐MMA) chains as verified by FTIR and XPS spectroscopies, which to the best of our knowledge is the first time in the literature providing the direct evidence for the polymer chains grafting onto the exfoliated MMT. TEM investigation of the stretched nanocomposite film revealed that the microcracks in the nanocomposite film appeared mainly in the bulk region of polymer matrix, implying that the interfacial strength between P(MA‐co‐MMA) and its grafted MMT nanoplatelets was higher than the cohesion strength of P(MA‐co‐MMA). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5891–5897, 2009     

Physically controlled,free‐radical polymerization of vaporized fluoromonomer on solid surfaces

Gas/vapor‐deposition polymerization (GDP) of vinyl monomer is expected to exhibit a unique polymerization behavior different from its polymerization in the liquid phase. Free‐radical GDP of 2,2,3,3,3‐pentafluoropropyl methacrylate (FMA) was carried out with a conventional free‐radical initiator (azobisisobutyronitrile) on substrate surfaces. A linear relationship between the number‐average molecular weight and polymer yield was observed, and the consecutive copolymerization of methyl methacrylate (MMA) and FMA led to the formation of block copolymer P(MMA‐block‐FMA). These results suggested that the GDP process on substrate surfaces has a living nature. During the process, the active species at growing chain ends may be immobilized on the deposit surface and restricted from the chain‐transfer reactions, resulting in a continuation of the propagation reaction. The GDP on substrate surfaces is therefore a physically controlled polymerization process. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2621–2630, 2004     

Thermoresponsive hyperbranched polymers via In Situ RAFT copolymerization of peg‐based monomethacrylate and dimethacrylate monomers

Here we report the preparation of PEG‐based thermoresponsive hyperbranched polymers via a facile in situ reversible addition‐fragmentation chain transfer (RAFT) copolymerization using bis(thiobenzoyl) disulphide to form 2‐cyanoprop‐2‐yl dithiobenzoate in situ. This novel one‐pot in situ RAFT approach was studied firstly using methyl methacrylate (MMA) monomer, then was used to prepare thermoresponsive hyperbranched polymers by copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMEMA, M_n = 475), poly(propylene glycol) methacrylate (PPGMA, M_n = 375) and up to 30 % of ethylene glycol dimethacrylate (EGDMA) as the branching agent. The resultant PEGMEMA‐PPGMA‐EGDMA copolymers from in situ RAFT were characterized by Gel Permeation Chromatography (GPC) and ¹H‐NMR analysis. The results confirmed the copolymers with multiple methacrylate groups and hyperbranched structure as well as RAFT functional residues. These water‐soluble copolymers with tailored compositions demonstrated tuneable lower critical solution temperature (LCST) from 22 °C to 32 °C. The phase transition temperature can be further altered by post functionalization via aminolysis of RAFT agent residues in polymer chains. Moreover, it was demonstrated by rheological studies and particle size measurements that these copolymers can form either micro‐ or macro photocrosslinked gels at suitable concentrations due to the presence of multiple methacrylate groups. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3751–3761     

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization of glycidyl methacrylate and its relevance to the electroless deposition of copper

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization and deposition of glycidyl methacrylate (GMA) was carried out. The effects of glow‐discharge conditions on the chemical structure and composition of the deposited GMA polymer were analyzed by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. XPS and FTIR results revealed that the epoxide groups in the plasma‐polymerized GMA (pp‐GMA) layer had been preserved to various extents, depending on the plasma deposition conditions. The morphology of the modified PTFE surface was investigated by atomic force microscopy (AFM). The pp‐GMA film with well‐preserved epoxide groups was used as an adhesion promotion layer to enhance the adhesion of the electrolessly deposited copper on the PTFE film. The T‐peel adhesion test results showed that the adhesion strength between the electrolessly deposited copper and the pp‐GMA‐modified PTFE (pp‐GMA‐PTFE) film was much higher than that between the electrolessly deposited copper and the pristine or the Ar plasma‐treated PTFE film. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3498–3509, 2000     

取代基对系列有机锡单体与MMA共聚活性的影响

本文采用红外光谱技术测定了共聚物的组成,用最小二乘曲线拟合法计算了甲基丙烯酸三甲基锡酯(TMTM),三乙基锡酯(TETM),三丁基锡酯(TBTM),和三苯基锡酯(TPTM)与甲基丙烯酸甲酯(MMA)的共聚合竞聚率,其数值分别为:r_1=1.07,r_2=0.63(TMTM/MMA);0.87,0.62(TETM/MMA);0.62,0.58(TBTM/MMA);0.68,0.60(TPTM/MMA),并计算了各单体的δ和e值,讨论了不同取代基结构对其共聚合相对活性的影响。     

The Use of ATR‐FTIR to Determine the Effects of Functional Groups on Interfacial Crosslinking of Reactive Nanoparticles

Abstract

The film formation and crosslinking of complementary reactive nanoparticle blends of acetoacetoxy (or acetoacetamido) functional particles with isocyanate functional particles were investigated using attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR) spectroscopy. A series of copolymers of 2‐ethylhexyl methacrylate (EHMA) with acetoacetoxy ethyl methacrylate (AA), 2‐methyl‐acrylic acid 2‐methyl‐2‐(3‐oxo‐butyrylamino)‐propyl ester (AM), and dimethyl meta‐isopropenyl benzyl isocyanate (TMI) were prepared by emulsion polymerization techniques at room temperature. These blends were air‐dried on ATR‐FTIR germanium (Ge) discs while the FTIR spectra were taken during the film formation process. The interfacial crosslinking reaction between functional moieties during the film formation process was determined using the FTIR data. The reactivity of acetoacetamido group is higher than that of acetoacetoxy group and the rate constant for the crosslinking reaction between two reaction moieties of terpolymer samples is higher as compared to the blended systems.     

Preparation of a copolymer of methyl methacrylate with a new monomer, 2,2,6,6‐tetramethyl‐4‐benzyloxyl‐piperidinyl methacrylate,and its initiation of the graft copolymerization of styrene with a controlled radical mechanism

A copolymer [P(MMA‐co‐TBPM)] was prepared by the radical polymerization of methyl methacrylate (MMA) and 2,2,6,6‐tetramethyl‐4‐benzyloxyl‐piperidinyl methacrylate (TBPM) with azobisisobutyronitrile as an initiator. TBPM was a new monomer containing an activated ester. Both the copolymer and TBPM were characterized with NMR, IR, and gel permeation chromatography in detail. It was confirmed that P(MMA‐co‐TBPM) could initiate the graft polymerization of styrene by the cleavage of the activated ester of the TBPM segment. This process was controllable, and the molecular weight of the graft chain of polystyrene increased with the increment of conversion. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4398–4403, 2002     

Effects of methyl methacrylate grafting and in situ silica particle formation on the morphology and mechanical properties of natural rubber composite films

The effects of methyl methacrylate (MMA) grafting and in situ formation of silica particles on the morphology and mechanical properties of natural rubber latex (NRL) were investigated. MMA grafting on NRL was carried out using cumyl hydroxy peroxide/tetraethylene pentamine (CHPO/TEPA) as a redox initiator couple. The grafting efficiency of the grafted NR was determined by solvent extractions and the grafted NRL was then mixed with tetraethoxysilane (TEOS), a precursor of silica, coated by adherence to a glass surface to form a film and cured at 80°C. The resultant products were characterized by FT‐IR and transmission electron microscopy. The influence of varying the MMA monomer weight ratio on the surface morphology of the composites was investigated by scanning electron and atomic force microscopy. The PMMA (poly MMA) grafted NRL particles were obtained as a core/shell structure from which the NR particles were the core seed and PMMA was a shell layer. The silane was converted into silica particles by a sol–gel process which was induced during film drying at 80°C. The silica particles were fairly evenly distributed in the ungrafted NR matrix but were agglomerated in the grafted NR matrix. The root‐mean‐square roughness increased with an increasing weight ratio of MMA in the rubber. The in situ silica particles in the grafted NR matrix slightly increased both the modulus and the tear strength of the composite film. Copyright © 2008 John Wiley & Sons, Ltd.     

Atom transfer radical polymerization initiated by N‐bromosuccinimide

N‐Bromosuccinimide (NBS) was used as the initiator in the atom transfer radical polymerizations of styrene (St) and methyl methacrylate (MMA). The NBS/CuBr/bipyridine (bpy) system shows good controllability for both polymerizations and yields polymers with polydispersity indexes ranging from 1.18 to 1.25 for St and 1.14 to 1.41 for MMA, depending on the conditions used. The end‐group analysis of poly(MMA) and polystyrene indicated the polymerization is initiated by the succinimidyl radicals formed from the redox reaction of NBS with CuBr/bpy. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5811–5816, 2004     

Determination of chain transfer constant to dodecanethiol in styrene/methyl methacrylate and butyl acrylate/methyl methacrylate copolymerization and effect of chain length on composition and stereochemical configuration of copolymers

Free radical copolymerization of styrene/methyl methacrylate (S/MMA) and butyl acrylate/methyl methacrylate (BA/MMA) in the presence of n-dodecanthiol (DDT) has been studied at 60°C in a 3 mol/L benzene solution using 2,2′-azobis(isobutyronitrile) (AIBN) as initiator. Overall chain transfer constant to DDT has been determined for both copolymerization systems, as a function of monomer feed composition using complete molecular weight distribution and the Mayo method. Overall transfer coefficients have values which are dependent on both monomer feed composition and individual comonomer transfer values. Composition, sequence distribution, and stereoregularity of copolymers obtained are, in our experimental conditions, independent of copolymer molecular weight. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2913–2925, 1998     

Studying anomalous diffusion in a liquid crystal/ polymer system using fast FTIR imaging

The diffusion of liquid crystal 4‐n‐pentyl‐4′‐cyanobiphenyl (5CB) into a poly(butyl methacrylate) (PBMA) matrix has been studied using fast FTIR imaging. The concentration profiles were obtained as a function of time at several temperatures above and below the nematic to isotropic transition temperature (T_NI) of 5CB and the T_g of PBMA. The time‐dependent progression of the diffusion front position, when fitted to a power law model, exhibited exponential values between 0.40 and 0.52. This, along with the observed progression of a sharp 5CB‐diffusion front into the PBMA matrix, indicates the presence of an anomalous diffusion process. It was shown that fast FTIR was able to correctly identify the diffusion process as anomalous, whereas a simple mass uptake analysis would have led to the conclusion that the process proceeded according to Fick's second law. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2261–2268, 1999     

In situ FTIR spectroscopic study on crystallization process of isotactic polystyrene

The melt crystallization process of isotactic polystyrene (i-PS) was studied by means of in situ Fourier transform infrared (FTIR) spectroscopy, with a focus on the conformational changes during the induction period. The spectra obtained during the induction period suggested the occurrence of some ordered structure that is characterized by higher regularity and packing of the helical moieties than observed in the melt. This ordered structure was clearly different from the amorphous structure, and close to the crystal structure. The Avrami analysis indicated that the formation process of the ordered structure at the late stage of the induction period is similar to the growth process of the crystallites after the induction period. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1227–1233, 1998     

Synthesis and Characterization of Nano-silica/Polyacrylate Composite Emulsions by Sol-gel Method and in-situ Emulsion Polymerization

Organic nano-silica was firstly synthesized by sol-gel method with methyl methacrylate (MMA) and butyl acrylate (BA) in the micelles as dispersing media, tetraethoxysilicate (TEOS) as precursor, hydrochloric acid as catalyst and methacryloylpropyl trimethoxysilane (A174) as modifier. Subsequently, the nano-silica/polyacrylate composite emulsions were directly prepared by in-situ emulsion polymerization under the action of the initiator. The structure and properties were characterized by Fourier transform infrared spectroscopy (FTIR), dynamic light-scattering (DSL), thermogracvimetry (TG) and transmission electron microscopy (TEM). The results showed that A174-modified nano-silica was successfully synthesized in the acrylate-based emulsions by the sol-gel method. The nano-silica was encapsulated by polyacrylate, and the composite latex particles exhibited an apparent core-shell structure. The A174 could improve the lipophilicity of nano-silica and increase the grafting efficiency of polyacrylate on nano-silica particles. The nano-silica/polyacrylate composite latex film had better thermal stability, and the composite latex particles had greater average size and broader size distribution in contrast to those of pure polyacrylate emulsions.     

Electroactive methacrylate‐based triblock copolymer elastomer for actuator application

A series of ABA triblock copolymers of methyl methacrylate (MMA) and dodecyl methacrylate (DMA) [poly(MMA‐b‐DMA‐b‐MMA)] (PMDM) were synthesized by Ru‐based sequential living radical polymerization. For this, DMA was first polymerized from a difunctional initiator, ethane‐1,2‐diyl bis(2‐chloro‐2‐phenylacetate) with combination of RuCl₂(PPh₃)₃ catalyst and nBu₃N additive in toluene at 80 °C. As the conversion of DMA reached over about 90%, MMA was directly added into the reaction solution to give PMDM with controlled molecular weight (M_w/M_n ≤ 1.2). These triblock copolymers showed well‐organized morphologies such as body centered cubic, hexagonal cylinder, and lamella structures both in bulk and in thin film by self‐assembly phenomenon with different poly(methyl methacrylate) (PMMA) weight fractions. Obtained PMDMs with 20–40 wt % of the PMMA segments showed excellent electroactive actuation behaviors at relatively low voltages, which was much superior compared to conventional styrene‐ethylene‐butylene‐styrene triblock copolymer systems due to its higher polarity derived from the methacrylate backbone and lower modulus. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Laser‐induced decomposition of 2,2‐dimethoxy‐2‐phenylacetophenone and benzoin in methyl methacrylate homopolymerization studied via matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry

Pulsed laser polymerization (PLP) experiments were performed on the bulk polymerization of methyl methacrylate (MMA) at ?34 °C. The aim of this study was to investigate the polymer end groups formed during the photoinitiation process of MMA monomer using 2,2‐dimethoxy‐2‐phenylacetophenone (DMPA) and benzoin as initiators via matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF) mass spectrometry. Analysis of the MALDI‐TOF spectra indicated that the two radical fragments generated upon pulsed laser irradiation show markedly different reactivity toward MMA: whereas the benzoyl fragment—common to both DMPA and benzoin—clearly participates in the initiation process, the acetal and benzyl alcohol fragments cannot be identified as end groups in the polymer. The complexity of the MALDI‐TOF spectrum strongly increased with increasing laser intensity, this effect being more pronounced in the case of benzoin. This indicates that a cleaner initiation process is at work when DMPA is used as the photoinitiator. In addition, the MALDI‐TOF spectra were analyzed to extract the propagation‐rate coefficient, k_p, of MMA at ?34 °C. The obtained value of k_p = 43.8 L mol^?1 s^?1 agrees well with corresponding numbers obtained via size exclusion chromatography (k_p = 40.5 L mol^?1 s^?1). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 675–681, 2002; DOI 10.1002/pola.10150     

PMMA-AES Blends Prepared by in situ Polymerization

Blends of poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-g-(ethylene-co-propylene-co-diene)-g-styrene) (AES) were prepared by in situ polymerization. AES, a commercial elastomer obtained by radical copolymerization of styrene and acrylonitrile in the presence of ethylene-propylene-diene terpolymer (EPDM), was dissolved in methyl methacrylate and the in situ polymerization was conducted at 60 °C. The blends were characterized by CHN analysis, infrared spectroscopy (FTIR), carbon-13 nuclear magnetic resonance (¹³C NMR), dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM). These blends are immiscible and present complex phase behavior. Selective extraction of the blends’ components showed that a fraction of the material is crosslinked and grafting reactions on EPDM chains take place during MMA polymerization. Syndiotactic PMMA was obtained in the presence of AES and this syndiotactic-specificity increased with increasing amount of AES. The morphology of polymerized specimens showed irregular domains of elastomeric phase and in some cases inclusions of PMMA could be observed.     

Polyurea microcapsules from isocyanatoethyl methacrylate copolymers

The synthesis of two types of isocyanate side chain containing copolymers, poly(methyl methacrylate‐co‐isocyanatoethyl methacrylate) (P(MMA‐co‐IEM)) and poly(benzyl methacrylate‐co‐isocyanatoethyl methacrylate) (P(BnMA‐co‐IEM)), which were synthesized by Cu(0)‐mediated radical polymerization, is reported. Polymerization proceeded to high conversion giving polymers of relatively narrow molar mass distributions. The incorporation of the bulky aromatic groups in the latter copolymer rendered it sufficiently stable toward hydrolysis and enabled the isolation of the product and its characterization by ¹H and ¹³C NMR, and FTIR spectroscopy and SEC. Both P(MMA‐co‐IEM) and P(BnMA‐co‐IEM) were functionalized with dibutylamine, octylamine, and (R)‐(+)‐α‐methylbenzyl‐amine, which further proved the successful incorporation of the isocyanate groups. Furthermore, P(BnMA‐co‐IEM) was used for the fabrication of liquid core microcapsules via oil‐in‐water interfacial polymerization with diethylenetriamine as crosslinker. The particles obtained were in the size range of 10–90 µm in diameter independent of the composition of copolymer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2698–2705     

Grafting of polymers onto a carbon‐fiber surface by ligand‐exchange reaction of poly(vinyl ferrocene‐co‐vinyl monomer) with polycondensed aromatic rings of the surface

To improve the surface of carbon fiber, the grafting reaction of copolymer containing vinyl ferrocene (VFE) onto a carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber was investigated. The copolymer containing VFE was prepared by the radical copolymerization of VFE with vinyl monomers, such as methyl methacrylate (MMA) and styrene, using 2,2′‐azobisisobutyronitrile as an initiator. By heating the carbon fiber with poly(VFE‐co‐MMA) (number‐average molecular weight: 2.1 × 10⁴) in the presence of aluminum chloride and aluminum powder, the copolymer was grafted onto the surface. The percentage of grafting reached 46.1%. On the contrary, in the absence of aluminum chloride, no grafting of the copolymer was observed. Therefore, it is considered that the copolymer was grafted onto the carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber. The molar number of grafted polymer chain on the carbon‐fiber surface decreased with increasing molecular weight of poly(VFE‐co‐MMA) because the steric hindrance of grafted copolymer on the carbon‐fiber surface increases with increasing molecular weight of poly(VFE‐co‐MMA). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1868–1875, 2002