Biodegradability of poly(vinyl acetate) containing a pyridinium group

An attempt has been made to give biodegradability to poly(vinyl acetate) by partial modification of the chemical structure. Poly(vinyl acetate) containing a small amount of N-benzyl-4-vinylpyridinium chloride (PVAc-co-VPC) and that containing 16 mol % of methyl acrylate and a small amount of the pyridinium group (PVAc-co-MA-co-VPC) showed significant degradation when placed in an aeration tank of sewage works. Control polymers possessed of no pyridinium group did not show significant degradation under these conditions, and the extent of weight reduction during the treatment increased with the content of the pyridinium group. The weight reduction exhibited an uppermost limit after 7 days of the treatment, and the pyridinium group disappeared from the polymer during the early period. Incorporation of the pyridinium group into poly(vinyl acetate) appeared to have improved the biodegradability. Gel permeation chromatographic analysis showed that the low molecular weight fraction was more easily degraded than was the high molecular weight fraction. In the degradation of PVAc-co-MA-co-VPC, the unit of methyl acrylate was more easily removed than that of vinyl acetate. © 1995 John Wiley & Sons, Inc.     

Impregnated concrete. I: Characterization of poly (methyl methacrylate) prepared in concrete matrices

Concrete specimens were impregnated with methyl methacrylate and after polymerization in situ, the extraction of polymer was carried out using appropriate solvents. The molecular weight and the stereochemical configuration of extracted polymer were determined by viscosity measurements and NMR spectroscopy respectively. The results obtained are discussed in relation to the increase of glass transition temperature of poly(methyl methacrylate) when the polymer is inside the concrete.     

Novel poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers through atom transfer radical polymerization

Poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers have been synthesized successfully through atom transfer radical polymerization of methyl methacrylate using telechelic bromo‐terminated polyurethane/CuBr/N,N,N,N″,N″‐pentamethyldiethylenetriamine initiating system. As the time increases, the number‐average molecular weight increases linearly from 6400 to 37,000. This shows that the poly methyl methacrylate blocks were attached to polyurethane block. As the polymerization time increases, both conversion and molecular weight increased and the molecular weight increases linearly with increasing conversion. These results indicate that the formation of the tri‐block copolymers was through atom transfer radical polymerization mechanism. Proton nuclear magnetic resonance spectral results of the triblock copolymers show that the molar ratio between polyurethane and poly (methyl methacrylate) blocks is in the range of 1 : 16.3 to 1 : 449.4. Differential scanning calorimetry results show T_g of the soft segment at ?35°C and T_g of the hard segment at 75°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of SBS/poly(styrene–methyl methacrylate) thermoplastic interpenetrating polymer network

SBS as polymer I, poly(styrene–methyl methacrylate) polymerized by atom transfer radical polymerization as polymer II, and a thermoplastic interpenetrating polymer network of SBS/poly(styrene–methyl methacrylate) were prepared by the sequential method. The effects of the polymerization temperature, the composition of the catalyst, the ratio of the monomers studied, and the kinetics at 90°C were also investigated. It was shown that when polymerization was initiated by a BPO/CuCl/bpy (BPO:CuCl:bpy = 1:1:3) system at 90°C, the mass averaged molecular weight of the poly(styrene–methyl methacrylate) increased with monomer conversion, and the polydispersities were kept very low. Fourier transform infrared spectroscopy and gel permeation chromatogram showed that poly(styrene–methyl methacrylate) with low polydispersities had been synthesized. Thus, a thermoplastic interpenetrating polymer network comprised of both narrow molecular‐weight‐distribution components was successfully prepared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2007–2011, 2003     

Synthesis of poly(vinyl acetate) containing diblock copolymer by DPE method

Diblock copolymer poly(methyl methacrylate)‐b‐poly(vinyl acetate) (PMMA‐b‐PVAc) was prepared by 1,1‐diphenylethene (DPE) method. First, free‐radical polymerization of methyl methacrylate was carried out with AIBN as initiator in the presence of DPE, giving a DPE containing PMMA precursor with controlled molecular weight. Second, vinyl acetate was polymerized in the presence of the PMMA precursor and AIBN, and PMMA‐b‐PVAc diblock copolymer with controlled molecular weight was obtained. The formation of PMMA‐b‐PVAc was confirmed by ¹H NMR spectrum. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) were used to detect the self‐assembly behavior of the diblock polymer in methanol. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Scission of the poly(methyl methacrylate‐co‐methacrylic acid) chain by excited‐state acridine

A photochemical reaction between acridine and poly(methyl methacrylate‐co‐methacrylic acid) (PMCA) was studied in benzene to build a recyclable polymer photodegradation system. The illumination of acridine in the presence of PMCA with 365‐nm light induced the bleaching of acridine and the degradation of PMCA. The average molecular weight of the degraded polymer decreased rapidly for the first 30 min of the photolysis. A nonvolatile product of this reaction was found to have a 2‐methyl‐2‐propenyl end group. The efficiency of the PMCA scission by this method was 30 times as large as that of poly(methyl methacrylate). These results suggest that an efficient photochemical polymer decomposition system can be built by adding the mixing process of a little methacrylic acid into the synthetic processes of general vinyl polymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1209–1212, 2005     

Surface properties for poly(perfluoroalkylethyl methacrylate)/poly(n-alkyl methacrylate)s mixtures

A poly(perfluoroalkylethyl methacrylate) and a series of poly(n-alkyl methacrylate)s such as poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate) were prepared and used to investigate the surface properties of polymer mixtures containing a fluorinated homopolymer and a nonfluorinated homopolymer and the effect of the side-chain length of poly(n-alkyl methacrylate) on the surface free energy for the polymer mixtures. Contact angles were measured for the surfaces of polymer mixtures by varying the concentration of poly(perfluoroalkylethyl methacrylate). From the contact angle data, it can be inferred that most of the poly(perfluoroalkylethyl methacrylate) added to poly(n-alkyl methacrylate)s is located in the outermost layer of polymer-mixture surface. Surface free energies for the outermost surfaces of polymer mixtures were calculated from the contact angle data using Owen and Wendt's equation. The decrease in the surface free energy for the polymer mixture with the poly(perfluoroalkylethyl methacrylate) addition is more pronounced as the side-chain length of poly(n-alkyl methacrylate) decreases. Due to the steric effect of the side chain of poly(n-alkyl methacrylate), the arrangement of the perfluoroalkylethyl group of poly(perfluoroalkylethyl methacrylate) to the air side is considerably hindered. The ESCA analysis of atomic compositions of the surface for the polymer mixture verified that poly(perfluoroalkylethyl methacrylate) is preferentially arranged and concentrates at the polymer mixture–air interface. The results of functional group compositions obtained by ESCA showed that the functional group composition of  CF₃ for the outermost layer has a more important effect on the surface free energy than that of  CF₂ and confirmed the hindrance of the arrangement of perfluoroalkylethyl group to the air side by the side chain of poly(n-alkyl methacrylate). © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(vinyl chloride‐co‐vinyl acetate)‐graft‐poly[(meth)acrylates] by atom transfer radical polymerization

The graft polymerization of methyl methacrylate and butyl acrylate onto poly(vinyl chloride‐co‐vinyl acetate) with atom transfer radical polymerization (ATRP) was successfully carried out with copper(I) thiocyanate/N,N,N′,N′,N″‐pentamethyldiethylenetriamine and copper(I) chloride/2,2′‐bipyridine as catalysts in the solvent N,N‐dimethylformamide. For methyl methacrylate, a kinetic plot of ln([M]₀/[M]) (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) versus time for the graft polymerization was almost linear, and the molecular weight of the graft copolymer increased with increasing conversion, this being typical for ATRP. The formation of the graft polymer was confirmed with gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The glass‐transition temperature of the copolymer increased with the concentration of methyl methacrylate. The graft copolymer was hydrolyzed, and its swelling capacity was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 183–189, 2005     

Well-defined poly(2-hydroxyethyl methacrylate) and its amphiphilic block copolymers via acidolysis of anionically synthesized poly(2-vinyloxyethyl methacrylate)

Summary A novel approach to a well-defined poly(2-hydroxyethyl methacrylate) [poly(HEMA)] and to its amphiphilic block copolymers was developed. The selective living anionic polymerization of the methacryloyl group of the bifunctional monomer 2-vinyloxyethyl methacrylate (VEMA) generated a functional polymer with a controlled molecular weight and a narrow molecular weight distribution (M_w/M_n= 1.05–1.09). This polymer is very stable under normal conditions. Being soluble in the common organic solvents, its characterization could be carried out easily. The unreacted vinyl groups in the side chains of the resulting polymer were further reacted with hydrochloric acid. This acidolysis changed poly(VEMA) to a well-defined poly(HEMA). In addition, the anionic block copolymerization of VEMA with styrene or methyl methacrylate also proceeded smoothly, generating the corresponding block copolymers. After acidolysis, these copolymers were turned into amphiphilic block copolymers containing a hydrophilic poly(HEMA) block. Received: 22 June 2001/Revised version: 15 August 2001/Accepted: 15 August 2001     

Synthesis of amphiphilic poly(methyl methacrylate)‐block‐poly(methacrylic acid) diblock copolymers by atom transfer radical polymerization

Atom transfer radical polymerization (ATRP) of 1‐(butoxy)ethyl methacrylate (BEMA) was carried out using CuBr/2,2′‐bipyridyl complex as catalyst and 2‐bromo‐2‐methyl‐propionic acid ester as initiator. The number average molecular weight of the obtained polymers increased with monomer conversion, and molecular weight distributions were unimodal throughout the reaction and shifted toward higher molecular weights. Using poly(methyl methacrylate) (PMMA) with a bromine atom at the chain end, which was prepared by ATRP, as the macro‐initiator, a diblock copolymer PMMA‐block‐poly [1‐(butoxy)ethyl methacrylate] (PMMA‐b‐PBEMA) has been synthesized by means of ATRP of BEMA. The amphiphilic diblock copolymer PMMA‐block‐poly(methacrylic acid) can be further obtained very easily by hydrolysis of PMMA‐b‐PBEMA under mild acidic conditions. The molecular weight and the structure of the above‐mentioned polymers were characterized with gel permeation chromatography, infrared spectroscopy and nuclear magnetic resonance. Copyright © 2005 Society of Chemical Industry     

Molecular weight fractionation of poly(methyl methacrylate) using Gas Anti-Solvent techniques

The solubility of poly(methyl methacrylate) in acetone, expanded by carbon dioxide, was studied at 20 °C for a variety of molecular weights and architectures. The suitability of the Gas Anti-Solvent method for fractionation of poly(methyl methacrylate) was investigated with positive results. The threshold pressure for precipitation of various monodisperse molecular weights was investigated, and the effectiveness of this technique to fractionate a polymer with a broad molecular weight distribution was evaluated. The pressure required to precipitate polymers was found to be low, generally below 60 bar.     

Water–ethanol permseparation by pervaporation through photocrosslinked poly(vinyl alcohol) composite membranes

Water–ethanol permselectivity was investigated by pervaporation through composite membranes which were prepared by coating photocrosslinkable poly(vinyl alcohol) containing pendant styrylpyridinium group (0.86–3.93 mol %) on porous films. These membranes were water-permselective, and the selectivity was dependent on the state of membranes; namely, incorporation ratio of styrylpyridinium group on poly(vinyl alcohol), molecular weight of the base polymer, coating thickness of a photopolymer, etc. Photocrosslinkable styrylpyridinium group showed, of course, the ionic character by a pyridinium moiety to work on permseparation of water effectively as well as preventing the dissolution of membranes by crosslinking. Membranes based on the higher molecular weight poly(vinyl alcohol) (P = 1700) gave the higher permselectivity of water in general than those of lower molecular weight (P = 500) one. Swelling of the polymers reached 160%, and permeation rate through the membranes increased with the increase of swelling. Selective diffusion of water was found to take place in swelling, and to play a part in the water-permseparation through the membranes.     

Miscibility of poly(vinylidene fluoride) and potassium salt of poly(methyl methacrylate-ran-methacrylic acid)

The crystalline–amorphous polymer pair of poly(vinylidene fluoride) and poly(methyl methacrylate) is known to be miscible over a wide composition range. The effects of ionic moieties on the miscibility were studied by replacing the poly(methyl methacrylate) with a series of random copolymers of methyl methacrylate and potassium salt of methacrylic acid. The interaction parameter (χ) for the miscible blends in their molten state was obtained by thermal analysis using a melting-point depression calculation. The parameter decreased to a minimum at c.2% ion content (χ=minus;0.514) and approached a positive value at above 10% ion concentration.     

The reinforcement of polystyrene and poly(methyl methacrylate) interfaces using alternating copolymers

Asymmetric double cantilever beam studies are presented that document the ability of alternating copolymers to strengthen a polymer/polymer interface. For polystyrene/poly(methyl methacrylate) interfaces, these results show that the alternating copolymer is the least effective sequence distribution of a linear copolymer at strengthening the polystyrene/poly(methyl methacrylate) interface, where the copolymers that are compared all have similar molecular weight and composition. The results also demonstrate that the effect of copolymer molecular weight on the ability of the copolymer to strengthen an interface is controlled by the balance between the increased entanglements and decreased miscibility of the copolymer with the homopolymers with increasing molecular weight.     

Modification of pristine multiwalled carbon nanotube by grafting with poly(methyl methacrylate) using benzoyl peroxide initiator

Multiwalled carbon nanotube was successfully grafted with poly(methyl methacrylate) by free radical mechanism using benzoyl peroxide initiator. The reaction was carried out in situ, where the initiator and methyl methacrylate monomer generated the polymer‐free radical that was subsequently grafted to the surface of the pristine multiwalled carbon nanotube. The multiwalled carbon nanotube grafted poly(methyl methacrylate) (MWCNT‐g‐PMMA) were characterized using Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, ¹³ C‐solid NMR spectroscopy, X‐ray photoelectron spectroscopy, and scan electron microscopy. From the result of the characterizations, the grafting of poly(methyl methacrylate) on to multiwalled carbon nanotube was confirmed, and a percentage grafting of 41.51% weight was achieved under optimized conditions with respect to the temperature and the amount of the initiator. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43270.     

Synthesis,structure, and thermal stability of poly(methyl methacrylate)‐co‐ poly(3‐tri(methoxysilyil)propyl methacrylate)/ montmorillonite nanocomposites

The structure and the thermodegradation behavior of both poly(methyl methacrylate)‐co‐poly(3‐tri(methoxysilyil)propyl methacrylate) polymer modified with silyl groups and of intercalated poly(methyl methacrylate)‐co‐poly(3‐tri(methoxysilyil)propyl methacrylate)/Cloisite 15A? nanocomposite have been in situ probed. The structural feature were comparatively studied by Fourier transform infrared spectroscopy (FTIR), ¹³C and ²⁹Si nuclear magnetic resonance (NMR), and small angle X‐ray scattering (SAXS) measurements. The intercalation of polymer in the interlayer galleries was evidenced by the increment of the basal distance from 31 to 45 Å. The variation of this interlayer distance as function of temperature was followed by in situ SAXS. Pristine polymer decomposition pathway depends on the atmosphere, presenting two steps under air and three under N₂. The nanocomposites are more stable than polymer, and this thermal improvement is proportional to the clay loading. The experimental results indicate that clay nanoparticles play several different roles in polymer stabilization, among them, diffusion barrier, charring, and suppression of degradation steps by chemical reactions between polymer and clay. Charring is atmosphere dependent, occurring more pronounced under air. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Graft copolymerization of methyl methacrylate from brominated poly(isobutylene‐co‐isoprene) via atom transfer radical polymerization

Commercial brominated poly(isobutylene‐co‐isoprene) (BIIR) rubber has been directly used for the initiation of atom transfer radical polymerization (ATRP) by utilizing the allylic bromine atoms on the macromolecular chains of BIIR. The graft copolymerization of methyl methacrylate (MMA) from the backbone of BIIR which was used as a macroinitiator was carried out in xylene at 85 °C with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as a catalytic complex. The polymerization conditions were optimized by adjusting the catalyst and monomer concentration to reach a higher monomer conversion and meanwhile suppress macroscopic gelation during the polymerization process. This copolymerization followed a first‐order kinetic behavior with respect to the monomer concentration, and the number‐average molecular weight of the grafted poly(methyl methacrylate) (PMMA) increased with reaction time. The resultant BIIR‐graft‐PMMA copolymers showed phase separation morphology as characterized by atomic force microscopy, and the presence of PMMA phase increased the polarity of the BIIR copolymers. This study demonstrated the feasibility of using commercial BIIR polymer directly as a macromolecular initiator for ATRP reactions, which opens more possibilities for BIIR modifications for wider applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43408.     

A study on the dissolution rate of irradiated poly(methyl methacrylate)

A detailed study of the factors affecting the dissolution rate of poly(methyl methacrylate), PMMA, showed that the magnitude of the increase in the dissolution rate of irradiated PMMA could not be entirely attributed to the reduction in the molecular weight, MW. The formation of non-polymeric volatile fragments by radiation exposure, i.e., CO, CO₂H₂, CH₃OH and CH₄ causes a large increase in the solvent flux into the polymer matrix, thereby causing a large increase in the dissolution rate of exposed PMMA. The volatilization of these low molecular weight fragments cause an increase in the “excess free volume” (microporosity) of the glassy PMMA. The relative magnitudes of the contribution of the MW reduction and the formation of volatile matter on the increase in the solubility rate of the irradiated polymer were found to depend on the molecular size of the solvent, and also on the enthalpy of mixing.     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

A novel method for preparing poly(alkyl methacrylates) and poly(methacrylic acids) of varying tacticity

In order to synthesize poly(methacrylic acid) and poly(alkyl methacrylates) over a wide range of polymer tacticity, the anionic polymerization of the following alkyl methacrylates (ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl, n-hexyl, n-octyl, n-decyl, n-lauryl, and n-octadecyl) in toluene using phenylmagnesium bromide initiation was studied. It was found that the amount of isotactic polymer structure generally decreased as the size of the ester group increased. In all cases, the polymers had greater than 50% isotactic triad structure. Whether the polymerization was carried out at 0° or ?78°C had little or no effect on the tacticity of the polymer produced. It was found that the poly(alkyl methacrylates) produced could be hydrolyzed in concentrated sulfuric acid to poly(methacrylic acid). The poly(methacrylic acid) produced in the hydrolysis could be esterified with diazomethane to give poly(methyl methacrylate) or with diazoethane to give poly(ethyl methacrylate) with the same tacticity as the poly(alkyl methacrylate) from which the poly(methacrylic acid) was derived. It is possible, therefore, to produce poly(alkyl methacrylates) of a desired tacticity by polymerizing the appropriate monomer, hydrolyzing, and reesterifying the resultant poly(methacrylic acid) with a diazoalkane to give the desired poly(alkyl methacrylate).