Branched poly(methyl methacrylates) modified by C60 fullerenes

The poly(methyl methacrylates) of branched structure with a covalently bonded fullerene were synthesized by three-dimensional radical polymerization of methyl methacrylate with triethylene glycol dimethacrylate or allyl methacrylate in toluene containing C₆₀. The kinetics of copolymerization of methyl methacrylate with multifunctional co-monomers in the absence of fullerene is compared with that in its presence. The physicochemical characteristics and thermal stability of the obtained copolymers are also compared. The electron spin resonance (ESR) method was applied to study the kinetics of accumulation of the fullerene radicals in the course of the (co)polymerization of methyl methacrylate.     

Symmetrical polymer systems prepared using a degradable bifunctional atom transfer radical polymerization initiator: Synthesis,characterization, and cleavage

Linear (co)polymers and dimethacrylate‐end‐linked polymer networks of methyl methacrylate with 2‐(dimethylamino)ethyl methacrylate, cleavable in the middle of the polymer chain, either under thermolysis or alkaline hydrolysis conditions, were prepared via atom transfer radical polymerization (ATRP) using a specially designed bifunctional degradable initiator. This initiator was 2,6‐pyridinediethanol di(2‐bromo‐2‐methyl propanoate) (PyDEDBrMeP), bearing two 2‐(pyridin‐2‐yl)ethyl ester moieties, known for their thermal and hydrolytic (alkaline conditions) lability. As a control, a more stable bifunctional ATRP initiator, 2,6‐pyridinedimethanol di(2‐bromo‐2‐methyl propanoate) (PyDMDBrMeP), was also synthesized together with the corresponding linear polymers and polymer networks prepared from it. Thermal or hydrolytic treatment of the polymers prepared using PyDEDBrMeP led to a reduction in the molecular weights of the linear polymers by a factor of two, and to the conversion of the polymer networks to soluble branched (star) structures, consistent with the expected cleavage of the initiator residue located in the middle of the polymer chain. Thermal treatment of the polymers prepared using PyDMDBrMeP did not affect their molecular weight due to the thermal stability of the (pyridin‐2‐yl)methyl ester group, while treatment under alkaline hydrolysis conditions resulted in complete cleavage, similar to the PyDEDBrMeP‐prepared polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2342–2355     

N‐Bromosuccinimide as a thermal iniferter for radical polymerization

N‐Bromosuccinimide (NBS) was used as a thermal iniferter for the initiation of the bulk polymerizations of methyl methacrylate, methyl acrylate, and styrene. The polymerizations showed the characteristics of a living polymerization: both the yields and the molecular weights of the resultant polymers increased linearly as the reaction time increased. The molecular weight distributions of the polymers were 1.42–1.95 under the studied conditions. The resultant polymers could be used as macroiniferters to reinitiate the polymerization of the second monomer. The copolymers poly(methyl methacrylate)‐b‐polystyrene and polystyrene‐b‐poly(methyl methacrylate) were obtained and characterized. End‐group analysis of the resultant poly(methyl methacrylate), poly(methyl acrylate), and polystyrene confirmed that NBS behaved as a thermal iniferter. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2567–2573, 2005     

Polymerization of methyl methacrylate and styrene in the presence of polyimides containing aliphatic moieties in the backbone

The radical homopolymerization of methyl methacrylate and styrene in the presence of polyimide that contains aliphatic moieties and is dissolved in the monomer is studied. The viscosity characteristics, heat resistances, and thermal stabilities of the resulting polymers and their solubilities in organic solvents are examined. It is found that the products of radical polymerization are polyimide-poly(methyl methacrylate) and polyimide-polystyrene copolymers, whose properties differ from those of the respective unmodified polymerization and polycondensation polymers.     

Thermal and photo induced reactions in blends of polypropylene and poly(methyl methacrylate)

Thermal Volatilization Analysis (TVA) demonstrates that poly(methyl methacrylate) (PMMA) is stabilized by blending with polypropylene (PP). Although well-defined radical reactions occur in both polymers under 2537 Å radiation, there is no evidence of the formation of block or graft copolymers when blends of the two are irradiated. Preirradiation suppresses the amount of monomeric methyl methacrylate formed on subsequent thermal degradation. The missing methyl methacrylate units appear in the chain fragment fraction. The characteristics of the thermal degradation of blends of unirradiated PP with preirradiated PMMA are similar to those of unirradiated rather than pre-irradiated blends, thus emphasizing the importance of the PP component in determining the thermal stability of blends after irradiation. These observations are discussed mechanistically.     

Study of photopolymer. XIX. Novel syntheses of the polymers with pendant ester and chloromethyl groups by addition reactions of the copolymer of glycidyl methacrylate with acid chlorides

Polymer with pendant cinnamic ester and chloromethyl groups was synthesized by the addition reaction of poly(glycidyl methacrylate–co–methyl methacrylate) (PGMA) with cinnamoyl chloride. Also, polymers with pendant benzoic esters and chloromethyl groups were synthesized by reaction of PGMA with the corresponding benzoyl chlorides. Furthermore, polymers with cinnamic or benzoic esters and alkylazide groups were prepared by the substitution reaction of the obtained polymers with sodium azide.     

Synthesis of inositol‐based star polymers through low ppm ATRP methods

The vitamin B₈‐based macroinitiator with six 2‐bromoisobutyric initiating sites was prepared for the first time by the transesterification reaction of meso‐inositol with 2‐bromoisobutyryl bromide. A series of six‐armed (co)polymers, containing hydrophilic poly(di(ethylene glycol) methyl ether methacrylate) and amphiphilic poly(di(ethylene glycol) methyl ether methacrylate)‐block‐poly(methyl methacrylate) as the arms and meso‐inositol as the core, were obtained by low ppm atom transfer radical polymerization (ATRP) methods, utilizing 30 ppm of catalyst complex. Under Fe⁰‐mediated supplemental activators and reducing agents ATRP, Cu⁰‐mediated supplemental activators and reducing agents ATRP, Ag⁰‐mediated activators regenerated by electron transfer ATRP, and simplified electrochemically mediated ATRP conditions, polymerization proceeded on to high conversion while maintaining low dispersity (?  = 1.05–1.16) giving well‐defined six‐armed star (co)polymers. ¹H NMR spectral results confirm the formation of new star‐shaped block (co)polymers. The absence of intermolecular coupling reactions during synthesis was confirmed by gel permeation chromatography analyses of the side chains of received star (co)polymers. These vitamin B₈‐based star (co)polymers may find biomedical applications as thermo‐sensitive drug delivery systems, biosensors, and tissue engineering solutions. Copyright © 2017 John Wiley & Sons, Ltd.     

“Clickable” polymers via a combination of RAFT polymerization and isocyanate chemistry

We describe a facile, one‐pot, two‐step polymerization towards synthesizing block co‐polymers bearing reactive isocyanate functional groups. Reversible addition fragmentation chain transfer (RAFT) polymerization is used to mediate the co‐polymerization of isocyanate‐bearing monomers dimethyl meta‐isopropenyl benzyl isocyanate (TMI) and 2‐isocyanatoethyl methacrylate (ICEMA) with styrene and methyl methacrylate (MMA), respectively. ICEMA was incorporated into the polymer at a faster rate than TMI and its unhindered isocyanate group was found to be more reactive than the hindered isocyanate group of TMI. Both the TMI/styrene and the MMA/ICEMA systems maintain the reactivity of the isocyanate functionality, which was exploited by attaching representative hydroxyl‐bearing small and large molecules as well as solid substrates to the block co‐polymers. Thus, we demonstrate the versatility of the block co‐polymer system as a basis for forming branched polymers or as grafts for a solid substrate. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Hydrophobic coatings from photochemically prepared hydrophilic polymethacrylates via electrospraying

Linear poly(hydroxyethyl methacrylate‐co‐methyl methacrylate) P(HEMA‐co‐MMA) and poly(dimehylaminoethyl methacrylate‐co‐methyl methacrylate) P(DMAEMA‐co‐MMA) and their corresponding hyperbranched copolymers were synthesized by conventional photoinitiated free radical polymerization and self‐condensing vinyl polymerization (SCVP) using Type I and Type II photoinitiators, respectively. Then, the polymers were processed by electrospraying in N, N‐dimethylformamide. The surface of the resulting electrospray coatings was examined by SEM, XPS, and WCA then compared with those prepared by drop casting. Regardless of the structural nature of the polymers, electrospraying allows the preparation of rough surface that shows more hydrophobic behavior. Electrospray coatings with linear and hyperbranched copolymers exhibited WCA as ～150° and ～130°, respectively, indicating that branching reduces the WCA. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1338–1344     

Resist polymers: Part IX—Thermolysis of chlorine-containing acrylate polymers

The thermal degradation of poly(chloroethyl methacrylate) (PCEMA), poly(trichloroethyl methacrylate) (PTCEMA), poly(methyl-α-chloroacrylate) (PMCA) and their copolymers with methyl methacrylate (MMA) has been investigated. Both ester decomposition and main chain scission occur for the chloroalkyl methacrylate polymers with the former playing the dominant role. In contradistinction, HCl elimination and aromatization prevail over other processes for PMCA. The thermolysis results are compared with radiolysis results.     

Polymeric Nitrofuran Derivatives. I. Radical-Initiated Homo- and Copolymerization of 5-Nitrofurfuryl Methacrylate

The radical homopolymerization of 5-nitrofurfuryl methacrylate (NFMA) and the copolymerization of NFMA with methyl methacrylate and various vinyl monomers, respectively, have been studied in dimethylformamide at 65°C. NFMA and poly(NFMA) have been characterized by ¹H-NMR, IR, and UV spectroscopy. The influence of polymerization conditions on monomer conversion and on the molecular weight of the polymers obtained has been investigated. The thermal behavior of the polymers obtained has been studied by TGA and DSC analysis.     

Thermal degradation of bromine-containing polymers: Part 11—Blends of poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) with poly(methyl methacrylate) and poly(methyl acrylate)

The products of degradation of blends of poly(2,3-dibromopropyl methacrylate) and poly(2,3-dibromopropyl acrylate) with poly(methyl methacrylate) and poly(methyl acrylate) are predominantly those to be expected from the degradation of the individual polymers. However, the appearance of methyl bromide and methanol from all four blends indicates that some interaction does occur across the phase boundary between the two constituent polymers. This is presumed to consist of the reaction of hydrogen bromide, formed by decomposition of the brominated polymers with the methyl groups of the acrylate and methacrylate polymers.     

具可调光学性质的富勒烯聚合物

聚（Ｃ６０ 甲基丙烯酸甲酯）与聚（Ｃ６０ 苯乙烯）的ＴＨＦ溶液的透射光谱随浓度的增大而不断红移．这种异常的光谱位移可能与富勒烯的纳级（１０－９）簇的形成有关．用简单的办法来“调改”一物质的性质是科学家们长期梦寐以求的，而含Ｃ６０的聚合物正代表了这一群新奇的物质，它们的光学性质可以预期地和可逆地调变，只要简单改变一下浓度．     

Synthesis,characterization, microstructure determination,thermal studies of poly (N-vinyl pyrrolidone-maleic anhydride-methyl methacrylate)

Synthesis of Poly (N-vinyl pyrrolidone-maleic anhydride-methyl methacrylate) terpolymer using azobisisobutyronitrile in 1,4-dioxan is described. The polymers with different composition were synthesized and characterized using FTIR, ¹HNMR, ¹³NMR, TGA and DSC techniques. The monomer-monomer interactions were studied using Finemann-Ross and Kelen-Tudos methods by calculating the reactivity ratio. The reactivity ratio r₁ and r₂ with respect to methyl methacrylate and N-vinylpyrrolidone-maleic anhydride complexomer are found to be 6.05 and 0.06 respectively. The study showed methyl methacrylate have higher reactivity than N-vinyl-2-pyrrolidone-maleic anhydride complex, i.e., the terpolymer contained methyl methacrylate in higher ratio. The thermal stability of poly (N-vinyl pyrrolidone-maleic anhydride-methyl methacrylate) was 165°C and the glass transition temperature was found to increase from 153°C to 182°C as MMA concentration increase. The studies indicate the activity of the polymer to inhibit bacterial growth is very poor.     

Photolabile carboxylic acid protected terpolymers for surface patterning. Part 1: Polymer synthesis and film characterization

We present the synthesis and characterization of a series of photolabile phenacyl derivative polymers and their subsequent thin film preparation. These systems are composed of up to three methacrylate units: a photolabile component including a p-methoxyphenacyl moiety which after selective irradiation (UV/laser) can provide free carboxylic groups in specific areas for further modification; an anchoring unit, trimethoxysiloxane or glycidyl methacrylate derivative, which allows the covalent attachment of the polymer to the substrate; and a spacer, methyl methacrylate or styrene, which in the appropriate proportion ensures the formation of films with good quality. Structural and thermal properties of these materials have been analyzed by means of NMR, FTIR, elemental analysis, UV, gel permeation chromatography, differental scanning calorimetry, and thermogravimetric analysis. The polymers have been subsequently processed by spin coating to render ultrathin films (<50 nm). Topographic and structural characterization studies of the films have been carried out with atomic force microscopy, contact angle measurements, and X-ray photoelectron spectroscopy. The extent of the substrate attachment of the polymers depending on the nature of the anchoring groups have been studied by ellipsometry and FTIR.     

Synthesis of a novel phosphate‐containing highly transparent PMMA copolymer with enhanced thermal and flame retardant properties

A novel poly(methyl methacrylate) (PMMA)‐based copolymer (PMMA‐co‐BDPA) rich in aromatic rings was synthesized via radical copolymerization between a phosphorus‐containing acrylic monomer (BDPA) and methyl methacrylate (MMA). UV‐vis spectroscopy demonstrated that the copolymer had high transparency. Thermogravimetric analysis (TGA) and a differential scanning calorimeter (DSC) were used to test the thermal properties of the composites. Additionally, the PMMA‐co‐BDPA‐15 copolymer exhibited a 23% increase in the limited oxygen index (LOI) value. A cone calorimeter test indicated that the peak heat release rate (pk‐HRR) of PMMA‐co‐BDPA was reduced by 29.2% compared with that of pure PMMA, and the carbon yield of burning was obviously increased. The combined test results demonstrated that the prepared copolymer material had good transparency, thermal stability, and flame retardancy.     

Studies on the thermotropic liquid crystalline polymer. XII. Synthesis and properties of crosslinkable thermotropic liquid crystalline homo- and copoly(ether-ester)s

A series of crosslinkable thermotropic liquid crystalline poly(ether-ester)s and copoly(ether-ester)s was prepared. All of the polymers were crosslinked by thermal treatment or photo-irradiation upon heating. The thermal stability and thermal crosslinking reaction of these polymers were investigated. These polymers also could be crosslinked by copolymerization with vinyl monomers, such as styrene or methyl methacrylate. The crosslinked polymers exhibited thermotropic liquid crystalline behavior after softening by heating. The phase behavior of linear polymers and crosslinked polymers was studied by differential scanning calorimetry (DSC) and an optical polarizing microscope equipped with a heating stage. © 1995 John Wiley & Sons, Inc.     

Uniform polyolefin and polymethacrylate

Preparations and properties of synthetic uniform polyolefins and polymethacrylates are described with emphasizing the necessity of their utilization for understanding the fundamental problems in polymer chemistry. Uniform polymer is a polymer composed of molecules uniform with respect to molecular weight and constitution. While classical organic chemistry provides means of constructing uniform polymers such as poly(methylene)s in stepwise manners, recent advances in separation technology such as supercritical fluid chromatography (SFC) have made it possible to isolate synthetic uniform polymers from its homologous mixture. Combinations of stereospecific polymerizations and the SFC technique have enabled us to prepare uniform polystyrenes and poly(methyl methacrylate)s with high stereoregularities, which are very useful for systematic studies on the nature of polymers. The thermal properties of these uniform polymers are discussed in some detail.     

Heat capacity of molten polymers

Heat capacities of molten polyethylene, polypropylene, poly-1-butene, polystyrene, and poly(methyl methacrylate) were measured over a wide range of temperature by using a differential scanning calorimeter. The upper limit of temperature was established for each polymer at about 10°K below the beginning of thermal decomposition. For poly-1-butene and poly(methyl methacrylate) the solid-state heat capacity was also measured starting from room temperature. Several samples of each polymer were used so that average values of heat capacities could be established (reported in 10°K intervals). The data revealed for all polymers a nearly linear increase of heat capacity with increasing temperature over the whole temperature range investigated.     

Precise Synthesis of New Triblock Co- and Terpolymers by a Methodology Combining Living Anionic Polymers with a Specially Designed Linking Reaction

Five A-B-A′, A-C-A′, B-A-B′, C-A-C′, and C-B-C′ triblock terpolymers with block orders difficult to synthesize by sequential polymerization have been successfully synthesized by a new methodology combining living anionic polymers with a specially designed linking reaction using α-phenylacrylate as the reaction site. Here, A(A′), B(B′), and C(C′) represent groups of polymers (having chain-end anions with different nucleophilicities), which are only polymerizable from A(A′) to B(B′) to C(C′) via sequential polymerization. The corresponding polymers are polystyrene (A) and poly(α-methylstyrene) (A′), poly(2-vinylpyridine) (B) and poly(4-vinylpyridine) (B′) and polymers from methacrylate type monomers like poly(methyl methacrylate) (C), poly(tert-butyl methacrylate) (C′), poly(2-hydroxyethyl methacrylate) (C′), poly(2,3-dihydroxypropyl methacrylate) (C′), and poly(ferrocenylmethyl methacrylate) (C′). Furthermore, three synthetically difficult B-A-B, C-A-C, and C-B-C triblock copolymers with molecular asymmetry in both side blocks have also been synthesized by the developed methodology. All of the polymers thus synthesized are quite new triblock terpolymers and copolymers with well-defined structures, i.e., precisely controlled molecular weights, compositions and narrow molecular weight distributions (M_w/M_n ≤ 1.05).