Synthesis and characterization of bulky side chain methacrylate polymers

The synthesis, and dilute solution behavior of poly(2,4-dimethylphenyl methacrylate) (2,4DMP), poly(2,5-dimethylphenyl methacrylate) (2,5DMP), and poly(3,5-dimethylphenyl methacrylate) (3,5DMP) is described. Comparison is made with results reported for other bulky side chain polymers. The Kuhn-Mark-Houwink-Sakurada (KMHS) relationships were established. The unperturbed dimensions 〈r²〉 ${}_{\text{½}}^{\text{0}}$ , the rigidity factor σ, the characteristic ratio C_∞, and the thermodynamic parameters were determined, using the Stockmayer-Fixman equation, from viscometric data in good solvents. The high rigidity observed for these polymers is explained assuming that these polymers behave as kinked-chains.     

Cyclolinear organosilicon copolymers with monocyclic fragments in the side chain

The reaction of heterofunctional condensation of organodichlorosiloxycyclotri(tetra, penta) siloxanes and organodichlorosililcarbocyclotrisiloxane with dihydroxydimethylsiloxanes in the presence of pyridine was investigated. It was shown that at small lengths of the linear dimethylsiloxane link (n ≤ 4) the reaction of heterofunctional condensation runs both intermoleculary with formation of polymers and intramoleculary with formation of bicyclo‐organosiloxanes. It was established that insertion of cyclic fragments in the side chain hinders the chain transfer reactions that proceed with release of the D‐type cycles during thermal depolymerization. The conformational and hydrodinamic properties of some polymethylsiloxane copolymers with cyclosiloxane fragments in the side chain have been studied. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 583–594, 1999     

Synthesis,modification, and porous properties of new glycidyl methacrylate copolymers

Synthesis, copolymerization, and physicochemical properties of new, of different degrees of crosslinker tetrafunctional bis[4(2‐hydroxy‐3‐methacryloyloxypropoxy)phenyl]sulfide and glycidyl methacrylate copolymers are presented. The monomers were used for the synthesis of porous microspheres in the presence of pore‐forming diluents, decan‐1‐ol, and toluene. Influence of diluents composition on their porous structures was studied. Porous structure of the obtained microspheres in dry (from nitrogen adsorption–desorption measurements) states was studied. Their chemical structures were studied by the use of Fourier transform infrared. The number of epoxy groups of the obtained copolymers, their thermal properties (thermogravimetric analysis), and swelling characteristics in 10 solvents of different chemical nature were examined. Selected copolymers were modified by amines in the epoxide ring‐opening reaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.     

Crosslinking reaction of glycidyl methacrylate copolymers containing oxime-urethane groups using photogenerated pendant amines

Summary Copolymers containing epoxy and oxime-urethane groups were prepared by copolymerization of glycidyl methacrylate (GMA) and benzophenone oxime allylurethane (BAU). The physical properties of these copolymers were characterized by GPC, NMR and DSC analyses. Photo-crosslinking reaction of the copolymers were studied by measuring the insoluble fraction of copolymer films under various reaction conditions. The degree of cross-linking reaction increased with irradiation time, heating temperature and the amount of BAU units in the copolymer. UV and IR absorption spectral studies indicate that thermal cross-linking reaction of the copolymer was catalyzed by the pendant photogenerated amines. Received: 3 March 1998/Revised version: 7 April 1998/Accepted: 15 April 1998     

Pyrolysis/gas chromatography/mass spectrometry of glycidyl methacrylate—alkyl acrylate copolymers

Thermal degradation pattern of copolymers of glycidyl methacrylate with alkyl acrylates have been studied by pyrolysis/gas chromatography/mass spectrometry method. Various degradation products have been identified and based on the products obtained, the mechanisms of polymer degradation have been elucidated.     

Monodisperse microspheres of copolymers of glycidyl methacrylate and its derivatives as materials for biomedical application

Monodisperse microspheres of copolymers of glycidyl methacrylate were prepared by dispersion polymerization in organic media. The microsphere diameter could be adjusted in the range from 0$md$5 μm to 5μm by changing the monomer concentration, the type of dispersion medium and the content of the comonomers. Terpolymers of glycidyl methacrylate, 2-hydroxyethyl methacrylate and tri(ethylene glycol) dimethacrylate were analysed by thermal decomposition gas chromatography and the compositions of the polymers agreed well with those of the monomer mixtures. The epoxide of the polymer microspheres was hydrolysed to α,β-diol with dilute sulphuric acid without side reactions except the slight formation of sulphate. It was confirmed by the ¹³CFT-NMR spectrum that the main structure of the hydrolysate was that of poly(glyceryl methacrylate). In the reaction of the epoxide with ammonia, the predominant production of tertiary amine was presumed by the relationship between the conversion of the epoxide and the nitrogen content of the reaction product. The amination of the epoxide with secondary amines resulted in the quantitative formation of the corresponding tertiary amines.     

Incorporation of terpyridine into the side chain of copolymers to create multi-functional materials

Polymer architectures containing metal-ligands in their side chain represent a diverse approach to generating multi-functional materials. The ability to define a versatile synthetic platform will enable many chemistries and architectures to be studied. This report describes our latest efforts to prepare these unique polymers by either a direct polymerization of functionalized monomers or a post-polymerization attachment. Random and block copolymers have been successfully prepared. Subsequent functionalization with metal ions leads to a variety of properties including metal induced gelation and solvochromic sensors.     

Functional copolymers of p‐cumyl phenyl methacrylate and glycidyl methacrylate: Synthesis,characterization, and reactivity ratios

Free‐radical polymerization of p‐cumyl phenyl methacrylate (CPMA) was performed in benzene using bezoyl peroxide as an initiator at 80°C. The effect of time on the molecular weight was studied. Functional copolymers of CPMA and glycidyl methacrylate (GMA) with different feed ratios were synthesized by free‐radical polymerization in methyl ethyl ketone at 70°C, and they were characterized by FTIR and ¹H‐NMR spectroscopy. The molecular weights and polydispersity indexes of the polymers and copolymers were determined by gel permeation chromatography. The copolymer composition was determined by ¹H‐NMR. The glass‐transition temperature of the polymer and the copolymers was determined by differential scanning calorimetry. The reactivity ratios of the monomers were determined by the Fineman–Ross and Kelen–Tudos methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 336–347, 2005     

Synthesis and characterization of binary copolymers of methyl methacrylate with glycidyl methacrylate and 2‐hydroxy ethyl methacrylate as carriers for cellulase

Cellulase was immobilized directly on methyl methacrylate‐glycidyl methacrylate copolymer (MMA‐co‐GMA) and methyl methacrylate‐2‐hydroxy ethyl methacrylate copolymer (MMA‐co‐HEMA) by covalent attachment and crosslinking methods. The properties of the immobilized cellulase were investigated and compared with those of the free one. For the assays carried out through crosslinking method at 25°C and pH 7, the retained activities were found to be 91.92% and 74.63%, respectively, for MMA‐co‐GMA and MMA‐co‐HEMA crosslinked with 0.1% of 1‐cyclohexyl‐3‐(2‐morpholino‐ethyl) carbodiimide metho‐p‐toluenesulfonate (CMCT), respectively. The immobilized cellulase had better stability and higher retained activities with respect to pH, temperature, and storage stability than the free one. In the repeated use experiments, the immobilized cellulase using (MMA‐co‐GMA)‐CMCT (0.1%) and (MMA‐co‐HEMA)‐CMCT (0.1%) did not change after 10 and eight times of repeated use and maintained 67% and 62% from their original activities after 25 times, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Viscoelastic properties of (cellulose oligo-oxymethylene ether) acylates with bulky side chain

A series of (cellulose oligo-oxymethylene ether) acylates (COAs) are characterized by the presence of the micro-Brownian motion of the side chain (β process) which appears separately from that of the main chain (α process). Both the alpha; and β processes are largely affected by the kind of acyl groups introduced in the side chain. To clarify the effect of the acyl group on these processes, we investigated the dynamic mechanical properties of newly prepared COAs with acyl side chain, bulky in chemical structure (iso-butyrate, privalate, and benzoate) in relation to those for COAs with linear acyl side chain (acetate, butyrate, and valerate). By substituting bulky acyl isomer for linear acyl group in COAs, we observed that the temperature region of both the α and β processes moved to higher temperature. Furthermore, with an increase in molecular size of bulky acyl group, the β region shifts were much larger than the α region, indicating that the mobility of the side chain became comparable to that of the main chain. Finally, when such a large bulky group, for example, benzoate was introduced, the micro-Brownian motion of the side chain prior to that of the main chain ceased. The apparent activation energy for a third process (γ) due to the motion of the oligo-oxymethylene parts in the side chain was estimated to be 10.3 kcal/mol.     

Laser irradiation of oligosiloxane copolymer thin films functionalized with side chain bulky carbosilane moieties

Linear oligosiloxanes functionalized with bulky side chain tris(trimethylsilyl)hexyl (TTSH) substituents were transformed into cross-linked materials by UV 193 nm excimer pulsed laser ablation. The process occurred without any catalyst, by reactions of radicals formed in UV laser induced photolysis of side tris(trimethylsilyl)hexyl groups. Chemical changes were monitored by FTIR, LC/UV, GC/MS and solubility tests.     

Synthesis,characterization and thermal properties of homo and copolymers of 3,5-dimethoxyphenyl methacrylate with glycidyl methacrylate: Determination of monomer reactivity ratios

The new methacrylic monomer, 3,5-dimethoxyphenyl methacrylate (DMOPM) was synthesized by reacting 3,5-dimethoxyphenol dissolved in ethyl methyl ketone (EMK) with methacryloyl chloride in presence of triethylamine as a catalyst. The homopolymer and copolymers of DMOPM with glycidyl methacrylate (GMA) were synthesized by free radical polymerization in EMK solution at 70 ± 1 °C using benzoyl peroxide as a free radical initiator. The copolymerization behaviour was studied in a wide composition interval with the mole fractions of DMOPM ranging from 0.15 to 0.9 in the feed. The homopolymer and the copolymers were characterized by FT-IR, ¹H NMR and ¹³C NMR spectroscopic techniques. The solubility was tested in various polar and non-polar solvents. The molecular weight and polydispersity indices of the polymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in DMOPM content. The thermogravimetric analysis of the polymers showed that the thermal stability of the copolymer increases with DMOPM content. The copolymer composition was determined using ¹H NMR spectra. The monomer reactivity ratios were determined by the application of conventional linearization methods such as Fineman–Ross (r₁ = 0.520, r₂ = 2.521), Kelen–Tudos (r₁ = 0.629, r₂ = 2.554) and extended Kelen–Tudos methods (r₁ = 0.600, r₂ = 2.502).     

Reactive polymers,XXVII. Kinetics of chemical reactions of metal ions with functional groups of glycidyl methacrylate — ethylenedimethacrylate copolymers modified by ethylenediamine

The conditions were followed which influence the rate of uptake of Cu(II) and Ag(I) ions by a copolymer of glycidyl methacrylate with ethylene dimethacrylate modified by ethylenediamine. In addition to the particle size (0.1–1 mm) of the chelating resin, the concentration of cations in solution affects substantially the rate of sorption. It follows from the calculated rate of diffusion and from the rate constants of the chemical reaction that the reaction kinetics is decisive for particles below 0.1 mm, whereas with increasing particle size the inner diffusion begins to play a more important role and becomes finally the rate-determining mechanism. The obtained results are supported by observations of morphology.     

含聚氧乙烯支链的两亲性(丙烯酸丁酯-甲基丙烯酸甲酯)接枝共聚物的性能

由聚氧乙烯(PEO)大单体与丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)合成含PEO支链的两亲性(BA-MMA)三元接枝共聚物,对该共聚物的乳化性、吸水性和物理机械性能进行了研究.结果表明,合成的共聚物具有良好的乳化性及吸水性,并在一定组成下呈现热塑性弹性体的性质.     

Kinetic model of block photopolymerization of glycidyl methacrylate to high conversion

The kinetics of glycidyl methacrylate block polymerization to high conversion was experimentally investigated with variations of the photoinitiator concentration, temperature, and power of UV illumination. The kinetic curves of this polymerization process contain three characterized sections of coordinates of “conversion–time,” namely: The first one is practically linear to a conversion of ≈0.5, the second represents, by itself, the autoacceleration process, and the third presents the autodecelation process. An additional peculiarity of such a polymerization process is poor reproduction of the kinetic measurements. This reproduction does not correspond to instrumental error. Derivation of a kinetic model for block linear polymerization was done. This model is, quantitatively, in good agreement with all the data of the experimental material. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3556–3569, 2002     

Polymer blends of poly(trimethylene terephthalate) and polystyrene compatibilized by styrene‐glycidyl methacrylate copolymers

The compatibilizing effects of styrene‐glycidyl methacrylate (SG) copolymers with various glycidyl methyacrylate (GMA) contents on immiscible blends of poly(trimethylene terephthalate) (PTT) and polystyrene (PS) were investigated using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and ¹³C‐solid‐state nuclear magnetic resonance (NMR) spectroscopy. The epoxy functional groups in the SG copolymer were able to react with the PTT end groups (? COOH or ? OH) to form SG‐g‐PTT copolymers during melt processing. These in situ–formed graft copolymers tended to reside along the interface to reduce the interfacial tension and to increase the interfacial adhesion. The compatibilized PTT/PS blend possessed a smaller phase domain, higher viscosity, and better tensile properties than did the corresponding uncompatibilized blend. For all compositions, about 5% GMA in SG copolymer was found to be the optimum content to produce the best compatibilization of the blend. This study demonstrated that SG copolymers can be used efficiently in compatibilizing polymer blends of PTT and PS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2247–2252, 2003     

Mechanical and dielectric properties of bulky side chain poly(methacrylates). Analysis of the low frequency phenomena. 1: Poly(5-indanyl methacrylate)

This paper composes the dynamic mechanical and dielectric relaxation properties for Poly (5-indanyl methacrylate) (P51M), a polymer with a bulky side chain. Measurements were carried out from about ?100°C to near 250°C. A secondary loss peak was observed in dielectric measurements at room temperature (20°C at 0.1 Hz.), whereas nothing was resolved in the mechanical spectrum. A prominent α relaxation associated with the glass transition was also observed near 107°C at 0.1 Hz. in the dielectric and the mechanical spectra. Dipolar dielectric loss overlapped with conductivity at high temperatures and low frequencies. A new method to split the conductive, interfacial, and dipolar contributions to the spectrum is proposed.     

Effect of side chain substituents on the electron injection abilities of unsymmetrical perylene diimide dyes

Three near-infrared (NIR) absorbing unsymmetrical perylene diimide D-A-D type dyes containing 6-undecanoxy as donor group were utilized in dye-sensitized nanocrystalline TiO₂ solar cells. Structure of the acceptor side of the molecules were improved by adding 4-[2-methyl-5-(cyanoacrylic acid)-3-thienyl]-phenyl (V), 3-carboxy-2-pyridil (VI) and 3-carboxy-2-pyrazyl (VII) moieties attached to one of the N-side of the dye. The relationship between the molecular structure of the acceptor sites of the dyes and the photovoltaic performances were discussed. Electrochemical measurements indicated that band gaps of the dyes were energetically favorable for electron injection from the excited state of the dyes to the conduction band of TiO₂ nanoparticles. However, three dyes gave lower conversion efficiency on DSSC applications. Strong electron-withdrawing nature of perylene core might not permit to transfer the photo-generated electrons to the carboxyl groups anchoring to TiO₂ surface, and then solar-to-electricity conversion efficiencies of the dyes were reduced.     

Styrene maleic anhydride and styrene glycidyl methacrylate copolymers as in situ reactive compatibilizers of polystyrene/nylon 6,6 blends

The reactive type copolymers styrene maleic, anhydride (SMA) and styrene glycidyl methacrylate (SG) are used as in situ compatibilizers in polyblends of polystyrene (PS) and nylon 6, 6 (N66). Both copolymers can react with N66 to form copolymers as effective compatibilizers to reduce interfacial tension and increase phase adhesion. However, the toughness of the compatibilized blends is significantly lower than of the corresponding noncompatibilized blends. Only a small fraction of SMA is actually reacted in a typical melt blending, and SG copolymer seems to be more reactive than SMA. The unreacted copolymers are expected to be distributed mostly in the PS phase because of their structural similarity. The reacted copolymers are not exclusively distributed along the interface; some may distribute in both matrices. SMA is known as a very brittle polymer, and the way it is distributed can greatly influence the toughness of the resulting blends. PS is also very brittle relative to N66, and moreover a high amount of SMA in the N66 phase is detrimental since N66 is responsible for the toughness of PS/N66 blends. The better compatibilized blends have the tendency to bring more SMA and reacted SMA into the N66 phase. The relative detrimental effect on the inherent toughness of N66 is much more severe than in case of PS, if they contain the same amount of SMA. This study demonstrates that polyblends with good compatibilizers do not guarantee toughness improvement. The way the compatibilizers affect the inherent properties of the matrix needs also to be taken into consideration.