Preparation and Thermo-Responsive Properties of Poly(Oligo(Ethylene Glycol)Methacrylate)Copolymers with Hydroxy-Terminated Side Chain

Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.

Polybutylacrylate/poly(methyl methacrylate) Core-Shell Elastic Particles as Epoxy Resin Toughener: Part I Design and Preparation

Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.

SYNTHETIC STUDIES ON BLOOD COMPATIBLE BIOMATERIALSⅡ. SYNTHESIS OF POLY(ETHYLENEGLYCOL MONOMETHYLLTHER ) METHACRYLATE AND ANTITHROMBOGENICITY OF ITS COPOLYMERS

Poly （ethyleneglycol monomethylether） methacrylate （PEGMM）was synthesized by means of the reaction of methacrylyl chloride with sodium monomethylpolyethyleneglycoxide and was characterized by FTIR,;H-NMR,and ultraviolet spectrometries. A series of poly （vinyl alcohol）-graft-PEGMM （PVA-g-PEGMM ）and methyl methacrylate-PEGMM copolymer （PMMA-PEGMM） were prepared and tested for antithrombogenicity in vitro. The results indicate that the antithrombogenicity of the copolymers basically increases with the increasing of the DP of polyoxyethylene （POE） chain and tends to a plateau after the DP around 114,i.e. the long chain structure of POE is favourable to the antithrombogenicityof its copolymers ;moreover, the extent of the improvement ofantithrombogenicity also relates to the PEGMM content of the copolymers and the kind of the matrix that the POE chains are located on. These results are consistent with the anticipation of the hypothesis of maintaining proteins normal conformations for blood compatible bioraaterials.

AN ATOMIC FORCE MICROSCOPY STUDY ON THE AGGREGATION OF ISOTACTIC POLY(METHYL METHACRYLATE)

Aggregation process of isotactic poly（methyl methacrylate） （i-PMMA） has been studied extensively for many years, and considerable progress has been made in both experimental and theoretical studies. They are, however, seldom sustained by real-space observations of the underlying morphology. In this paper, the aggregation process of i-PMMA in concentrated acetone solutions and the fractal structure of the resulting three-dimensional clusters were characterized on the basis of real-space AFM observations of their two-dimensional projection. It was found that spherical multiple-chain particles formed upon collapse and aggregation of the involving chains as a whole during quenching the solution to room temperature. By keeping the solution at room temperature, the initially formed particles stick together upon contact to form larger particles through reassembling very slowly. The succeeding collision of the enlarged spherical particles leads to the formation of small clusters. These newly formed small clusters grow when they meet with other clusters or single Brownian particles. This leads to the formation of large clusters with fractal dimension of 1.95 ± 0.05, which suggest a reaction-limited cluster aggregation of i-PMMA in a concentrated acetone solution. This is in accordance with the conclusion obtained by light scattering measurements.

PREPARATION OF POLY(METHYL METHACRYLATE)/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate intercalated LDHs（MgAl-VBS LDHs）. MgAl-VBS LDHs was prepared by the ion exchange method, and the structure and composition of the MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy and elemental analysis. XRD and transmission electron microscopy （TEM） were employed to examine the structure of LDHs/PMMA nanocomposite. It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix. The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.

Synthesis of Comblike Poly(methyl methacrylate) by Atom Transfer Radical Polymerization with Poly(ethyl 2-bromoacrylate) as Macroinitiator

Comblike poly(methyl methacrylate) was synthesized by atom transfer radical polymerization of methyl methacrylate with poly(ethyl 2-bromoacrylate) as a macroinitiator, which was prepared by conventional free radical polymerization of ethyl 2-bromoacrylate. The obtained comblike polymers were characterized by GPC and 1H NMR.

Effect of Low-Pressure Nitrogen DC Plasma Treatment on the Surface Properties of Biaxially Oriented Polypropylene, Poly (Methyl Methacrylate) and Polyvinyl Chloride Films

In this study, commercial biaxially oriented polypropylene （BOPP）, polyvinyl chlo- ride （PVC） and poly （methyl methacrylate） （PMMA） films were treated with nitrogen plasma over different exposure times in a Pyrex tube surrounded by a DC variable magnetic field. The chemi- cal changes that appeared on the surface of the samples were investigated using Fourier transform infrared （FT4R） spectroscopy and attenuated total reflectance Fourier transform infrared （ATR- FTIR） spectroscopy after treatment for 2 min, 4 min and 6 rain in a nitrogen plasma chamber. Effects of the plasma treatment on the surface topographies and contact angles of the untreated and plasma treated films were also analyzed by atomic force microscopy （AFM） and a contact angle measuring system. The results show that the plasma treated films become more hydrophilic with an enhanced wettability due to the formation of some new polar groups on the surface of the treated films. Moreover, at higher exposure times, the total surface energy in all treated films increased while a reduction in contact angle occurred. The behavior of surface roughness in each sample was completely different at higher exposure times.

Experimental and density functional theory computational evaluation of poly(N-vinyl caprolactam-co-butyl methacrylate) kinetic hydrate inhibitors

Natural gas hydrate inhibitor has been serving the oil and gas industry for many years. The development and search for new inhibitors remain the focus of research. In this study, the solution polymerization method was employed to prepare poly(N-vinyl caprolactam-co-butyl methacrylate)(P(VCap-BMA)), as a new kinetic hydrate inhibitor(KHI). The inhibition properties of P(VCap-BMA) were investigated by tetrahydrofuran(THF) hydrate testing and natural gas hydrate forming and compared with the commercial KHIs. The experiment showed that PVCap performed better than copolymer P(VCap-BMA). However,low doses of methanol or ethylene glycol are compounded with KHIs. The compounding inhibitors show a synergistic inhibitory effect. More interesting is the P(VCap-BMA)-methanol system has a better inhibitory effect than the PVCap-methanol system. 1% P(VCap-BMA) + 5% methanol presented the best inhibiting performance at subcooling 10.3 °C, the induction time of natural gas hydrate was 445 min.Finally, the interaction between water and several dimeric inhibitors compared by natural bond orbital(NBO) analyses and density functional theory(DFT) indicated that inhibitor molecules were able to form the hydrogen bond with the water molecules, which result in gas hydrate inhibition. These exciting properties make the P(VCap-BMA) compound hydrate inhibitor promising candidates for numerous applications in the petrochemical industry.

SYNTHESIS AND CHARACTERIZATION OF FOUR-ARMED BLOCK POLY(STYRENE-b-p-NITROPHENYL METHACRYLATE)PREPARED BY THE ATRP METHOD

A novel tetrafunctional initiator, C [CH_2O (CH_2)_3 OOCCH(Br)CH_3]_4 (1), was synthesized through the reaction oftetraol with α-bromopropionyl chloride, and then was used as initiator of atom transfer radical polymerization (ATRP) in thepreparation of 4-armed polystyrene (PSt) with narrow polydispersity. The structure, molecular weight and molecular weightdistribution (MWD) of each arm were studied by ~1H-NMR and GPC data of hydrolyzed products of the 4-armed PSt. TheATRP of St using 1/CuBr/bpy as initiator system is of 'living' character based on the following evidence: narrow MWD,constant concentration of chain radical during the polymerization, control of molecular weight by the molar ratio of monomerconsumed to 1. The 4-armed poly(St-b-p-nitrophenyl methacrylate) [poly(St-b-NPMA)] was prepared by the ATRP ofNPMA using 4-armed PSt with terminal bromine as the initiator, and characterized by FT-IR, ~1H-NMR spectra and GPCcurves. The micelles with PSt as core, and PNPMA as shell were formed by dropping DMSO into a solution of 4-armedpoly(St-b-NPMA) in DMF, as proved by laser light scatter (LLS) method.

Effect of Methyl Methacrylate– Acrylonitrile -Butadiene–Styrene (MABS) on the Mechanical and Thermal Properties of Poly (Methyl Methacrylate) (PMMA)-Fly Ash Cenospheres (FAC) Filled Composites

With the advent of plastics and the wide range of fillers that are available have made modifications as precise as the tailored resins themselves. To modify the properties of polymer either by using fillers or by preparation of polymer blends gives rise to new materials with tailored properties. More complex, three-component systems, obtained by the addition of polymeric modifier to polymer filled composites may be of interest. Use of Fly ash cenospheres is very attractive because it is inexpensive and its use can reduce the environmental pollution to a significant extent. In the present study, Poly (Methyl Methacrylate) (PMMA)-Fly ash cenospheres composites were prepared using extrusion followed by Injection molding. The effect of matrix modification with Methyl methacrylate– acrylonitrile -butadiene–styrene (MABS) on the performance of PMMA- Fly ash cenospheres compositions was also, studied. It was found that with the addition of Fly ash cenospheres particulate as filler in PMMA showed marginal reduction in Tensile Strength, % Elongation and Impact strength and improvement in Flexural Strength, Heat Deflection Temperature and Vicat Softening Point. Compared with PMMA-cenospheres composites, the notched Impact Strength of the PMMA/MABS/cenospheres composites showed marginal enhancement in values at higher loading of cenospheres. The optimum performances in mechanical and thermal properties were obtained when the ratio of MABS to cenospheres was 1:2.

Synthesis and Characterization of Novel Hybrid Poly(methyl methacrylate)/Iron Nanowires for Potential Hyperthemia Therapy

Externally applied magnetic fields have been used in this study to fabricate bamboo-like iron nanowires with or without a layer of Poly(methyl methacrylate) (PMMA). The hybrid PMMA/Fe nanowires were synthesized via hard X-ray synchrotron radiation polymerization with various treatment parameters. The results of XRD show that an oxide layer formed on the surface of the iron nanowires. The Fe2O3 and Fe3O4 phases coexist in the iron nanowires without X-ray irradiation. After X-ray irradiation, the Fe2O3 phase transformed into Fe3O4, which stabilized the iron nanowires. The results of XAS proved this phase transformation. TGA analysis confirmed the thermal properties and solid contents in these specimens. Their ferromagnetic behaviors were examined by magnetic hysteresis measurement, which indicated that the magnetic and structural properties of the nanowires can be manipulated by irradiation treatment. This may lead to a novel synthesis for iron nanowires that can be used in high thermal efficiency hyperthermia therapy.

Antibiotic-free antimicrobial poly (methyl methacrylate) bone cements:A state-of-the-art review

Prosthetic joint infection(PJI)is the most serious complication following total joint arthroplasty,this being because it is associated with,among other things,high morbidity and low quality of life,is difficult to prevent,and is very challenging to treat/manage.The many shortcomings of antibiotic-loaded poly(methyl methacrylate)(PMMA)bone cement(ALBC)as an agent for preventing and treating/managing PJI are well-known.One is that microorganisms responsible for most PJI cases,such as methicillin-resistant S.aureus,have developed or are developing resistance to gentamicin sulfate,which is the antibiotic in the vast majority of approved ALBC brands.This has led to many research efforts to develop cements that do not contain gentamicin(or,for that matter,any antibiotic)but demonstrate excellent antimicrobial efficacy.There is a sizeable body of literature on these socalled“antibiotic-free antimicrobial”PMMA bone cements(AFAMBCs).The present work is a comprehensive and critical review of this body.In addition to summaries of key trends in results of characterization studies of AFAMBCs,the attractive features and shortcomings of the literature are highlighted.Shortcomings provide motivation for future work,with some ideas being formulation of a new generation of AFAMBCs by,example,adding a nanostructured material and/or an extract from a natural product to the powder and/or liquid of the basis cement,respectively.

PREPARATION AND MECHANICAL PROPERTIES OF POLY(METHYL METHACRYLATE)/ URETHANE ACRYLATE COPOLYMERS

The urethane acrylate(UA) was made of poly(tetramethylenc oxide), 4,4’-diphenylmethane diisocyanate, and 2-hydroxyethyl methacrylate. A series of poly(methyl methacrylate) / urethane acrylate copolymers was prepared by using a redox initiating system. The copolymers had cross linked structures and two-phase morphologies as indicated by the results of the dynamic mechanical measurement and swelling test.

EFFECT OF TEMPERATURE ON COPOLYMERIZATION PARAMETERS OF HYDROXYETHYL ACRYLATE AND METHYL METHACRYLATE

The copolymerization of 2-hydroxyethyl acrylate (HEA, M//1) and methyl methacrylate (MMA, M//2) in cyclohexanone was studied. The multiple experiments of solution copolymerization with low conversion were carried out at two sensitive composition feed points at 60, 80, 100, 120 and 140 degree C, respectively. The composition of the copolymers was analyzed by **1H-NMR. The reactivity ratios which were estimated by the Error-in-Variable Method (EVM) of Mayo-Lewis equation were found to be r//1 equals 0.328, r//2 equals 1.781 for 60 degree C; 0.375, 1.709 for 80 degree C; 0.406, 1.654 for 100 degree C; 0.439, 1.540 for 120 degree C and 0.455, 1.400 for 140 degree C, and the 95% joint confidence intervals of the reactivity ratios were also determined. According to r//1 and r//2, Arrhenius relations and the activity energy difference between the homo- and cross-propagation were calculated. (Author abstract) 12 Refs.

STUDY ON METHANOLYSIS STABILITY OF OPTICALLY ACTIVE COPOLYMERS OF TRIPHENYLMETHYL METHACRYLATE AND METHYL METHACRYLATE

The methanolysis of poly(triphenylmethyl methacrylate) (PTrMA) and its copolymers P(TrMA-co-MMA), P(TrMA-b-MMA) has been studied in the presence of anhydrous methanol at 40 degrees C by electroconductometric method. It has been found that the methanolysis stability can be obviously improved for the copolymer, especially, the radom copolymer, P(TrMA-co-MMA).

PREPARATION OF LOW MOLECULAR WEIGHT POLY(GLYCIDYL METHACRYLATE) BY PHOTOPOLYMERIZATION

Low molecular weight poly（glycidyl methacrylate）s （PGMAs） were prepared by photopolymerization in ethyl acetate, with benzophenone （BP） as photoinitiator, and triethylamine （TEA） as hydrogen donor. The existence of semipinacol dormant end groups in PGMA was confirmed by FT-IR and ^1H-NMR, and the content of the semipinacol dormant groups was determined quantitatively by ^1H-NMR measurement. The effects of various thctors, such as reaction time, BP concentration and monomer concentration on the synthesis of the polymers were investigated systematically. The molecular weights of the polymers were also investigated with GPC. It is shown that increasing BP concentration and decreasing irradiation time and monomer concentration led to a significant decrease of the molecular weights.

MECHANICAL PROPERTIES OF CARBON/GLASS FIBER REINFORCED POLY(METHYL METHACRYLATE)COMPOSITES

Artificial bone, carbon/glass fiber reinforced PM-MA composites have been prepared by hot press moulding of pre-preg -which monofilments of CF and GF impregnated by MMA prepolymer. When the PMMA volume fraction in com-posites is 50% > theoretical and experimental results show that strength and modules of these hybrid composites are in accord with 'rule of mixture'. The tensile and flexure strength are the lowest when the raletive volume fraction of carbon fiber in rein-forcements is 50%,SEM examinations further explained re-sults.

Synthesis and characterization of poly(methyl methacrylate-co-polyhedral oligomeric silsesquioxane)hybrid nanocomposites

A novel poly（methyl methacrylate-co-polyhedral oligomeric silsesquioxane） hybrid nanocomposite was synthesized by free radical polymerization and characterized by 1H NMR, 29Si NMR, and TGA technologies. Compared with PMMA homopolymer, the nanocomposite has better thermal stability.

EFFECTS OF ω-ACRYLOYL POLY (ETHYLENE OXIDE) MACROMONOMER ON EMULSIFIER-FREE EMULSI0N COPOLYMERIZATION OF METHYL METHACRYLATE AND n-BUTYL ACRYLATE

Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.

INTERACTION OF POLY(SODIUM SULFODECYL METHACRYLATE)WITH CETYLTRIMETHYL AMMONIUM BROMIDE IN AQUEOUS SOLUTION

The interaction of poly(sodium sulfodecyl methacrylate) (PSSM) with cetyltrimethyl ammonium bromide (CTAB)was studied. It was found that the precipitate formed from PSSM and CTAB will be dissolved by excessive CTAB, resultingin the appearance of two maxima of the solution viscosity at the molar ratio (CTAB/-SO_3^-) of≈ 0.68 and≈1.30,respectively. The first one is related closely to the aggregation of polymer chains via CTAB molecules and the second oneshould be ascribed to the formation of the mixed micelles comprising surfactant and the polymer's hydrophobic chains. Theeffect of NaCl on the viscosity, the transmittance of the aqueous solution and the solubility of oil-soluble dye (dimethyl yellow) in the mixed system were also investigated.