Poly(Glycidyl Methacrylates)-grafted Zinc Oxide Nanowire by Surface-initiated Atom Transfer Radical Polymerization

Poly(glycidyl methacrylates)(PGMA) was grafted from zinc oxide(ZnO) nanowires via surface-initiated atom transfer radical polymerization(SI-ATRP) technique.Firstly,the ZnO nanowires were synthesized by the one-pot hydrothermal technique.Subsequently,the ZnO was functionalized with 3-aminopropyl triethoxysilane,which was converted to macroinitiator by the esterification of them with 2-bromopropionyl bromide.PGMA grafted ZnO nanowires(PGMA-ZnO) were then synthesized in an ATRP of the GMA with CuCl/2,2`-bipyridine as the catalyst system.Kinetics studies revealed an approximate linear increase in weight of polymer with reaction time,indicating that the polymerization process owned some "living" character.The structure and composition of PGMA-ZnO were characterized with scanning electron microscope(SEM),energy-dispersive X-ray(EDX) spectrometer,fourier transform infrared spectroscopy(FT-IR) and thermogravimetric analysis(TGA).

SYNTHESIS OF LIQUID CRYSTALLINE ALKYLOXY BIPHENYL METHACRYLATES

The synthesis and liquid crystalline behaviour of a series of alkyloxy biphenyls were described.These includes 4-alkyloxy-4 -hydroxy biphenyls,p-alkyloxy biphenyl meth acrylytes,and the polymer of p-ethoxy biphenyl meth acrylate (PEBPMA).The effects of reaction conditions on the yields of products were investigated.The liquid crystalline behaviour of the products was characterized by DSC, polarizing microscopy..It was found that the PEBPMA showed smectic phase.

^(13)C NMR STUDIES ON DYNAMICS OF POLY (n - ALKYL METHACRYLATES)

The dynamics of a series of poly(n-alkyl methacrylates) is investigated by means of ^(13)C spin-lattice relaxation experiments. The results show that the dynamics has the polymer property dependence.

Evaluation of three-dimensional biofilms on antibacterial bonding agents containing novel quaternary ammonium methacrylates

Antibacterial adhesives are promising to inhibit biofilms and secondary caries. The objectives of this study were to synthesize and incorporate quaternary ammonium methacrylates into adhesives, and investigate the alkyl chain length effects on three-dimensional biofilms adherent on adhesives for the first time. Six quaternary ammonium methacrylates with chain lengths of 3, 6, 9, 12, 16 and 18 were synthesized and incorporated into Scotchbond Multi-Purpose. Streptococcus mutans bacteria were cultured on resin to form biofilms. Confocal laser scanning microscopy was used to measure biofilm thickness, live/dead volumes and live-bacteria percentage vs. distance from resin surface. Biofilm thickness was the greatest for Scotchbond control; it decreased with increasing chain length, reaching a minimum at chain length 16. Live-biofilm volume had a similar trend. Dead-biofilm volume increased with increasing chain length. The adhesive with chain length 9 had 37% live bacteria near resin surface, but close to 100% live bacteria in the biofilm top section. For chain length 16, there were nearly 0% live bacteria throughout the three-dimensional biofilm. In conclusion, strong antibacterial activity was achieved by adding quaternary ammonium into adhesive, with biofilm thickness and live-biofilm volume decreasing as chain length was increased from 3 to 16. Antibacterial adhesives typically only inhibited bacteria close to its surface; however, adhesive with chain length 16 had mostly dead bacteria in the entire three-dimensional biofilm. Antibacterial adhesive with chain length 16 is promising to inhibit biofilms at the margins and combat secondary caries.

POLYMERIC IONIC CONDUCTORS MODIFIED WITH POLAR GROUPS:PART Ⅰ. IONIC CONDUCTION AND MECHANICAL PROPERTY OF LI-COMPLEX BASED ON ACRYLAM ID E-COPOLYMERIZED METHACRYLATES

Acrylamide was introduced onto the chain of poly[oligo(oxyethylene) methacrylate] as a polar constituent, and the effect of its presence on the mechanical strength and ionic conduction properties of Li-salt complex based on the resultant copolymer was investigated. The introduction of the polar constituent raises chain rigidity, retards crystallization of oligo(oxyethylene) domain and promotes the dissociation of lithium salt. The factors work on the mechanical and conduction properties synergistically, therefore both of the properties are improved simultaneously as the consequence of acrylamide-introduction.

THE SYNTHESIS OF NEW POLED CROSSLINKED POLYMETHACRYLATES AND THEIR SECOND ORDER NONLINEAR OPTICAL PROPERTIES

Films were prepared from mixtures of copolymers of 4-nitro-4'-[N-methylacryloyloxyethyl, N'-ethyl] amino azobenzene with glycidyl methacrylate (chromophore content: 6 mol%) and copolymers containing anhydride units, which was obtained by the reaction of 4-nitro-4'-[N-hydroxyethyl, N'-ethyl] amino azobenzene with polymethacryloyl chloride (chromophore content: 25 mol %). During thermal poling process the anhydride reacts with the epoxy group and the resulting crosslinked network structure will stabilize the second harmonic generation in the poled film. The second harmonic generation of the poled film shows a maximum with the variation of composition this is presumed to be due to the effects of the increasing of concentration, orientation order as well as orientation stability of chromophore groups during crosslinking.

ANIONIC POLYMERIZATION OF ALKYL METHACRYLATES INITIATED BY nBuCu(NCy_2)Li

Anionic polymerization of methyl methacrylate (MMA), n-butyl methacrylate (nBMA) and glycidyl methacrylate (GMA) initiated by nBuCu(NCy2)Li (1) in tetrahydrofuran (THF) at -50 degrees C to -10 degrees C was investigated. It was found that the polymerization of MMA and nBMA initiated by 1 proceeded quantitatively in THF to afford PMMA and PBMA with polydispersity index 1.15-1.30 and nearly 100% initiator efficiencies at -10 degrees C. The molecular weights increased linearly with the ratio of [monomer]/[1]. However, a post-polymerization experiment carried out on this system revealed a double polymer peak by GPC when fresh monomer was added after an interval of 10 min. Polymerization of styrene could be initiated by 1, but the initiator efficiency was low.

POLYMERIC IONIC CONDUCTORS MODIFIED WITH POLAR GROUPS: PART Ⅱ. STRUCTURE-IONIC CONDUCTION RELATION IN LI-COMPLEX BASED ON MALEIC ANHYDRID E-COPOLYMERIZED METHACRYLATES

Ringlike polar monomer maleic, anhydride (MAn) was copolymerized with oligo (oxyethylene) methacrylate (MEO_n), and its effect on ion conduction property of the corresponding polymer-salt complexes was studied. As a consequence the introduction of MAn onto polymer chain retards crystallization of the ether pendants considerably, and improves the ion conductivity to a larger degree compared with other polar groups once investigated (σ_(max),25℃=8.5×10^(-5) S/cm). The structure-ion conduction relation in the polymer-salt matrix is also analyzed macroscopically through the correspondence between composition-dependences of polymerization conversion and isothermal ion conductivity, and microscopically through the measurements of cross polarized light and electron transmission.

Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs

Chemoselective,living/controlled polymerizations of allyl methacrylate(AMA) and vinyl methacrylate(VMA) with/without methyl methacrylate(MMA) by using the phosphonium ylide/organoaluminum based Lewis pairs(LPs) have been realized.The P-ylide-2/AIMe(BHT)_(2)(Pylide-2=Ph_(3)P=CHMe and BHT=2,6-iBu_(2)-4-MeC_(6)H_(2)O) was demonstrated to be superior by which homopolymers PAMAs(M_(n)=27.6-111.5kg/mol and ■=1.14-1.25) and PVMAs(M_(n)=28.4-78.4 kg/mol and ■=1.12-1.18) and block copolymers PMMA-b-PAMA,PAMA-b-PVMA,PAMA-bPMMA,PMMA-b-PAMA-b-PMMA,PAMA-b-PMMA-b-PAMA,and PAMA-b-PVMA-b-PAMA were synthesized.In the polymerizations,all of the monomers were reacted by the conjugated ester vinyl groups leaving intactly the nonconjugated acryloxy groups.The pendant acryloxy groups attached to the main chain enable further to post-functionalization by the AIBN-induced radical "thiol-ene" reaction using PhCH_(2)SH.The thiolether side group-containing polymers PAMA-SCH_(2)Ph and PAMA-SCH_(2)Ph-b-PMMA-b-PAMA-SCH_(2)Ph were thus prepared.

Development and characterization of 3D-printed electroconductive pHEMA-co-MAA NP-laden hydrogels for tissue engineering

Tissue engineering(TE)continues to be widely explored as a potential solution to meet critical clinical needs for diseased tissue replacement and tissue regeneration.In this study,we developed a poly(2-hydroxyethyl methacrylate-co-methacrylic acid)(pHEMA-co-MAA)based hydrogel loaded with newly synthesized conductive poly(3,4-ethylene-dioxythiophene)(PEDOT)and polypyrrole(PPy)nanoparticles(NPs),and subsequently processed these hydrogels into tissue engineered constructs via three-dimensional(3D)printing.The presence of the NPs was critical as they altered the rheological properties during printing.However,all samples exhibited suitable shear thinning properties,allowing for the development of an optimized processing window for 3D printing.Samples were 3D printed into pre-determined disk-shaped configurations of 2 and 10 mm in height and diameter,respectively.We observed that the NPs disrupted the gel crosslinking efficiencies,leading to shorter degradation times and compressive mechanical properties ranging between 450 and 550 kPa.The conductivity of the printed hydrogels increased along with the NP concentration to(5.10±0.37)×10^(−7)S/cm.In vitro studies with cortical astrocyte cell cultures demonstrated that exposure to the pHEMA-co-MAA NP hydrogels yielded high cellular viability and proliferation rates.Finally,hydrogel antimicrobial studies with staphylococcus epidermidis bacteria revealed that the developed hydrogels affected bacterial growth.Taken together,these materials show promise for various TE strategies.

Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance.The results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

Synthesis and Characterization of Poly Styrene-Co-Poly 2-Hydroxyethylmethacrylate (HEMA) Copolymer and an Investigation of Free-Radical Copolymerization Propagation Kinetics by Solvent Effects

A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The samples obtained from the synthesis were characterized by Fourier Transform-Infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H NMR), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). The results show that the synthesis of the polymers is more feasible under neat conditions rather than solvent directed reaction. Moreover, the DSC data shows that the polystyrene obtained is amorphous in nature and therefore displayed only a glass transition signal rather than crystallization and melting peaks. In addition, this study indicates that homolopolymerization of styrene via free radical polymerization tends to be preferable in less polar solvents like THF than in non-polar solvents like benzene. Benzene might destabilize the formation of the reactive radicals leading to the formation of the products. In summary, the homolpolymerization of styrene is more feasible than the homopolymerization 2-hydroxyethyl methacrylate under the experimental setup used. Styrene is more reactive than 2-hydroxyethyl methacrylate than free radical polymerization reaction due in part of the generation of the benzylic radical intermediate which is more stable leading to the formation of products than alkyl radical which are less stable. Furthermore, polymerization of styrene under neat conditions is preferable in solvent-assisted environments. The choice of solvent for the synthesis of these polymers is crucial and therefore the selection of solvent that leads to the formation of a more stable reaction intermediate is more favorable. It is worth noting that the structure of the proposed copolymer consists of a highly polar and hydrophilic monomer, 2-hydroxyethyl methacrylate and a highly non-polar and hydrophobic monomer, styrene. These functionalities constitute an amphiphilic copolymer with diverse characteristics. A plausible explanation underlying our observations is that the reaction conditions employed in the synthesis of these copolymers might not be the right route required under free radical polymerization.

Influence of Ca/P ratio on the catalytic performance of hydroxyapatite for decarboxylation of itaconic acid to methacrylic acid

Methacrylic acid,an important organic chemical,is commercially manufactured starting from fossil feedstock.The decarboxylation of itaconic acid derived for biomass is a green route to the synthesis of methacrylic acid.In view of the problems existing in the researches on this route such as use of noble metal catalyst,harsh reaction conditions and low desired-product yield,we prepared a series of hydroxyapatite catalysts with different Ca/P molar ratios and evaluated their catalytic performance.The results showed that the hydroxyapatite catalyst with a Ca/P molar ratio of 1.58 had the best catalytic activity.The highest yield of MAA up to 61.2%was achieved with basically complete conversion of itaconic acid under the suitable reaction conditions of 1 equivalent of NaOH,2 MPa of N_(2),250℃,and 2 h.On this basis,a reaction network for the decarboxylation of itaconic acid to methacrylic acid catalyzed by hydroxyapatite was established.With the aid of catalyst characterization using X-ray powder diffraction,NH3/CO2 temperature-programmed desorption,N_(2)physisorption,inductively coupled plasma optical emission spectrometry,and scanning electron microscopy,we found that the distribution of surface acid sites and basic sites,crystal growth orientation,texture properties and morphology of hydroxyapatite varied with the Ca/P molar ratio.Furthermore,the change of the crystal growth orientation and its influence on the surface acidity and alkalinity were clarified.

Cerium Methacrylate Assisted Preparation of Highly Thermally Conductive and Anticorrosive Multifunctional Coatings for Heat Conduction Metals Protection

Preparing polymeric coatings with well corrosion resistance and high thermal conductivity(TC)to prolong operational life and ensure service reliability of heat conductive metallic materials has long been a substantive and urgent need while a difficult task.Here we report a multifunctional epoxy composite coating(F-CB/CEP)by synthesizing cerium methacrylate and ingeniously using it as a novel curing agent with corrosion inhibit for epoxy resin and modifier for boron nitride through"cation-π"interaction.The prepared F-CB/CEP coating presents a high TC of 4.29 W m^(−1)K^(−1),which is much higher than other reported anti-corrosion polymer coatings and thereby endowing metal materials coated by this coating with outstanding thermal management performance compared with those coated by pure epoxy coating.Meanwhile,the low-frequency impedance remains at 5.1×10^(11)Ωcm^(2)even after 181 days of immersion in 3.5 wt%NaCl solution.Besides,the coating also exhibits well hydrophobicity,self-cleaning properties,temperature resistance and adhesion.This work provides valuable insights for the preparation of high-performance composite coatings with potential to be used as advanced multifunctional thermal management materials,especially for heat conduction metals protection.

Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor:Experimental and kinetic studies

The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor.The reaction was conducted in the temperature range of 323.15 to 368.15 K with the molar ratio of reactants from 0.8 to 1.4 under certain pressure.The measurement data were regression with the pseudo-homogeneous(P-H),Eley-Rideal(E-R),and Langmuir-Hinshelwood(L-H)heterogeneous kinetic models.Independent adsorption experiments were implemented to gain the adsorption equilibrium constants of four components.Among the above three models,the L-H model exhibited the best fitting results.The stability of NKC-9 was evaluated by long-term running with the yield of methyl methacrylate no decrease during 3000 h operation.The structure and physicochemical properties of the new and used catalyst were performed by several characterizations including thermogravimetric analysis(TG),scanning electron microscope(SEM),X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FT-IR)and so on.

Fabrication and Characterization of PMMA/MWCNTs Composite Materials

In order to improve the mechanical properties and thermal conductivity of polymethyl methacrylate(PMMA),multi-walled carbon nanotubes(MWCNTs)were used as reinforcement through in situ polymerization method to prepare PMMA/MWCNTs composites by changing the reaction time,polymerization temperature and the content of MWCNTs.The effects of different reaction conditions on the properties of the composites were studied.The results show that the mechanical properties,thermal/electrical conductivity and thermal stability of the composites are improved compared with the PMMA matrix.The tensile strength of the composites is increased by up to 24%.The bending strength of the composite material increases from20.41 to 68.04 MPa,and the maximum increase is 233%.Meanwhile,when the content of MWCNTs is 3 wt%,the thermal conductivity of the composite is 0.335 W/(m·K),which increases by138%,and the electrical conductivity is 3.94 S/m.The thermal stability of the composite has been significantly enhanced.The modified PMMA will be widely used in medicine,communications,electronics and other fields.

Surface Characterization and Tribology Behavior of PMMA Processed by Excimer Laser

Polyoxymethylene methacrylate (PMMA) is widely used in ophthalmic biomaterials. Misuse of PMMA in extreme environments is likely to damage the ocular surface and intraocular structures. The surface characterization and tribological behavior of PMMA processed using an excimer laser were investigated in this study by contrasting diferent lubrication conditions and friction cycles. The results show that the roughness of the material surface increases with laser processing, which changes its physical structure. Under lubrication, the laser-treated PMMA exhibits better hydrophilicity, especially during the use of eye drops. No obvious relationship exists between the laser-processing time and friction behavior. However, the laser treatment may contribute to the formation of friction and wear mechanisms of PMMA materials. Laser-treated PMMA in saline solution exhibits better abrasive resistance by showing a lower wear rate than that in eye drops, although it has a higher friction coefcient. In this study, the diferent friction stages in laser-treated PMMA were clarifed under two lubrication conditions. The wear rates of the laser-treated PMMA were found to decrease with the number of cycles, and the friction coefcient has a similar variation tendency. The wear behavior of the laser-treated PMMA is dominated by the main abrasive wear and secondary transferred flm formation. This study provides a theoretical basis for the development and application of ophthalmic biomaterials in complex environments by examining the material surface interface behavior and wear mechanism after laser processing using PMMA as the research matrix.

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.

Studies on the Syntheses and Properties of UV-sensitive Organosilicon Monomers and Polymers

Photosensitive organosilicon monomers and polymers containing furylacrylate, cinnamate or methacrylate groups were synthesized. The chemical structure of these organosilicon monomers were confirmed by 1H NMR and elemental analysis.The curing rates of these photosensitive polysiloxanes were also determined, all of them show a good UV-sensitivity. The UV-sensitivity of polysiloxanes containing pendent furylacrylates are comparable to that of polysiloxanes with either pendent cinnamate or pendent methacrylate groups.

Effect of anti-biofilm glass–ionomer cement on Streptococcus mutans biofilms

Dental restorative materials with antimicrobial properties can inhibit bacterial colonization, which may result in a reduction of caries at tooth-filling interaction zones. This study aimed to develop antibacterial glass-ionomer cements （GIC） containing a quaternary ammonium monomer （dimethylaminododecyl methacrylate, DMADDM）, and to investigate their effect on material performance and antibacterial properties. Different mass fractions （0, 1.1% and 2.2%） of DMADDM were incorporated into the GIC. The flexure strength, surface charge density, surface roughness and fluoride release were tested. A Streptococcus mutans biofilm model was used. Exopolysaccharides （EPS） staining was used to analyze the inhibitory effect of DMADDM on the biofilm matrix. In addition, biofilm metabolic activity, lactic acid metabolism and the expression of glucosyltransferase genes g/fB, gtfC and gtfD were measured. GIC containing 1.1% and 2.2% DMADDM had flexural strengths matching those of the commercial control （P〉0.1）. DMADDM was able to increase the surface charge density but reduced surface roughness （P〈0.05）. The incorporation of 1.1% and 2.2% DMADDM elevated the release of fluoride by the GIC in the first 2 days （P〈0.05）. The novel DMADDM-modified GIC significantly reduced biofilm metabolic activity （P〈 0.05） and decreased lactic acid production （P〈 0.05）. The quantitative polymerase chain reaction （qPCR） results showed that the expression of gtfB, g/fC and gtfD decreased when mass fractions of DMADDM increased （P〈0.05）. EPS staining showed that both the bacteria and EPS in biofilm decreased in the DMADDM groups. The incorporation of DMADDM could modify the properties of GIC to influence the development of S. mutans biofilms. In this study, we investigated the interface properties of antibacterial materials for the first time. GIC containing DMADDM can improve material performance and antibacterial properties and may contribute to the better management of secondary caries.