Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate(nano-CaCO3) surface modified with γ-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl ...Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate(nano-CaCO3) surface modified with γ-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ emulsion polymerization.展开更多
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 sa...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 (<sup>1</sup>H 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.展开更多
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...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.展开更多
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-ethylen...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.展开更多
The crystallization modification of poly(vinylidene fluoride) (PVDF) was investigated for the blend films of PVDF and poiy(methyl methacrylate) (PMMA). The mass crystallinity (Xc) and further, the β-phase c...The crystallization modification of poly(vinylidene fluoride) (PVDF) was investigated for the blend films of PVDF and poiy(methyl methacrylate) (PMMA). The mass crystallinity (Xc) and further, the β-phase content (F(β)) of PVDF, were studied for the asprepared blend films with different mass ratios. In addition, the variations of Xc and F(β) were systematically probed once the PMMA component was removed from the related blend systems. DSC, FTIR and XRD measurements all indicated that 1)Xc, F(β) and even the content of a-phase (F(a)) decreased with the addition of PMMA; 2) with the extraction of PMMA, both Xc and F(β) increased while F(a) decreased. It is worth noting that the increase of Xc and F(β) depended on the relative amount of extracted PMMA (EpMMA), i.e., the more PMMA was removed, the more Xc and F(β) increased. These results reveal the hindrance effect from the PMMA constituent to the crystallization of PVDF, and consequently, this restriction would be released when the PMMA was extracted.展开更多
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, howe...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.展开更多
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 Py...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.展开更多
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...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.展开更多
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 existen...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.展开更多
The photochemical kinetics of phenanthrenequinone (PQ) doped poly (methyl methacrylate) photopolymer in holographic recording was studied theoretically and experimentally. The diffusion of PQ molecules during holo...The photochemical kinetics of phenanthrenequinone (PQ) doped poly (methyl methacrylate) photopolymer in holographic recording was studied theoretically and experimentally. The diffusion of PQ molecules during holographic recording was negligible because of its small diffusion coefficient at room temperature. A photochemical reaction kinetics model of PQ/PMMA was established. The analytical expressions for the temporal variations of transmittance and diffraction efficiency were derived. By fitting the experimental curves, some parameters related with the polymer components were obtained by the proposed model, which can be used to analyze the photochemical process and will be helpful to the optimization of material preparation.展开更多
The effects of the concentration of sodium chloride in an aqueous solution(cNacl and the temperature on the molecular size of poly(sulfobetaine methacrylate)(PSBMA) were studied via viscometry and dynamic light s...The effects of the concentration of sodium chloride in an aqueous solution(cNacl and the temperature on the molecular size of poly(sulfobetaine methacrylate)(PSBMA) were studied via viscometry and dynamic light scattering(DLS). The morphology of single-chain PSBMA was determined by atomic force microscopy(AFM). The results demonstrate that the hydrodynamic diameter of PSBMA can be expressed as a continuous function of CNaCl, with the molecular size of PSBMA increasing and eventually approaching an asymptotic value with increasing CNaCl. The molecular size of PSBMA at a lower CNaCI(0.04 mol/L) increases with increasing temperature, which is the opposite of the temperature effect at a higher CNaCl(2.0 mol/L). Therefore, the internal structure of PSBMA chains in solutions with a low salt concentration differs from that in solutions with a high salt concentration. In addition, the morphology of single chains of PSBMA appears to be spherical, containing 89% void space, and the apparent size of the dried chains is almost identical to that in solution.展开更多
Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Th...Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.展开更多
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...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.展开更多
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 alk...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.展开更多
Objective To evaluate the genotoxic and nongenotoxic effects of short-term exposure to glycidyl mathacrylate (GMA) on human lung fibroblast cells (2BS cells) in vitro. Methods DNA strand breakage was determined by sin...Objective To evaluate the genotoxic and nongenotoxic effects of short-term exposure to glycidyl mathacrylate (GMA) on human lung fibroblast cells (2BS cells) in vitro. Methods DNA strand breakage was determined by single cell gel electrophoresis, and DNA ladder formation assay and flow cytometric analysis were carried out to detect apoptic responses of cells to GMA exposure. The HPRT gene mutation assay was used to evaluate the mutagenicity, and the effect of GMA on gap junctional intercellular communication (GJIC) in the exposed cells was examined with the scrape loading/dye transfer technique. The ability of GMA to transform 2BS cells was also tested by an in vitro cell transformation assay. Results Exposure to GMA resulted in a dose-dependent increase in DNA strand breaks but not apoptic responses. GMA was also shown to significantly induce HPRT gene mutations and morphological transformation in 2BS cells in vitro. In contrast, GMA produced a concentration-dependent inhibition of GJIC. Conclusions GMA elicits both genotoxic and nongenotoxic effects on 2BS cells in vitro. The induction of DNA damage and gene mutations and inhibition of GJIC by GMA may casually contribute to GMA-induced cell transformation.展开更多
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 ultra...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.展开更多
Antibacterial dimethylaminododecyl methacrylate (DMADDM) was recently synthesized. The objectives of this study were to: (1) investigate antibacterial activity of DMADDM-containing primer on Streptococcus mutans ...Antibacterial dimethylaminododecyl methacrylate (DMADDM) was recently synthesized. The objectives of this study were to: (1) investigate antibacterial activity of DMADDM-containing primer on Streptococcus mutans impregnated into dentin blocks for the first time, and (2) compare the antibacterial efficacy of DMADDM with a previous quaternary ammonium dimethacrylate (QADM). Scotchbond Multi-Purpose (SBMP) bonding agent was used. DMADDM and QADM were mixed into SBMP primer. Six primers were tested: SBMP control primer P, P+2.5% DMADDM, P+5% DMADDM, P+7.5% DMADDM, P+10% DMADDM, and P+10% QADM. S. mutans were impregnated into human dentin blocks, and each primer was applied to dentin to test its ability to kill bacteria in dentinal tubules. Bacteria in dentin were collected via a sonication method, and the colony-forming units (CFU) and inhibition zones were measured. The bacterial inhibition zone of P+10% DMADDM was 10 times that of control primer (P〈0.05). CFU in dentin with P+10% DMADDM was reduced by three orders of magnitude, compared with control. DMADDM had a much stronger antibacterial effect than QADM, and antibacterial efficacy increased with increasing DMADDM concentration. Dentin shear bond strengths were similar among all groups (P〉0.1). In conclusion, antibacterial DMADDM-containing primer was validated to kill bacteria inside dentin blocks, possessing a much stronger antibacterial potency than the previous QADM. DMADDM-containing bonding agent was effective in eradicating bacteria in dentin, and its efficacy was directly proportional to DMADDM mass fraction. Therefore, DMADDM may be promisine for use in bonding agents as well as in other restorative and oreventive materials to inhibit bacteria.展开更多
Synthesis and characterization of the copolymers (PAG) of α-methyl styrene (AMS) and glycidyl methacrylate (GMA) are presented. The copolymers of PAG were characterized by gel permeation chromatography (GPC),...Synthesis and characterization of the copolymers (PAG) of α-methyl styrene (AMS) and glycidyl methacrylate (GMA) are presented. The copolymers of PAG were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (^1H-NMR) and thermogravimetery (TG). Based on the copolymer compositions determined by ^1H-NMR, the reactivity ratios of AMS and GMA were found to be 0.105 ± 0.012 and 0.883 ± 0.046 respectively by Kelen-Tudos method. TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers, which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures. Under heating, the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.展开更多
Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) employing ethyl 2-bromoisobutyrate (EBiB)/ CuBr as the initiating system was investigated at 50 ℃ in the absence of any additional ligand...Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) employing ethyl 2-bromoisobutyrate (EBiB)/ CuBr as the initiating system was investigated at 50 ℃ in the absence of any additional ligand in the three room temperature ionic liquids (RTILs), 1-methyl-imidazolium acetate ([mim][CH3COO]), 1-methylimidazolium propionate ([mim][CH3CH2COO]) and 1-methylimidazolium butyrate ([mim][CH3CH2CH2COO]), respectively. All the polymerization in the three RTILs proceeded in a well-controlled manner. The sequence of the apparent polymerization rate constants was kapp([mim][CH3COO]) 〉 kapp([mim] [CH3CH2COO]) 〉 kapp ([mim][CH3CH2CH2COO]).展开更多
文摘Methyl methacrylate (MMA) emulsion polymerization in the presence of nanometer calcium carbonate(nano-CaCO3) surface modified with γ-methacryloxypropyltrimethoxysilane (MPTMS) was carried out to prepare poly (methyl methacrylate) (PMMA)/nano-CaCO3 composite. The reaction between nano-CaCO3 and MPTMS, and the grafting of PMMA onto nano-CaCO3 were confirmed by infrared spectrum. The grafting ratio and grafting efficiency of PMMA on nano-CaCO3 modified with MPTMS were much higher than that on nano-CaCO3 modified with stearic acid. The grafting ratio of PMMA increased as the weight ratio between MMA and nano-CaCO3 increased, while the grafting efficiency of PMMA decreased. Transmission electron micrograph showed that nano-CaCO3 covered with PMMA was formed by in-situ emulsion polymerization.
文摘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 (<sup>1</sup>H 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.
基金supported by the National Science Foundation for Distinguished Young Scholars of China(Grant No.51925403)Major Research plan of the National Natural Science Foundation of China(Grant No.91934302)+2 种基金the National Science Foundation of China(21676052,21606042)Independent Innovation Fund of Tianjin University(2023XJD0050)Funding for National Key R&D Program of China(2022YFB3808800).
文摘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.
基金Fujian External Cooperation project of Natural Science Foundation,China(No.2022I0042)。
文摘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.
基金Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant No. 21072221), the President Fund of Graduate University of CAS (Grant No. 095101CY00), and the State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences (KF2008-04).
文摘The crystallization modification of poly(vinylidene fluoride) (PVDF) was investigated for the blend films of PVDF and poiy(methyl methacrylate) (PMMA). The mass crystallinity (Xc) and further, the β-phase content (F(β)) of PVDF, were studied for the asprepared blend films with different mass ratios. In addition, the variations of Xc and F(β) were systematically probed once the PMMA component was removed from the related blend systems. DSC, FTIR and XRD measurements all indicated that 1)Xc, F(β) and even the content of a-phase (F(a)) decreased with the addition of PMMA; 2) with the extraction of PMMA, both Xc and F(β) increased while F(a) decreased. It is worth noting that the increase of Xc and F(β) depended on the relative amount of extracted PMMA (EpMMA), i.e., the more PMMA was removed, the more Xc and F(β) increased. These results reveal the hindrance effect from the PMMA constituent to the crystallization of PVDF, and consequently, this restriction would be released when the PMMA was extracted.
基金This work was supported by the National Natural Science Foundations of China.
文摘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.
文摘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.
基金This work was supported by the Zhejiang Grant Science and Technology Program(No.2005C11039).
文摘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.
基金The authors are grateful to the National Natural Science Foundation of China (No. 50433040) for the financial support.
文摘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.
基金Project supported by the Fundamental Research Foundation of COSTIND (Grant No 2320060089)the MOST of China (973 Project Grant No 2007CB307001)Program of Excellent Team in Harbin Institute of Technology
文摘The photochemical kinetics of phenanthrenequinone (PQ) doped poly (methyl methacrylate) photopolymer in holographic recording was studied theoretically and experimentally. The diffusion of PQ molecules during holographic recording was negligible because of its small diffusion coefficient at room temperature. A photochemical reaction kinetics model of PQ/PMMA was established. The analytical expressions for the temporal variations of transmittance and diffraction efficiency were derived. By fitting the experimental curves, some parameters related with the polymer components were obtained by the proposed model, which can be used to analyze the photochemical process and will be helpful to the optimization of material preparation.
基金Supported by the National Natural Science Foundation of China(No.21174053).
文摘The effects of the concentration of sodium chloride in an aqueous solution(cNacl and the temperature on the molecular size of poly(sulfobetaine methacrylate)(PSBMA) were studied via viscometry and dynamic light scattering(DLS). The morphology of single-chain PSBMA was determined by atomic force microscopy(AFM). The results demonstrate that the hydrodynamic diameter of PSBMA can be expressed as a continuous function of CNaCl, with the molecular size of PSBMA increasing and eventually approaching an asymptotic value with increasing CNaCl. The molecular size of PSBMA at a lower CNaCI(0.04 mol/L) increases with increasing temperature, which is the opposite of the temperature effect at a higher CNaCl(2.0 mol/L). Therefore, the internal structure of PSBMA chains in solutions with a low salt concentration differs from that in solutions with a high salt concentration. In addition, the morphology of single chains of PSBMA appears to be spherical, containing 89% void space, and the apparent size of the dried chains is almost identical to that in solution.
基金This work was supported by the National Natural Science Foundation of China (Grants 20174001, 29992590-4) and the Ministry of Education of China for the teaching and research award fund for outstanding young teacher in higher education institutions.
文摘Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.
文摘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.
基金supported by NIH R01 DE17974West China School of Stomatologya Seed Grant from Department of Endodontics,Prosthodontics and Operative Dentistry,University of Maryland
文摘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.
基金This work was supported by a grant from the National Natural Science Foundation of China (grant no. 39840017).
文摘Objective To evaluate the genotoxic and nongenotoxic effects of short-term exposure to glycidyl mathacrylate (GMA) on human lung fibroblast cells (2BS cells) in vitro. Methods DNA strand breakage was determined by single cell gel electrophoresis, and DNA ladder formation assay and flow cytometric analysis were carried out to detect apoptic responses of cells to GMA exposure. The HPRT gene mutation assay was used to evaluate the mutagenicity, and the effect of GMA on gap junctional intercellular communication (GJIC) in the exposed cells was examined with the scrape loading/dye transfer technique. The ability of GMA to transform 2BS cells was also tested by an in vitro cell transformation assay. Results Exposure to GMA resulted in a dose-dependent increase in DNA strand breaks but not apoptic responses. GMA was also shown to significantly induce HPRT gene mutations and morphological transformation in 2BS cells in vitro. In contrast, GMA produced a concentration-dependent inhibition of GJIC. Conclusions GMA elicits both genotoxic and nongenotoxic effects on 2BS cells in vitro. The induction of DNA damage and gene mutations and inhibition of GJIC by GMA may casually contribute to GMA-induced cell transformation.
文摘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.
基金supported by NIH R01 DE17974 (Hockin HK Xu)a scholarship from West China School of Stomatology (Chen Chen)+3 种基金Program for New Century Excellent Talents in University (Lei Cheng)Youth Grant of Science and Technology Department of Sichuan Province China (2014JQ0033) (Lei Cheng)a bridge fund from University of Maryland Baltimore School of Dentistry (Hockin HK Xu)a seed grant from University of Maryland Baltimore (Hockin HK Xu)
文摘Antibacterial dimethylaminododecyl methacrylate (DMADDM) was recently synthesized. The objectives of this study were to: (1) investigate antibacterial activity of DMADDM-containing primer on Streptococcus mutans impregnated into dentin blocks for the first time, and (2) compare the antibacterial efficacy of DMADDM with a previous quaternary ammonium dimethacrylate (QADM). Scotchbond Multi-Purpose (SBMP) bonding agent was used. DMADDM and QADM were mixed into SBMP primer. Six primers were tested: SBMP control primer P, P+2.5% DMADDM, P+5% DMADDM, P+7.5% DMADDM, P+10% DMADDM, and P+10% QADM. S. mutans were impregnated into human dentin blocks, and each primer was applied to dentin to test its ability to kill bacteria in dentinal tubules. Bacteria in dentin were collected via a sonication method, and the colony-forming units (CFU) and inhibition zones were measured. The bacterial inhibition zone of P+10% DMADDM was 10 times that of control primer (P〈0.05). CFU in dentin with P+10% DMADDM was reduced by three orders of magnitude, compared with control. DMADDM had a much stronger antibacterial effect than QADM, and antibacterial efficacy increased with increasing DMADDM concentration. Dentin shear bond strengths were similar among all groups (P〉0.1). In conclusion, antibacterial DMADDM-containing primer was validated to kill bacteria inside dentin blocks, possessing a much stronger antibacterial potency than the previous QADM. DMADDM-containing bonding agent was effective in eradicating bacteria in dentin, and its efficacy was directly proportional to DMADDM mass fraction. Therefore, DMADDM may be promisine for use in bonding agents as well as in other restorative and oreventive materials to inhibit bacteria.
文摘Synthesis and characterization of the copolymers (PAG) of α-methyl styrene (AMS) and glycidyl methacrylate (GMA) are presented. The copolymers of PAG were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (^1H-NMR) and thermogravimetery (TG). Based on the copolymer compositions determined by ^1H-NMR, the reactivity ratios of AMS and GMA were found to be 0.105 ± 0.012 and 0.883 ± 0.046 respectively by Kelen-Tudos method. TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers, which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures. Under heating, the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.
基金Financial support from Zhejiang Provincial Natural Science Foundation (No.R203154, Y405124) is gratefully acknowledged.
文摘Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) employing ethyl 2-bromoisobutyrate (EBiB)/ CuBr as the initiating system was investigated at 50 ℃ in the absence of any additional ligand in the three room temperature ionic liquids (RTILs), 1-methyl-imidazolium acetate ([mim][CH3COO]), 1-methylimidazolium propionate ([mim][CH3CH2COO]) and 1-methylimidazolium butyrate ([mim][CH3CH2CH2COO]), respectively. All the polymerization in the three RTILs proceeded in a well-controlled manner. The sequence of the apparent polymerization rate constants was kapp([mim][CH3COO]) 〉 kapp([mim] [CH3CH2COO]) 〉 kapp ([mim][CH3CH2CH2COO]).