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1.
We describe here the first example of the synthesis of 4‐arm star poly(acrylic acid) for use as a water‐soluble drag reducing agent, by applying Cu(0)‐mediated polymerization technique. High molecular weight 4‐arm star poly(tert‐butyl acrylate) (Mn = 3.0–9.0 × 105 g mol?1) was first synthesized using 4,4′‐oxybis(3,3‐bis(2‐bromopropionate)butane as an initiator and a simple Cu(0)/TREN catalyst system. Then, 4‐arm star poly(tert‐butyl acrylate) were subjected to hydrolysis using trifluoroacetic acid resulting in water‐soluble 4‐arm star poly(acrylic acid). Drag reduction test rig analysis showed 4‐arm star poly(acrylic acid) to be effective as a drag reducing agent with drag reduction of 24.3%. Moreover, 4‐arm star poly(acrylic acid) exhibited superior mechanical stability when compared with a linear poly(acrylic acid) and commercially available drag reducing polymers; Praestol and poly(ethylene oxide). The linear poly(acrylic acid), Praestol, and poly(ethylene oxide) all showed a large decrease in drag reduction of 8–12% when cycled 30 times through the drag reduction test rig while, in contrast, 4‐arm star poly(acrylic acid) demonstrated much higher mechanical stability. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 335–344  相似文献   

2.
The kinetics of hydroquinone-inhibited oxidation of acrylic acid and methyl methacrylate was studied volumetrically by measuring the oxygen uptake in the presence of an initiator (azobisisobutyronitrile) at T = 333 K and P O 2 = 1 and 0.21 atm. The oxidation of acrylic acid inhibited by 4-methoxyphenol was studied under the same conditions for comparison. The rate constants of the reactions of the peroxyl radicals of acrylic acid (∼CH2CH(COOH)O2·) and methyl methacrylate (∼CH2CMe(COOMe)O2·) with hydroquinone (HOC6H4OH) (1.20 × 105 and 7.16 × 104 l mol−1 s−1, respectively) and of the reaction of peroxyl radicals of acrylic acid with 4-methoxyphenol (p-CH3OC6H4OH) (3.25 × 104 l mol−1 s−1) were measured. The stoichiometric inhibition factors f were determined. The reaction between the semiquinone radical and oxygen, O2 + HOC6H4O·, plays an important role, decreasing the factor f and the efficiency of the inhibition effect of hydroquinone. The rate constants of this reaction were calculated from kinetic data: k = 5.72 × 102 (in acrylic acid) and 4.60 × 102 l mol−1 s−1 (in methyl methacrylate).  相似文献   

3.
We report here our results on the investigation of the chain dynamics of poly(acrylic acid) in aqueous solution. The concentration of poly(acrylic acid) was approximately 3.8×10~(-4) mol/L, two orders of magnitude higher than that reported in the literature. The p H value of the solution was 3.9, and the hydrogen bonds between the intrinsic and ionized carboxylic acid groups formed dynamic networks, which captured aggregation-induced emission-active molecules(a tetra-quaternary ammonium modified tetraphenylethene derivative) inside the polymer coils and induced fluorescence emission. The hydrogen bonds can be classified as intra- or intermolecular; both can be probed based on the emission change of the tetra-quaternary ammonium modified tetraphenylethene probes. The effects of different external stimuli on the polymer chain dynamics were investigated using different metal cations(including Na~+, Li~+, Zn~(2+), Ni~(2+), Ca~(2+), and Co~(2+)), different cation concentrations(1×10~(-6) to 4×10~(-4) mol/L), different poly(acrylic acid) molecular weights(5, 240, and 450 k Da), and different copolymers. The experimental results indicate that the long poly(acrylic acid) chains(high molecular weight) tend to form dense globular coils and exclude the probe molecules outside, which are robust and unsusceptible to water-soluble metal cations. However, the shorter poly(acrylic acid) chains tend to form intermolecular hydrogen bonds, which are helpful in capturing more probe molecules inside the networks, thus inducing stronger emission. Because of the dual functions of forming hydrogen bonds with carboxylic groups and acting as an acceptor of protons from the carboxylic acid group to form cationic species, copolymerization with acrylate amide [poly(acrylic acid)-co-poly(acrylamide)] can greatly affect the chain dynamics of poly(acrylic acid) segments, which is reflected by the drastically decreased emission intensity from the fluorescent probes.  相似文献   

4.
We have analyzed fractionated samples of poly(methacrylic acid) produced in a propagating front for the amount of anhydride that formed and determined that a large percentage of acid groups exist as anhydrides (>20%). By analyzing the samples after cleavage, we found that the molecular weight dropped significantly (from Mn = 1.4 × 105 to Mn = 1.0 × 104). We conclude that the high molecular weights observed previously were the result of intermolecular anhydride formation. Poly(butyl acrylate), which cannot form anhydride bonds, produced in fronts had broad (Mw/Mn = 1.7–2.0) but unimodal molecular weight distributions with Mu < 105. The average molecular weight decreased with increasing initiator concentrations. © 1996 John Wiley & Sons, Inc.  相似文献   

5.
A series of narrow-MMD polymers with the molecular mass from 33 × 103 to 123 × 103 (polydispersity coefficient 1.08–1.16) were synthesized by bulk polymerization of n-butyl acrylate [2,2′-azobis(isobutyronitrile), 60°C] in the presence of a low-molecular-mass RAFT agent, dibenzyl trithiocarbonate. Then, polymerization of acrylic acid was performed in aqueous-alcoholic solution (ammonium persulfate, 70°C) in the presence of the obtained polymers, and a series of n-butyl acrylate–acrylic acid block copolymers with the molecular masses from 22 × 103 to 81 × 103 (polydispersity coefficient 1.07–1.13) were prepared. In aqueous-alcoholic solutions of the synthesized copolymers, there are nanoparticles whose size varies from 5 tо 65 nm and increases with an increase in the molecular mass of the copolymer and in the concentration of water in the solvent.  相似文献   

6.
Soap‐free poly(methyl methacrylate‐ethyl acrylate‐acrylic acid or methacrylic acid) [P(MMA‐EA‐AA or MAA)] particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and acrylic acid (AA) or methacrylic acid (MAA), and the influences of the mass ratio of core/shell monomers used in the two stages of polymerization ([C/S]w) and initiator amount on polymerization, particle size and its distribution were investigated by using different monomer addition modes. Results showed that when the batch swelling method was used, the monomer conversion was more than 96.0% and particle size distribution was narrow, and the particle size increased first and then remained almost unchanged at around 600 nm with the [C/S]w decreased. When the drop‐wise addition method was used, the monomer conversion decreased slightly with [C/S]w decreased, and large particles more than 750 nm in diameter can be obtained; with the initiator amount increased, the particle size decreased and the monomer conversion had a trend to increase; the particle size distribution was broader and the number of new particles was more in the AA system than in the MAA system; but the AA system was more stable than the MAA system at both low and high initiator amount. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

7.
Films of low-density polyethylene grafted with various amounts of polyacrylic acid were prepared by the direct irradiation method, using a 10 MeV linear electron accelerator. Aqueous solutions of acrylic acid were used with FeSO4 · 7H2O as a redox system. The best graft/homopolymer ratios were obtained at radiation doses between 2 and 3 Mrad, at acrylic acid concentrations of 40–60% and at FeSO4 · 7H2O concentrations of 0.25-0.5% by weight. The grafted films were tested for reverse osmosis properties. A membrane with 60% polyacrylic acid content gave 87% salt rejection and a water flux of 0.75 × 10?5 gm/cm2 per sec.  相似文献   

8.
The effects of the concentration of polyoxyethylene octylphenyl ether (OP-10) as a nonionic surfactant and the molecular weight of polymers (polystyrene (PS) and poly(methyl methacrylate) (PMMA)) on the morphology of anisotropic PS/PMMA composite particles were investigated. In the case of polymers with lower molecular weight (M w ≈ 6.0 × 104 g/mol), the PS/PMMA composite particles have dimple, via acorn, to hemispherical shapes along with the increase of the OP-10 concentration. On the other hand, when the polymers have higher molecular weight (M w ≈ 3.3 × 105 g/mol), the morphology of PS/PMMA composite particles changed from dimple, via hemispherical, to snowman-like structure while the concentration of OP-10 was increased. Furthermore, thermodynamic analysis was first simply made by spreading coefficients, and the results indicated that both the concentration of OP-10 aqueous solution and the molecular weight of polymers were very important to the final morphology of anisotropic composite particles.  相似文献   

9.
Pulsed laser polymerization (PLP) coupled to size exclusion chromatography (SEC) is considered to be the most accurate and reliable technique for the determination of absolute propagation rate coefficients, kp. Herein, kp data as a function of temperature were determined via PLP‐SEC for three acrylate monomers that are of particular synthetic interest (e.g., for the generation of amphiphilic block copolymers). The high‐Tg monomer isobornyl acrylate (iBoA) as well as the precursor monomers for the synthesis of hydrophilic poly(acrylic acid), tert‐butyl acrylate (tBuA), and 1‐ethoxyethyl acrylate (EEA) were investigated with respect to their propagation rate coefficient in a wide temperature range. By application of a 500 Hz laser repetition rate, data could be obtained up to a temperature of 80 °C. To arrive at absolute values for kp, the Mark‐Houwink parameters of the polymers have been determined via on‐line light scattering and viscosimetry measurements. These read: K = 5.00 × 105 dL g−1, a = 0.75 (piBoA), K = 19.7 × 105 dL g−1, a = 0.66 (ptBA) and K = 1.53 × 105 dL g−1, a = 0.85 (pEEA). The bulky iBoA monomer shows the lowest propagation rate coefficient among the three monomers, while EEA is the fastest. The activation energies and Arrhenius factors read: (iBoA): log(A/L mol−1 s−1) = 7.05 and EA = 17.0 kJ mol−1; (tBuA): log(A/L mol−1 s−1) = 7.28 and EA = 17.5 kJ mol−1 and (EEA): log(A/L mol−1 s−1) = 6.80 and EA = 13.8 kJ mol−1. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6641–6654, 2009  相似文献   

10.
A sensitive molecularly imprinted electrochemical sensor with specific recognition ability for oleanolic acid was synthesized by modification of multiwalled carbon nanotubes (MWNTs) decorated with tin oxide nanoparticles (nano‐SnO2/MWNTs) and polypyrrole‐imprinted polymer on a carbon electrode. The morphology and electrochemical performance of the imprinted sensor were investigated by using scanning electron microscope (SEM), X‐ray diffraction (XRD), cyclic voltammetry (CV), linear sweep voltammetry (LSV) and amperometric it curve. The results showed that the imprinted sensor displayed excellent selectivity toward oleanolic acid. A linear relationship between the response currents and oleanolic acid concentrations ranging from 5.0×10?8 g/L to 2.0×10?5 g/L was obtained for the imprinted sensor. The limit of detection (LOD) of the imprinted sensor toward oleanolic acid was calculated as 8.6×10?9 g/L at a signal to noise ratio (S/N) of 3. This imprinted sensor was successfully applied to the determination of oleanolic acid in Acitinidia deliciosa root samples.  相似文献   

11.
The preparation and evaluation of polymeric oil sorbent based on styrene acrylate ester and ethylhexyl acrylate (EHA) are the main target of this work. In this respect, poly styrene-co-p-chloromethyl styrene (PSCMS) was synthesized through radical copolymerization of p-CMS with styrene in the presence of benzoyl peroxide initiator. Then, the PSCMS was reacted with acrylic acid to produce macromonomer containing polymerizable C?C poly {styrene-co-[4-(methyl acrylate) styrene]} (PSSMA) that subsequently copolymerized with EHA in the presence of a cross-linker to obtain the cross-linked copolymers PSSMA/EHA (organogel). The prepared compounds were characterized by using FTIR, 1H NMR, and gel permeation chromatography. The thermal properties of the cross-linked oil absorbents were investigated using thermogravimetric analysis, and the morphology was characterized by scanning electron microscope (SEM). The oil absorbency of oil gel was determined through oil absorption tests; the highest oil absorbencies of oil gel were found to be 82.6, 74.4, 46.7, and 38.1 g/g in N,N-dimethyl formamide, CHCl3, toluene, and diesel, respectively.  相似文献   

12.

The graft copolymerization of acrylonitrile (AN) and ethyl acrylate (EA) comonomers onto cellulose has been carried out using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 35±0.1°C. The addition of ethyl acrylate as comonomer has shown a significant effect on overall and individual graft copolymerization of acrylonitrile on cellulose. The graft yield (%GY) and other grafting parameters viz. true grafting (%GT), graft conversion (%CG), cellulose number (Ng) and frequency of grafting (GF) were evaluated on varying the concentration of comonomers from 6.0–30.0×10?1 mol dm?3 and ceric (IV) ions concentration from 2.5–25×10?3 mol dm?3 at constant feed composition (fAN 0.6) and constant concentration of nitric acid (7.5×10?2 mol dm?3) in the reaction mixture. The graft yield (%GY) and other grafting parameters were optimal at 15×10?1 mol dm?3 concentration of comonomers and at 10×10?3 mol dm?3 concentration of ceric ammonium nitrate. The graft yield (%GY) and composition of grafted chains (FAN) was optimal at a feed composition (fAN) of 0.6. The energy of activation (Ea) for graft copolymerization has been found to be 16 kJ mol?1. The molecular weight (Mw) and molecular weight distribution (Mw/Mn) of grafted chains was determined by GPC and found to be optimum at 15×10?1 mol dm?3 concentration of comonomer in the reaction mixture. The composition of grafted chains (FAN) determined by IR method was used to calculate the reactivity ratios of monomers, which has been found to be 0.62 (r1) and 1.52 (r2), respectively for acrylonitrile (AN) and ethyl acrylate (EA) monomers used for graft copolymerization. The energy of activation for decomposition of cellulose and grafted cellulose was determining by using different models based on constant and different rate (β) of heating. Considering experimental observations, the reaction steps for graft copolymerization were proposed.  相似文献   

13.
High molecular weight polyelectrolyte: poly(dimethylaminoethyl methacrylate) [PDMAEMA] with molecular weights MW = 28.0×106, 20.0×106, 15.0×106 was investigated in dilute solution by light scattering, flow birefringence and viscometry (at different rate gradients) in a water-acetone system by varying the weight fraction of acetone r in the mixture. At r=0.76 the polymer undergoes a reversible coil-globule transition accompanied by a drastic decrease in intrinsic viscosity [n], mean-square radius of gyration R2z1/2 and second virial coefficient A2, with no change in molecular weight. The coil asymmetry parameter p (p=2.5 at r=0.50) decreases with increasing r and attains unity (completely symmetrical particle) at the transition point (r=0.76). The anomalous behavior of the viscosity of PDMAEMA-water-acetone solutions, detected near the transition point (r=0.6+0.7), is interpreted by formation of local knots of compactization on the molecular chain under the influence of a hydrodynamic field.  相似文献   

14.
The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA),2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate(HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solidcontent. The effects of monomer emulsion feed rates (R_a) and (R/E)_E values, the ratio ofemulsifier amount between the initial charge (R) and the addition monomer emulsion (E),on the polymerization reaction features, the viscosities, surface tensions,particle sizes andparticle sizes distributions of latexes,T_g and the insoluble fractions of films, the 180° peelstrength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, preparedfrom the latexes, were studied. Experimental study shows that the grafting and cross-linking fraction in the PSA tapes must be controlled within a suitable range to keep thebalance of the 180° peel strength, tack and holding power.  相似文献   

15.
Nanocrystalline powders of super-refractory complex carbides Ta4HfC5 and Ta4ZrC5 were synthesized using a hybrid method comprising sol-gel technology for preparing highly dispersed metal oxidescarbon starting mixtures and a relatively low-temperature (1300–1500°C) carbothermal synthesis under a dynamic vacuum (P = 1 × 10−3 to 1 × 10−5 MPa). The elemental and phase compositions of the products and average crystallite sizes were determined. TEM was used to study particle morphology and dispersion. Microstructures were observed by SEM. BET specific surface areas were determined for powders prepared at 1400°C.  相似文献   

16.
The bulk polymerization of 2‐ethylhexyl acrylate (2‐EHA), induced by a pulsed electron beam, was investigated with pulse radiolysis, gravimetry, and Fourier transform infrared spectroscopy. The roles of the dose rate, pulse frequency, and added acrylic acid (AA) in the polymerization of 2‐EHA were examined at ambient temperature. In the range of 12.6–71.2 Gy/pulse, the polymerization of 2‐EHA was dose‐rate‐dependent: at the same total dose, a lower dose rate yielded a higher conversion. Also, a lower pulse rate gave a higher conversion at the same total dose. The addition of up to 10 wt % AA showed no increase in the conversion of 2‐EHA at a low conversion (8 kGy), but at a higher conversion (16 kGy), a 20 wt % increase in the conversion of 2‐EHA was observed. The estimated values (1.6 ± 0.3) × 10?3 (dm3 s)3/2 mol?1 s?1/2 for kp(G/2kt)1/2 and 2.6 ± 0.8 dm3 s J?1 for 2ktG (where kp is the rate constant of propagation, kt is the rate constant of bimolecular termination, and G is the yield of free radicals) were obtained at relatively low conversions. The reaction rate constant of the addition of 2‐EHA· free radicals to the monomer was measured by pulse radiolysis and found to be 2.8 × 102 mol?1 dm3 s?1. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 196–203, 2003  相似文献   

17.
Fenfluramine-imprinted polymer was prepared by self assembly with acrylic amide as functional monomer and ethylene glycol dimethacrylate as crosslinker. The binding characteristics of the imprinted polymer to fenfluramine were evaluated by equilibrium binding experiments and the morphology was studied by SEM. Taking the imprinted polymer as recognition material, using the new 3-p-nitrylphenyl-5-(4′-methyl-2′-sulfonophenylazo)rhodanine (M4NRASP) synthesized by the authors as chemiluminescence reagent, a new highly selective flow injection chemiluminescence sensor for trace fenfluramine with good sensitivity was established which utilized the chemiluminescence reaction between fenfluramine, M4NRASP, and potassium permanganate in hydrochloric acid. The traditional flow-through cell was replaced with a polymethyl methacrylate module, with Y-shaped flow path, through which the above three reactants were injected simultaneously. Under optimum conditions the relative chemiluminescence intensity shows a linear relationship with the concentration of fenfluramine over the range of 5×10–7 to 8×10–6 g/mL with a lower detection limit of 3.4×10–8 g/mL. The relative standard deviation for the determination of 1.0×10–6 g/mL fenfluramine solution was 2.4% (n = 11). This proposed sensor could be satisfactorily applied to the determination of fenfluramine in weight-reducing capsules.  相似文献   

18.
The radiation-induced graft copolymerization of styrene with ethyl acrylate onto preirradiated polyethylene powder was carried out at 20°C. The grafting yield decreased in the following order: ethyl acrylate ? styrene > styrene–ethyl acrylate mixture. On the other hand, the amount of absorption of liquid monomers in polyethylene powder decreased as follows: styrene > styrene–ethyl acrylate mixture > ethyl acrylate. By kinetic analysis of the grafting yield and amount of absorption of monomers it was elucidated that the value Kp/Kt in an ethyl acrylate system (7.7 × 10?2) was much larger than those in styrene–ethyl acrylate systems and in a styrene system (ca. 1.0 × 10?2).  相似文献   

19.
Abstract

The feasibility of grafting poly(methyl acrylate) and poly[1-(methoxycarbonyl) ethylene] onto chitosan, poly-β(1←-4)-2-amino-2-deoxy-d-glucose, was investigated. The grafting reaction was carried out in aqueous solution by using ferrous ammonium sulfate (FAS) in combination with H2O2 as redox initiator. The effects of such reaction variables as chitosan, monomer and initiator concentrations, reaction time, and reaction temperature were determined. Through this study the grafting reaction could be optimized. The grafting yield reached its maximum value of 332% when 0.3 g chitosan was copolymerized with 3 mL monomer at 70°C for 120 minutes with [FAS] = 6 × 10?5 M, [H2O2] = 6 × 10?3 M, and 8 mL water. The grafted chitosan was found to be insoluble in solvents for chitosan and solvents for poly(methyl acrylate), but did show swelling in dilute acetic acid, methanol, acetone, and in an ethanol/2% acetic acid 1:1 mixture. The thermal stability of chitosan and grafted chitosan were studied by dynamic thermogravimetric analysis. The results show that the graft copolymer is thermally more stable than pure chitosan. The overall activation energy for graft copolymerization was estimated to be 32.8 kcal/mol.  相似文献   

20.
Yan Zhang  Jing Zheng  Mandong Guo 《中国化学》2016,34(12):1268-1276
An innovative molecularly imprinted electrochemical sensor was fabricated based on reduced graphene oxide (RGO) and gold nanocomposite (Au) for rapid detection of vincristine (VCR). The RGO‐Au composite membrane was obtained via direct one‐step electrodeposition technique of graphene oxide (GO) and chloroauric acid (HAuCl4) on the surface of a glassy carbon electrode (GCE) by means of cyclic voltammetry (CV) in the potential range between ?1.5 and 0.6 V in phosphate buffer solution (PBS) of pH 9.18, which is capable of effectively utilizing its superior electrical conductivity, larger specific surface area due to its synergistic effect between RGO and Au. The molecularly imprinted polymers (MIPs) were synthesized on the RGO‐Au modified glassy carbon electrode surface with VCR as the template molecular, methyl acrylic acid (MAA) as the functional monomer, and ethylene glycol maleic rosinate acrylate (EGMRA) as a cross‐linker. The performance of the sensor was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) in detail. Under the optimum conditions, the fabricated sensor exhibited a linear relationship between oxidation peak current and VCR concentration over the range of 5.0×10?8–5.0×10?6 mol·L minus;1 with a correlation coefficient of 0.9952 and a detection limit (S/N=3) of 2.6×10minus;8 mol·Lminus;1. The results indicated that the imprinted polymer films exhibited an excellent selectivity for VCR. The imprinted sensor was successfully used to determine VCR in real samples with recoveries of 90% –120% by using the standard addition method.  相似文献   

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