Kinetics and Mechanism of Hydration of Acrylic Acid over Ion-exchanged Resin:Experimental Exploration and DFT Calculation

Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects of catalystscreening and exploring reaction conditions, with few accurate descriptions of the reaction kinetics and determination ofthe reaction mechanism. Here, we combined kinetics experiments and theoretical calculations to elucidate the kinetics andmechanism of acrylic acid hydration on a resin catalyst. The pseudo-homogeneous model, and Langmuir-Hinshelwood-Haugen-Watson and Elie-Riedel (ER) heterogeneous models were used to explain the experimental kinetics data. TheER model can explain the experimental data very well, suggesting strong adsorption of acrylic acid on the surface of theresin catalyst. Furthermore, density functional theory calculations show that the hydration follows a stepwise, rather than aconcerted, reaction pathway. The present study provides theoretical insights into the reaction mechanism and kinetics, fillingthe gap in our understanding of the reaction on a fundamental level.

Enhance of Grafting Reaction of Acrylic Acid and Acrylamide onto Preirradiated Polypropylene Film

Grafting of acrylic acid (AAc) and acrylamide (AAm) onto preirradiated PP film was performed in aqueous solution of AAc and AAm, respectively. Electron beam accelerator was used as irradiation source. The effect of ferrous sulfate, sodium nitrate, methanol and glucose on the degree of grafting was demonstrated. The function of the different additives was compared by the grafting of different monomers (AAc and AAm). The results show that the four of these additives are elective on the grafting of AAc. Only two of these additives, ferrous sulfate and methanol were effective on the grafting of AAm.

Removal of manganese from waste water by complexation-ultrafiltration using copolymer of maleic acid and acrylic acid

Copolymer of maleic acid and acrylic acid （PMA-100）, combining with polyvinyl butyral （PVB） ultrafiltration membrane was used for the removal of Mn（II） from waste water by complexation-ultrafiltration. The carboxylic group content of PMA-100 and the rate of complexation reaction were measured. Effects of the mass ratio of PMA-100 to Mn（II） （n）, pH, background electrolyte, etc on the rejection rate （R） and permeate flux （J） were investigated. The results show that carboxylic group content of PMA-100 is 9.5 mmol/g. The complexation of Mn（II） with PMA-100 is rapid and completed within 5 min at pH 6.0. Both R and J increase with pH increasing in the range of 2.5-7.0, and R increases with the increase of n at pH 6.0 while J is little affected. The background electrolyte leads to the decrease of R, and CaCl2 has much greater effect on R than NaCl at the same ionic strength.

Alkali-metal-modified ZSM-5 zeolites for improvement of catalytic dehydration of lactic acid to acrylic acid

Various ZSM-5 zeolites modified with alkali metals （Li, Na, K, Rb, and Cs） were prepared using ion exchange. The catalysts were used to enhance the catalytic dehydration of lactic acid （LA） to acrylic acid （AA）. The effects of cationic species on the structures and surface acid-base distributions of the ZSM-5 zeolites were investigated. The important factors that affect the catalytic performance were also identified. The modified ZSM-5 catalysts were characterized using X-ray diffraction, tempera- ture-programmed desorptions of NH3 and CO2, pyridine adsorption spectroscopy, and N2 adsorption to determine the crystal phase structures, surface acidities and basicities, nature of acid sites, specific surface areas, and pore volumes. The results show that the acid-base sites that are adjusted by alkali-metal species, particularly weak acid-base sites, are mainly responsible for the formation of AA. The KZSM-5 catalyst, in particular, significantly improved LA conversion and AA selectivity because of the synergistic effect of weak acid-base sites. The reaction was conducted at different reaction temperatures and liquid hourly space velocities （LHSVs） to understand the catalyst selectivity for AA and trends in byproduct formation. Approximately 98% LA conversion and 77% AA selectivity were achieved using the KZSM-5 catalyst under the optimum conditions （40 wt% LA aqueous solution, 365 ℃, and LHSV 2 h-1）.

Antimicrobial Expanded Polytetrafluoroethylene Film Prepared by 3-ray Radiation Induced Grafting of Poly（acrylic acid）

The simultaneous γ-ray-radiation-induced grafting polymerization of acrylic acid on ex- panded polytetrafluoroethylene （ePTFE） film was investigated. It was found that the degree of grafting （DG） of poly（acrylic acid） （PAA） can be controlled by the monomer concentration, absorbed dose, and dose rate under an optimal inhibitor concentration of [Fe2＋]=18 mmol/L. SEM observation showed that the macroporous structure in ePTFE films would be covered gradually with the increase of the DG of PAA. The prepared ePTFE-g-PAA film was im- mersed in a neutral silver nitrate solution to fabricate an ePTFE-g-PAA/Ag hybrid film after the addition of NaBH4 as a reduction agent of Ag＋ to Ag atom. SEM, XRD, and XPS results proved that Ag nanoparticles with a size of several tens of nanometers to 100 nanometers were in situ immobilized on ePTFE film. The loading capacity of Ag nanoparticles could be tuned by the DG of PAA, and determined by thermal gravimetric analysis. The quart- titative antibacterial activity of the obtained ePTFE-g-PAA/Ag hybrid films was measured using counting plate method. It can kill all the Escherichia coli in the suspension in 1 h. Moreover, this excellent antibacterial activity can last at least for 4 h. This work provides a facile and practical way to make ePTFE meet the demanding antimicrobial requirement in more and more practical application areas.

Advances in the Research and Development of Acrylic Acid Production from Biomass

The shortage of petroleum has resulted in worldwide efforts to produce chemicals from renewable resources. Among these attempts, the possibility of producing acrylic acid from biomass has caught the eye of many researchers. Converting the carbohydrates first to lactic acid by fermentation and then dehydrating lactic acid to acrylic acid is hitherto the most effective way for producing acrylic acid from biomass. While the lactic acid fer- mentation has been commercialized since longer times, the dehydration process of lactic acid is still under development because of its low yield. Further efforts should be made before this process became economically feasible. Because of the existence of acrylic acid pathways in some microorganisms, strain improvement and metabolic engineering provides also a possibilitv to produce acrylic acid directly from biomass by fermentation.

Poly-Acrylic Acid Derivatives as Diesel Flow Improver for Paraffin-Based Daqing Diesel

Since the diesel products from paraffin-based Daqing crude oil showed low sensitivity to certain commercial diesel pour point depressant （PPDs） that resulted from the high content of paraffin, certain poly-acrylic acid derivatives （PADE） with-COOR, -COOH,-CONHR, and -COO-NH3^＋R groups by molecular design on the mechanics of diesel; PPDs were synthesized and evaluated as cold flow improver for Daqing 0^# diesel in this paper. The pure PADE was superior to the commercial PPDs and displayed a substantial ability of wax crystals dispersion. There was a synergistic effect among the PADE and T1804 and secondary amine. The synergism clearly improved the low temperature performance of Daqing diesel products and could reduce the cold filter plugging point of 0^# diesel by 6-7 ℃.

Selective oxidation of propane to acrylic acid over mixed metal oxide catalysts

The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 ℃ showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio （Mo1V0.31Te0.23Nb0.12）. The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H8 ：O2 ： H2O ： N2 = 4.4： 12.8 ： 15.3 ： 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.

NATURAL PRODUCTIVITY OF ACRYLIC ACID AND DIMETHYL SULPHIDE DURING A SUMMER BLOOM OF PHAEOCYSTIS POUCHETII IN ANTARCTIC COASTAL WATER

Water samples were collected over P. ponchetii bloom period beginning in November 1988, in 15m water column, from 10km offshore of Davis Station, Vestfold Hill, Antarctica. The concentrations of acrylic acid and dimethyl sulphide (DMS), which are toxic compounds in the water samples, were determined by HPLC and GC. The result shows that the concentration of acrylic acid varies in 0. 001 - 0. 510μmol ?L-1 and the concentration of DMS in 0. 003-0. 588 μmol ?L-1 during P. pouchetii bloom. Both the increased since late December 1988 and reached the highest concentration in early January 1989, then they decreased rapidly and returned to lower level from middle January to February in agreement with variation in cell number of the unicell alga P. pouchetii. The correlation coefficients between acrylic acid and P. pouchetii and between DMS and P. pouchetii are all 0. 998. It is undoubted that P. pouchetii produced acrylic acid and DMS. The highest productivity of acrylic acid and DMS were 9. 76X 10-8 umol cell-1 and 13. 09 ×10-8 μmol ?cell-1, respectively, during P. pouchelii bloom. A cellular product, dimethylsulphonium propionate (DMSP), is decomposed into acrylic acid and DMS, and the formation of DMSP is probably from methionine which could be utilized by P. pouchelii.

HZSM-35 zeolite catalyzed aldol condensation reaction to prepare acrylic acid and its ester:Effect of its acidic property

Acrylic acid(AA)and its ester,methyl acrylate(MA),were produced by a green one‐step aldol condensation reaction of dimethoxymethane and methyl acetate.The reaction was conducted over ZSM‐35 zeolites with different concentrations of Bronsted acid,which were prepared by the sodium ion‐exchange process with H‐form zeolite.The acidic property of HZSM‐35 was studied in detail through infrared experiments.About 51%of all bridging OH groups were distributed in cages,while 23%and 26%,respectively,were distributed in 10‐and 8‐ring channels.The catalytic performance was enhanced by a high concentration of Bronsted acid,indicating that Bronsted acid is an active site for the aldol condensation reaction.The ZSM‐35 zeolite possessing a concentration of Bronsted acid as high as 0.049 mmol/g demonstrated excellent performance with a MA+AA selectivity of up to 73%.

Studies on Graft Copolymerization of Acrylic Acid onto Ramie Fibers with Chromic Acid Initiation System

The graft copolymerization of acrylic acid (AA) with unswollen and swollen ramie fibers using chromic acid (H 2CrO 4) as the initiator has been studied in the presence of air. The effects of initiator concentration, monomer concentration, perchloric acid (HClO 4) concentration, time of polymerization, reaction temperature, and amount of ramie fibers on the graft percentage have been found out. The graft copolymer was characterized by IR spectra, scanning electron microscopy(SEM), differential thermal analysis (DTA), and thermogravimertric analysis (TGA).

Oxidation of propane to acrylic acid and acetic acid over alkaline earth-doped Mo-V-Sb-O_x catalysts

Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.The catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and XRD.Influence of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been studied.The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x catalysts.The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid.The catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.

Pretreatment of poly(acrylic acid) sodium by continuous diafiltration and time revolution of filtration potential

The pretreatment for the removal of small molecules from poly(acrylic acid) sodium (PAAS) solution by continuous diafiltration was investigated using ultrafiltration membrane. The effects of PAAS concentration, pH, trans-membrane pressure and pretreatment time on the permeate concentration and permeate flux were studied. The results show that the necessary pretreatment time (NPT) increases with PAAS concentration, decreases with TMP. The change trend of permeate flux with time is affected by pH. The permeate fluxes rapidly decrease from the start, and then increase gradually to stable values at pH 5.0, pH 7.0 and pH 9.3. However, it decreases gradually with time till a state value at pH 3.0 (iso-electric point, IEP). The removal of small molecules is easy at pH greater than iso-electric point (IEP). The change of filtration potential with time indicates the similar trend to that of permeation concentration, but the former is more convenient for indication of NPT.

Redox active polymer metal chelates for use in flexible symmetrical supercapacitors:Cobalt-containing poly(acrylic acid)polymer electrolytes

The novel polymer metal chelate electrolytes(polychelates)were prepared by incorporation of cobalt sulfate(Co)into poly(acrylic acid)(PAA)host matrix.Quasi-solid state supercapacitor devices were fabricated using polychelates,PAA-Co X(X:3,5,7,and 10)where X represents the doping fraction(w/w)of Co in PAA.All polymer metal electrolytes were showed excellent bending-stretching properties,thermal stability and electrochemical durability with an optimum ionic conductivity of 3.15×10^(-4) S cm^(-1).Hierarchically porous activated carbon and nano-sized conductive carbon were used to form carbon composite symmetrical device electrodes.The electric double-layer capacitor(EDLC)and redox reactions of Co-incorporated polychelates at the interfaces of porous activated carbon provided an optimum specific capacitance of 341.33 F g^(-1) with a device of PAA-Co7,which is at least 15 times enhancement compared to the device of pristine PAA.The PAA-Co7 device also provided energy density of 21.25 Wh kg^(-1) at a power density of 117.69 W kg^(-1).A prolonged cyclic stability of the device exhibited superior capacitive performance after 10,000 charge-discharge cycles and the maintained 90%of its initial performance.In addition,the supercapacitor with a dimension of 1.5 cm×3 cm containing PAA-Co7 successfully operated the red-blue-green(RGB)LED light.

PREPARATION OF POLY(ETHYLENEGLYCOL-co-ACRYLIC ACID) MICROSPHERES WITH DIVINYLBENZNE AS CROSSLINKER BY DISTILLATION-PRECIPITATION POLYMERIZATION

Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.

A MORPHOLOGICAL STUDY OF POLY(DIVINYLBENZENE-co-ACRYLIC ACID) IN CROSSLINKING PRECIPITATION POLYMERIZATION

Divinylbenzene-80 （DVB-80） and polar monomer acrylic acid （AA） having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2＇-azobis（isobutyronitrile） （AIBN） as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units.

CONFORMATIONAL CHARACTERISTICS OF POLY(ACRYLIC ACID) AND POLY(METHACRYLIC ACID)

A full-relaxation optimization of molecule and the Dreiding force field are employed to obtain the geometry parameters and the conformational energy surfaces of meso or racemic dyad of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA). Three different carbonyl-bond orientations of side-groups resulted in the differences in depth of potential wells in their energetic contours for a meso or a racemic dyad. These discrepancies are interpreted as a result of various fine structures corresponding to grid search conformations as well as thereby different interactions. The analysis on the most stable conformations of PMAA confirmed that the ester groups are nearly perpendicular to the plane defined by the two adjacent skeletal bonds but may possibly change their relative orientations to meet the requirement of lower energy during the conformational state transition. For each polymer, two global energy maps of a meso and a racemic dyad were finally constructed from the superposition of energy data for the three kinds of side-group orientations by the Boltzmann factors. From an ensemble average, the proposed scheme with three rotational isomeric states (RIS) allowed us to access the experimentally unperturbed dimensions of PAA chain via the configurational statistical mechanics. Although the calculation was based on the short-range, local interactions, it was interested to note that the experimental characteristic ratios just fell within the range calculated for atactic chains.

Graft Polymerization of Acrylic Acid on a Polytetrafluoroethylene Panel by an Inductively Coupled Plasma

Surface modification on a polytetrafluoroethylene （PTFE） panel was performed with sequential nitrogen plasma treatments and surface-initiated polymerization. By introducing COO- groups to the surface of the PTFE panel through grafting polymerization of acrylic acid （AA）, a transparent poly （acrylic acid） （PAA） membrane was achieved from acrylic acid solution. Grafting polymerization initiating from the active group5 was achieved on the PTFE panel surface after the nitrogen plasma treatment. Utilizing the acrylic acid as monomers, with COO- groups as cross link sites to form reticulation structure, a transparent poly （acrylic acid） membrane with arborescent macromolecular structure was formed on the PTFE panel surface. Analysis meth- ods, such as fourier transform infrared spectroscopy （FTIR）, microscopy and X-ray photoelectron spectroscopy （XPS）, were utilized to characterize the structures of the macromolecule membrane on the PTFE panel surface. A contact angle measurement was performed to characterize the modified PTFE panels. The surface hydrophilicities of modified PTFE panels were significantly enhanced after the plasma treatment. It was shown that the grafting rate is related to the treating time and the power of plasma.

The Application of Polytetrafluoroethylene (PTFE) Fiber Grafted Acrylic Acid as a Cation Exchanger for Removing Cu^(12)

The polytetrafluoroethylene fiber grafted acrylic acid was used as a cation exchanger. The exchange capacity of the cation fiber is 3.06 mmol/g. The maximum Cu2+ adsorption capacity is 107.48 mg/g. It could be desorbed completely by 1mol/L HCl.