Superabsorbent hydrogel of acrylic acid/potassium acrylate copolymers by ultraviolet photopolymerization: Synthesis and properties

Synthesis of superabsorbent hydrogel (SAHG) of acrylic acid‐potassium acrylate copolymer by direct Ultraviolet (UV) photopolymerization is a new method. The effects of degree of neutralization of acrylic acid (AA), photoinitiators, crosslinking agents, and exposure time of UV light on water absorbent properties were investigated. The results showed that the water absorbency (Q) and the salt solution (NaCl, 0.9%) absorbency (Qs) of SAHG, based on Irgacure 651, are high, reaching about 1400 and 130 mL/g, respectively. UV absorption spectrum proved that peak of UV absorption of Irgacure 651 matched the UV light source we used. Among the crosslinking agents, N,N′‐methylene bisacrylamide is more efficient than others, because of its very small content and high Q. ¹³C NMR spectrometry was used to identify the mechanism of crosslinking reaction through esterification of hydroxyethyl acrylate (HEA) and 2‐hydroxypropyl acrylate (HPA) with carboxylic acid group in acrylic acid‐ammonium acrylate copolymerization, but efficiency of crosslinking reaction by esterification was lower than that of copolymerization of vinyl group in crosslinking agent. The Q of acrylic acid‐potassium acrylate copolymer of SAHG reaches 1592 mL/g under the following conditions: degree of neutralization of acrylic acid is 80%, content of Irgacure 651 is 0.25 wt %, content of HEA is 0.2 wt %, and exposure time is 10 min. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1181–1187, 2006     

Synthesis and photopolymerization of acrylic acrylate copolymers

Acrylate‐functionalized copolymers were synthesized by the modification of poly(butyl acrylate‐co‐glycidyl methacrylate) (BA/GMA) and poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate). ¹³C‐NMR analyses showed that no glycidyl methacrylate block longer than three monomer units was formed in the BA/GMA copolymer if the glycidyl methacrylate concentration was kept below 20 mol %. We chemically modified the copolymers by reacting the epoxy group with acrylic acid to yield polymers with various glass‐transition temperatures and functionalities. We studied the crosslinking reactions of these copolymers by differential scanning calorimetry to point out the effect of chain functionality on double‐bond reactivity. Films formed from acrylic acrylate copolymer precursors were finally cured under ultraviolet radiation. Network heterogeneities such as pendant chains and highly crosslinked microgel‐like regions greatly influenced the network structure and, therefore, its viscoelastic properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 753–763, 2002     

Synthesis of superabsorbent resin by ultraviolet photopolymerization

Synthesis of superabsorbent resin (SAR) was achieved by a new method, that of direct UV photopolymerization, and in particular the synthesis of a SAR of acrylic acid–potassium acrylate copolymer by UV photopolymerization was investigated. Influences of ratio (mol) of acrylate monomer to acrylic acid monomer, photoinitiators, crosslinking agents, and exposure time of UV light on the water‐absorbent properties were investigated. The results showed that the water absorbency (Q) of SAR based on Irgacure 1700 or Irgacure 1800 was 545–530 mL/g, but under the same conditions Q was 450 mL/g for the SAR based on Irgacure 651. N,N′‐Methylene bisacrylamide, hydroethyl acrylate, and glycerol were used as crosslinking agents, of which N,N′‐methylene bisacrylamide was the most effective. It crosslinked the molecular chains through attending the copolymerization with acrylic acid (AA) and potassium acrylate. When the exposure time was 5 min, the value of Q was 1368 mL/g (the content of N,N′‐methylene bisacrylamide was 100 ppm). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1618–1624, 2004     

Synthesis of novel macrophotoinitiator for the photopolymerization of acrylate

A new kind of macrophotoinitiator (MPI) was synthesized through the copolymerization of acrylic monomers and the polymerizable photoinitiator monomer 2959‐AA. Monomer 2959‐AA was obtained by an esterification reaction between acrylic acid (AA) and the water‐soluble photoinitiator Irgacure 2959 [2‐hydroxy‐4‐(2‐hydroxyethoxy)‐2‐methylpropiophenone]. By adjusting the monomer proportions in the MPIs, two series of MPIs with different 2959‐AA contents and different glass transition temperatures were obtained. The molecular structure of 2959‐AA was characterized by Fourier‐transform infrared spectroscopy, nuclear magnetic spectrometry, and mass spectrometry. Polymerization of 1, 6‐hexanediol diacrylate was initiated using Irgacure 2959 and 2959‐AA, and two series of MPIs to be polymerized were studied with a photo‐DSC test. Results showed that 2959‐AA had higher chemical reactivity than Irgacure 2959 because of the higher solubility of the former. It was evident from the experiments that 2959‐AA content in the MPI progressively increased the polymerization rate and monomer conversion when the glass transition temperatures of MPIs were similar. At the same 2959‐AA content, the polymerization rate slightly slowed down with increased glass transition temperature. However, the radical lifetime and polymerization time were prolonged. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40352.     

pH‐response superabsorbant hydrogel synthesized by ultraviolet photopolymerization

A new synthesis method of pH‐response superabsorbent hydrogels (SHG) was achieved by direct ultraviolet (UV) photopolymerization, and in particular, the synthesis of SHGs of acrylic acid (AA), sodium acrylate (AANa), and methacrylcholine chloride (MACC) tricomponent copolymer by UV photopolymerization were investigated. The pH value responsive behavior of SHG with different monomer ratios of MACC and AA was researched, and SHG showed large swelling properties at pH value approximately 7. Influences of monomer ratio (mol) of AANa to AA, photoinitiators, crosslinking agents, and exposure time of UV light on the water absorbent properties were studied. The results showed that the water absorbent capacity of SHG based on photoinitiators: Esacure KTO46 or Irgacure 651 can reach comparatively high, N,N′‐Methylene bisacrylamide and diethylene glycol diacrylate (DEGDA) were high efficient crosslinking agents for its crosslinking the molecular chains through attending the copolymerization with monomers. When the exposure time was 10 min, the distilled water absorbency of SHG was 1503 mL/g under the condition: content of MACC, 14.3 wt %; monomer ratio (mol) of AANa to AA: 5.67; content of DEGDA and Irgacure 651, 0.0025 and 0.25 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1847–1852, 2007     

A novel porous epoxy acrylate resin monolith prepared by the low-temperature phase separation photopolymerization

A novel porous epoxy acrylate resin monolith has been successfully prepared by low-temperature phase separation photoinitiated polymerization. The process parameters of low-temperature photopolymerization, including photoinitiators type, concentration, and sample thickness were studied. The optimum conditions for the preparation of the sample were also evaluated. The results showed that the porous morphology of the prepared monolith was affected by monomer concentration, freezing speed and temperature of the solution. The average pore size increased with increasing solvent amount, decreasing freezing temperature and speed.     

Preparation and characterization of acrylic resin/titania hybrid nanocomposite coatings by photopolymerization and sol–gel process

Titania‐containing coatings were prepared through a dual‐cure process involving radical photopolymerization of a polysiloxane diacrylate and subsequent condensation of alkyltitanate groups. The kinetics of photopolymerization and condensation reaction was investigated as a function of the inorganic phase precursor (titanium tetraisopropoxide) content. AFM analysis gave evidence of a strong interaction between the organic and inorganic phase with the formation of titania domains in the nanoscale region. An increase of hydrophilicity in the coatings surface with increasing TiO₂ content was evidenced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4659–4664, 2006     

Degradation kinetics of acrylonitrile/ammonium acrylate copolymers

acrylonitrile (AN)/ammonium acrylate (AAT) copolymers were prepared by H₂O/dimethyl formamide suspension polymerization technique. Differential scanning calorimetry results of the degradation of AN/AAT copolymers in air are presented. The apparent activation energy of degradation of the copolymer was calculated by using Kissinger method. Effects of copolymerization conditions on the apparent activation energy of copolymer were studied. It has been found that increasing dimethyl formamide concentration in the solvent mixture leads to a rapid increase in the degradation apparent activation energy of AN/AAT copolymer. The value of the degradation apparent activation energy of the copolymer synthesized in dimethyl formamide solvent increases up to 141.7 kJ mol^?1. The apparent activation energy decreases quickly, along with increase in AAT concentration, and this change becomes less prominent as the weight ratio of AAT/AN goes beyond 6/94. The apparent activation energy shows a trend of increase with increasing copolymerization temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4649–4653, 2006     

Preparation of bentonite–poly[(acrylic acid)‐acrylamide] water superabsorbent by photopolymerization

A novel bentonite–poly[(acrylic acid)‐acrylamide] superabsorbent composite with water and salt solution absorbencies of 450 and 108 times its own weight, respectively, was successfully synthesized by photopolymerization of acrylic acid with acrylamide in the presence of bentonite powder using 30 min of ultraviolet irradiation at room temperature. The results show a synergetic effect of Michler's ketone and benzophenone mixed photoinitiators on the water absorbency, and incorporation of bentonite below 10 wt% into the water superabsorbent can slightly increase the water and salt solution absorbencies, and improve water retention, as demonstrated using thermogravimetric analysis and differential scanning calorimetry. Fourier transform infrared spectroscopy allowed the determination of the structure of the bentonite composite superabsorbent. Copyright © 2006 Society of Chemical Industry     

Resultant synergism in the shear resistance of acrylic pressure‐sensitive adhesives prepared by emulsion polymerization of n‐butyl acrylate/2‐ethyl hexyl acrylate/acrylic acid

Acrylic emulsion pressure‐sensitive adhesives (PSAs) were synthesized by the copolymerization of n‐butyl acrylate with various levels of 2‐ethyl hexyl acrylate (2EHA) and a small constant amount of acrylic acid. The effect of varying the n‐butyl acrylate/2EHA monomer composition on the kinetic behavior of the polymerization and the characteristics of the copolymers prepared in a batch process were investigated. The results showed that increasing the amount of 2EHA in the monomer caused the polymerization rate and the glass‐transition temperature of the acrylic copolymers to decrease. Increasing the amount of 2EHA caused the gel content of the copolymers to decrease, reaching a minimum at 50 wt %; thereafter, the gel content increased at higher 2EHA levels. For the acrylic emulsion, the peel‐fracture energy of the PSAs decreased as the amount of 2EHA in the monomer was increased up to 50 wt %. At higher 2EHA levels, the peel‐fracture energy was relatively constant. Interestingly, a synergistic effect of increased shear resistance at 25 wt % 2EHA was observed without a significant trade‐off in terms of the peel and tack properties. This behavior was attributed to a good interconnection between the microgels and the free polymer chains inside the contacting particles in the adhesive film. Cooperation between various levels of 2EHA in the copolymer structure simultaneously changed the crosslink molecular weight (M_c) of the microgels and the entanglement molecular weight (M_e) of the free chains in the adhesive network morphology. The adhesive performance of the PSAs was found to be correlated with their M_c/M_e values as the 2EHA proportion was varied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Removal of Basic Blue 3 by sorption onto a weak acid acrylic resin

A weak acid acrylic resin was used as an adsorbent for the investigation of Basic Blue 3 (BB3) adsorption kinetics, isotherms, and thermodynamic parameters. Batch adsorption studies were carried out to evaluate the effect of pH, contact time, initial concentration (28–100 mg/g), adsorbent dose (0.05–0.3 g), and temperature (290–323 K) on the removal of BB3. The adsorption equilibrium data were analyzed by the Langmuir, Temkin, and Freundlich isotherm models, with the best fitting being the first one. The adsorption capacity (Q_o) increased with increasing initial dye concentration, adsorbent dose, and temperature; the highest maximum Q_o (59.53 mg/g) was obtained at 323 K. Pseudo‐first‐order and pseudo‐second‐order kinetic models and intraparticle diffusion models were used to analyze the kinetic data; good agreement between the experimental and calculated amounts of dye adsorbed at equilibrium were obtained for the pseudo‐second‐order kinetic models for the entire investigated concentrations domain. Various thermodynamic parameters, such as standard enthalpy of adsorption (ΔH^o = 88.817 kJ/mol), standard entropy of adsorption (ΔS^o = 0.307 kJ mol^?1 K^?1), and Gibbs free energy (ΔG^o < 0, for all temperatures investigated), were evaluated and revealed that the adsorption process was endothermic and favorable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

紫外光引发聚(丙烯酸-丙烯酰胺)/膨润土高吸水性复合材料的制备研究

以N,N-亚甲基双丙烯酰胺(MBAM)为交联剂,Irgacure184为光引发剂,采用紫外光引发聚合的方法制备了聚(丙烯酸-丙烯酰胺)/膨润土高吸水性复合材料。研究了膨润土用量、光引发剂、交联剂、中和度等因素对吸水性能的影响,并用红外吸收光谱(FTIR)、X射线衍射(XRD)和扫描电镜(SEM)的方法表征了复合材料的结构和形态。     

Role of phenolic derivatives in photopolymerization of an acrylate coating

The photopolymerization of acrylate resins on wood surfaces suffers from retardation and inhibition effects due to the phenolic derivatives present at the interface. This article details the study of the effect of a set of phenolic compounds on the initiation step. The global effect was recorded by differential scanning calorimetry and photocalorimetry. A comparison between a direct photocleavable initiator such as 2,2‐dimethyloxy‐2‐phenylacetophenone (DMPA) and a two‐component system like benzophenone/N‐methyldiethanolamine (BP/MDEA) suggests that the retardation effect observed in the latter case is due to the interaction between phenols and the triplet state of BP. Subsequently, nanosecond transient absorption (NTA) spectroscopy was used to measure in acetonitrile the quenching rate constants k_Q. A hydrogen abstraction occurred, and the ketyl radical quantum yield was also determined by NTA experiments. In comparison with the photoreduction mechanisms proposed in the literature, the high k_Q values obtained were tentatively correlated to the half‐wave oxidation potentials of phenols in order to discuss the involvement of an electron transfer within the reaction. Some EPR experiments were done to confirm in situ the photoreduction process at the wood surface and the creation of phenoxyl radicals. The interaction of phenols with some initiating radicals was also studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2061–2074, 2000     

小麦秸秆接枝丙烯酸制备高吸水性树脂

以N,N'-亚甲基双丙烯酰胺为交联剂,过硫酸钾一硫代硫酸钠为引发剂,采用水溶液聚合法合成了小麦秸秆接枝丙烯酸系列高吸水树脂。研究了单体配比、丙烯酸中和度、引发剂及交联剂用量对吸去离子水的影响。结果表明,该树脂具有良好的吸水性能,吸收去离子水达617 g/g。     

Study of in-situ photopolymerization of chiral liquid crystal acrylate

The effect of the smectic and isotropic phase on the photo-polymerization of the chiral liquid crystalline 4-acryloxy-undecanyloxy-4′-[S(?)-2-methylbutyloxy]-biphenyl (monomer ( I )) was studied using FTIR. The effect of temperature on the birefringence of surface-oriented monomer ( I ) and its polymer obtained by in-situ photopolymerization was also investigated. The results show that photopolymerization in the isotropic phase proceeds at a higher rate than in the smectic phase, when monomer conversion is less than 60%; however, when monomer conversion is above 60%, the photopolymerization rate is independent of the initial phase state of monomer ( I ), and a highly oriented liquid crystalline polyacrylate film can be prepared by in-situ photopolymerization of the surface-oriented chiral acrylate ( I ).     

环氧有机硅油改性丙烯酸树脂的合成及性能

以偶氮二异丁腈为引发剂,通过丙烯酰氧基硅油与丙烯酸酯类单体的自由基共聚合反应,同时环氧828与丙烯酸共聚侧链羧基进行开环反应,合成以乙醇为主要溶剂的单相均匀牛顿型环氧有机硅油改性丙烯酸树脂。并对树脂涂膜的稳定性及硬度、耐水煮性,附着力等性能进行了研究。得到的树脂具有良好的热储稳定性,颜料广泛润湿性。环氧有机硅油改性丙烯酸树脂涂膜具有光泽高、硬度好、丰满度高、玻璃附着力强、耐水煮性好与透明性高等优异性能,适用于高档玻璃烤漆。     

Influence of ammonium polyphosphate on the mechanism of thermal degradation of an acrylic binder resin

The thermal behavior of an acrylic binder resin used in back coatings for textile applications was studied. The influence of the crystalline form of the fire‐retardant additive on the thermal behavior was investigated. This resin formed a carbon char during its thermal degradation, so it may be assumed that it acts as a charring agent in intumescent systems with ammonium polyphosphate (APP) as the acid source. Thermogravimetric and spectroscopic analyses of acrylic binder resin/APP mixtures demonstrated the influence of the crystalline form of APP. The degradation mechanism of the binder resin could be described by ring closure and the formation of unsaturations. APP leads to the formation of a phosphocarbon structure that is thermally stable, whatever the crystalline form was of APP. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 717–729, 2004     

Kinetic study on the UV‐induced photopolymerization of epoxy acrylate/TiO2 nanocomposites by FTIR spectroscopy

The kinetics of the photopolymerization of epoxy acrylate/TiO₂ nanocomposites, with 2′2‐dimethoxy‐1,2‐diphenylethan‐1‐one (Irgacure 651) or benzophenone/N‐methyl diethanolamine as photoinitiators, were studied by FTIR spectroscopy. It was found that nanocomposites had a decreasing photopolymerization rates in comparison with pure epoxy acrylate. The photopolymerization rate of the nanocomposite could also be influenced by initiator types, oxygen, film thickness, irradiation intensity, dispersing media of TiO₂ slurry, and so forth. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3281–3287, 2006     

环保型木薯淀粉接枝丙烯酸共聚物的合成研究

以N,N'-亚甲基双丙烯酰胺为交联剂、过硫酸铵为引发剂,采用水溶液聚合法制备了木薯淀粉接枝丙烯酸高吸水性树脂.考察了淀粉含量、中和度、引发剂用量、交联剂用量等因素对反应的影响.结果表明:在木薯淀粉含量为10%,引发剂用量为0.3%,交联剂用量为0.025%,丙烯酸与氢氧化钠的中和度为85%的条件下,制备得到的吸水性树脂吸水率达1355 g·g-1,其吸水速率快、加压保水能力强、热稳定性好.     

Synthesis and photopolymerization of 4‐(1‐propenyl)oxybutyl acrylate

Hybrid monomer, 4‐(1‐propenyl)oxybutyl acrylate, with cationic and free radical polymerizable group was synthesized. Real‐time Fourier transform infrared spectroscopy (FTIR) was used to monitor the photopolymerization kinetics of the monomer. Photopolymerization processing conditions, such as light intensity, photoinitiator concentrations have been evaluated. It was found that hybrid monomer showed higher efficiency of photopolymerization in comparison with the blend system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008