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.

Water-Based Processing of Fiberboard of Acrylic Resin Composites Reinforced With Cellulose Wood Pulp and Cellulose Nanofibrils

Despite the great potential of cellulose wood pulp and cellulose nanofibrils as reinforcing filler in thermoplastics,its use is limited due to its tendency to form agglomerates and due to its high hydrophilic character.Here we describe fiberboard composites with high contents of wood pulp or cellulose nanofibrils,and a resin of poly(styrene-methyl-methacrylate-acrylic acid)used as water-based emulsion.Cellulose wood pulp and cellulose nanofibrils were used directly in the form of water suspensions.The method is based on the flocculation of the polymer emulsion followed by agglomeration of a mixture of the polymer emulsion and cellulose suspension,leading to the co-precipitation of the composite material,which can be easily separated from the water phase.Composites with acrylic polymer/cellulose fibers in the proportions of 75:25,50:50 and 25:75 wt%were prepared.Composites were characterized by scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),thermogravimetric analysis(TGA),dynamic mechanical analysis(DMA)and water absorption tests.SEM analysis revealed a very good dispersion of the fibers without evidence of agglomeration,which led to superior mechanical properties.These results showed the effectiveness of the methodology and the potential of cellulose wood pulp and CNF as reinforcement fillers in fiberboard composites and any other high fiber-content materials.

Preparation and Characterization of Two-component Waterborne Polyurethane Comprised of Water-soluble Acrylic Resin and HDI Biuret

A two-component waterborne polyurethane(2K-WPU) was prepared by mixing water-soluble acrylic resin and hexamethylene diisocyanate biuret, and then diluted for phase inversion with water. Compared with water-soluble acrylic resin, the phase inversion of 2K-WPU occurs at lower water content. It is indicated by TEM that 2K-WPU parti-cles show a core-shell structure, in which HDI biuret is encapsulated by hydrophilic acrylic resin. 2K-WPU emulsion with HDI biuret has larger particle size and narrower distribution index, while for 2K-WPU emulsion with HDI iso-cyanurate, the latex not only has large particle size, but also has two-peak distribution. FTIR shows that the reaction be-tween HDI biuret and acrylic resin can complete in 12h. In addition, studies on effect of composition of acrylic resin on performance of 2K-WPU show that narrowing the polar difference between water-soluble acrylic resin and HDI biuret and improving the miscibility of two components are the key to prepare the transparent and high gloss films with high crosslinking density.

Synthesis and Application of a New Acrylic Ester Resin for Recycling SIPA from its Water Solution

A new acrylic ester polymer YWB-7 resin was prepared and characterized. The properties of YWB-7 resin were compared with those of the commercial Amberlite XAD-7, Diaion HP2MG and hypercrosslinked macroporous polymer NDA-150 resins. Both surface area and micropore area of YWB-7 resin were bigger than those of XAD-7 resin and HP2MG resin. The YWB-7 resin was successfully employed to recycle 5-sodiosulfoisophthalic acids （SIPA） from its solutions with and without methanol.

Application of reactive acrylate microgels in water-base coatings

Reactive acrylate microgels with different reactive groups such as carboxyl, hydroxide groups had excellent properties such as quick-dry, low viscosity, high adhesion and hardness, which made them extensively used in preparing paints or in coating-modification. Reactive acrylate microgels were prepared by emulsion co-polymerization with zwitterions surfactant, anionic surfactant and nonionic surfactant as co-emulsifier. The water-base baking paints made from reactive acrylate microgels and melamine-formaldehyde resin had excellent combination properties. The aluminium powder can be well-dispersed in the paints. The influences of monomer components on the properties of the water-base baking paints were discussed in this paper. And the baking paints were also compared with the marketing solvent acrylate baking paints. It was found that the water-base acrylate amino baking paints had better combination properties than the organic solvent acrylate baking paints, which means that the water-base baking paints had a bright marketing future.

PHOTOCURING STUDY OF NEW DENTAL RESINS BASED ON MULTIFUNCTIONAL ACRYLIC ISOCYANURATE BY PHOTOCALORIMETRY

Photocuring of new dental resins composed of tri(2-hydroxyethyl) isocyanurate triacrylate (THITA) alone and its mixtures with trimethylolpropane triacrylate (TMPTA) or pentaerythritol triacrylate (PETA) initiated by camphorquinone/amine system was studied by photocalorimetry. Among several different amines as coinitiators, 2-ethyl-4-dimethylaminobenzoate (AM-3), N,N-dimethylbenzylamine (AM-5) and 2,4,6-[tri(dimethylaminomethyl)]phenol (AM-6) are most effective. Upon irradiation, photopolymerization can occur immediately and no induction period appears in N-2 nor in air. Comparing the THITA/TMPTA and THITA/PETA mixtures, the parameters of photopolymerization and hardness of photocured samples show a small difference and only change slightly with varying molar ratios of mixture. In the presence of inorganic filler, the hardness of photocuring resins is almost the same as that for commercial products.

CURING KINETICS AND PROPERTIES OF ACRYLIC RESIN CURED WITH AZIRIDINE CROSSLINKER

A kind of aziridine crosslinkers was synthesized and used to crosslink acrylate copolymers. The crosslinking properties and curing kinetics of the resin were studied. It was found that with the increase of the content of crosslinker in the emulsion, the mechanical properties and solvent resistance of the resin will be apparently improved, but its glass transition temperature (T.) is very low. The lowest amount of crosslinker used in the acrylic resin emulsion is 0.25%. Curing kinetics studied by DSC show that this curing reaction occurs readily because the apparent activation energy of the reaction is low (65.1 kJ/mol). These results demonstrate that the aziridine crosslinker is indeed a low temperature crosslinking agent and can be used at room temperature.

Effects of Chairside Polishing and Brushing on SurfaceRoughness of Acrylic Denture Base Resins

The effects of 3 chairside polishing kits and mechanical brushing on the surface roughness of 3 different acrylic denture base resins were compared. Acrylic denture base resins （auto-polymerizing, heat-polymerizing, injected heat-polymerizing resins） were examined after a tungsten carbide bur, and after chairside polishing using 3 polishing kits and pumice. The specimens were subjected to mechanical brushing using a wear tester to simulate 30 000 strokes of brushing. The surface roughness of the acrylic denture base resin specimens was measured using a contact pro-filometer. After the test, the random polished acrylic resins were evaluated by scanning electron mi-croscopy （SEM） and atomic force microscopy （AFM）. Acrylic denture base resins polished using the 3 types of polishing kits had a smoother surface than those finished with the tungsten carbide bur （p〈0.05）. The surface of the resin polished by a TC cutter exceeded the Ra of 0.2 μm （p〈0.05）. The auto-polymerizing resin showed a significantly higher surface roughness than the heat-polymerizing resin and injected heat-polymerizing resin （p〉0.05）. In the case of polishing step wise, there was almost no change in surface roughness after brushing （p〉0.05）.

Effect of Zirconium Oxide Nano-Fillers Addition on the Flexural Strength, Fracture Toughness, and Hardness of Heat-Polymerized Acrylic Resin

Purpose: The mechanical strength of polymethyl methacrylate (PMMA) remains far from ideal for maintaining the longevity of denture. The purpose of this study was to evaluate the effect of Zirconium oxide (ZrO2) nanofillers powder with different concentration (1.5%, 3%, 5% and 7%) on the flexural strength, fracture toughness, and hardness of heat-polymerized acrylic resin. Materials and methods: Zirconium oxide powders with different concentrations (1.5%, 3%, 5% and 7%) were incorporated into heat-cure acrylic resin (PMMA) and processed with optimal condition (2.5:1 Powder/monomer ratio, conventional packing method and water bath curing for 2 hours at 95。C) to fabricate test specimens of PMMA of dimensions (50 × 30 × 30 mm) for the flexural strength, fracture toughness, and (50 × 30 × 30 mm) were fabricated for measuring hardness. PMMA without additives was prepared as a test control. Three types of mechanical tests;flexural strength, fracture toughness and hardness were carried out on the samples. The recorded values of flexural strength in (MPa), fracture toughness in (MPa.m1/2), and hardness (VHN) were collected, tabulated and statistically analyzed. One way analysis of variance (ANOVA) and Tukey’s tests were used for testing the significance between the means of tested groups which are statistically significant when the P value ≤ 0.05. Results: Addition of Zirconium oxide nanofillers to PMMA significantly increased the flexural strength, fracture toughness and hardness. Conclusion: These results indicate that Zirconium oxide nanofillers added to PMMA has a potential as a reliable denture base material with increased flexural strength, fracture toughness, and hardness. According to the results of the present study, the best mechanical properties were achieved by adding 7%wt ZrO2 concentration.

Effect of Titanium Dioxide Nano Particles Incorporation on Mechanical and Physical Properties on Two Different Types of Acrylic Resin Denture Base

The aim of this study is to clarify the effect of different concentrations of titanium dioxide nanoparticles (Nps) on the properties of two types of heat polymerized acrylic resin. The tested parameters were flexural strength, impact strength, and microhardness. The two types of acrylic resin used in this study were conventional unmodified (Implacryl, Vertex) and high impact heat polymerized acrylic resin (Vertex-Dental, Netherlands). Both types of acrylic resin were modified by using 1% and 5% TiO2 Nps powder. Specimen’s dimensions were prepared according to the American Dental Association Specification No. 12. Three types of specimens were prepared: 1) flexural strength specimens 50 mm × 10 (±0.2) mm × 3 (±0.2) mm, 2) impact strength test specimens 60 mm × 6.0 mm × 4.0 mm, 3) microhardnesss specimens 25 mm × 10 mm × 3 (±0.2) mm. For each test 6 groups were prepared (each group containing 5 samples). Thirty specimens were prepared in each of the three tests, amounting to a total number of 90 specimens. Mechanical properties such as flexural strength (FS), impact strength and microhardness of the above mentioned specimens were determined using universal testing machine, Izod pendulum impact testing machine and Vickers microhardness tester, respectively. ISO Specification No. 1567 was followed in microhardness test. The data was collected and statistically analyzed. Flexural strength considerably decreased by increasing TiO2 concentration in both types of acrylic resin. Impact strength of the conventional acrylic resin modified by 1% of additives significantly increased. The microhardness is significantly increased by addition of 5% of TiO2 Nps. The Incorporation of TiO2 nanoparticles into acrylic resins can adversely affect its flexural strength. Meanwhile, the impact strength can be modified by small percentage of additives (abt. 1%). This effect is directly correlated with the concentration of nanoparticles. On the other hand, concentrations of TiO2 Nps (abt. 5%) positively affect the microhardness of both types of acrylic resin used in the present study.

EFFECTS OF PHENOL RESIN ADDITIVE ON DYNAMIC MECHANICAL PROPERTIES OF ACRYLATE RUBBER AND ITS BLENDS

The dynamic mechanical properties of a new blend system consisting of phenol resin and polar polymer (acrylaterubber and/or chlorinated polypropylene) were investigated. It was found that the addition of phenol resin to acrylate rubberand its incompatible blend can cause a remarkable improvement in the temperature dependence of the loss tangent. As a result, the present blends are very good damping materials.

Preparation, morphology and mechanical properties of acrylate-modified polyurethane/unsaturated polyester resin graft-IPNs

Acrylate modified polyurethane resin was first synthesized, and interpenetrated with unsaturated polyester resin to form IPNs and gradient IPNs which cured at room temperature. The polymerization process was traced by an IR spectroscopy technique and the simultaneous interpenetrating techniques were determined. The morphology of these IPNs were estimated by TMA and TEM methods. The results indicated that large amount of interpenetrating and entanglement make T g linked up effectively, and domains between two phases can be in nanometre ranges, which changed with composition ratios. The mechanical properties results showed that IPNs varied from elastomeric to plastic materials. It was noteworthy that, with the introduction of modified groups and the formation of graft construction in IPNs, the miscibility in the systems was improved a lot. These further led to the improved mechanical properties of IPNs with elastomer reinforced and plasticizer toughened as well. The reinforced miscibility between the networks can apparently change mechanical property especially for the gradient ones when the materials are elongated.

SYNTHESIS OF SOAP-FREE ACRYLIC HYDROSOLS

Poly(methyl methacrylate/ethyl acrylate/acrylic acid) hydrosols were prepared by employing soap-free polymerization, and (acrylic acid/butyl acrylate) oligomer was used as the polymeric surfactant. The effect of reaction condition on the morphology and particle size of the hydrosols was investigated. The minimum amount of acrylic acid in the hydrosols is 2%. The maximum weight average molecular weight (M-w) of polymer that assures soap-free emulsion conversion into hydrosol is about 1.2 x 10(5)-1.3 x 10(5). The particle transforming process was investigated, and an obvious change of particle diameter and morphology was observed.

PREPARATION AND PROPERTIES OF THERMOSETTING ACRYLIC COATINGS USING TITANIUM-OXO-CLUSTER AS A CURING AGENT

Thermosetting acrylic coatings were prepared by using carboxyl acid group-containing acrylic oligomer and curing with titanium-oxo-clusters which were first pre-hydrolyzed from titanium n-butoxide.The curing ability of the titanium-oxo-cluster was examined using a microdielectric analytical(DEA)curing monitor,Fourier transformed infrared spectroscopy(FTIR),and Soxhlet extraction experiments,and the properties of the resulted coatings were investigated with pendulum hardness tester,dynamic mechanical analysis(DMA),thermogravimetric analysis(TGA)and ultraviolet-visible spectrometer.The effect of titania-oxo-cluster in leading acrylic oligomers to form thermosetting acrylic coatings was confirmed.An increasing pendulum hardness and modulus of acrylic coatings with increasing titania content was observed, which resulted from the increment of crosslinking degree rather than of the titania content.The thermosetting acrylic/titania coatings also showed better thermal stability and higher UV-blocking properties than those coatings using organic curing agent.

Studies on interacting Blends of Acrylated Epoxy resin based Poly(Ester-Amide)s and Vinyl EsterResin

Epoxy resin based Unsaturated poly(ester-amide) resins (UPEAs) can be prepared by many methods but here these were prepared by reported method [1]. These UPEAs were then treated with acrylotl chloride to afford acrylated UPEAs resin (i.e. AUPEAs). Interacting blends of equal proportional AUPEAs and vinyl ester epoxy (VE) resin were prepared. APEAs and AUPEAs were characterized by elemental analysis, molecular weight determined by vapour pressure osmometer and by IR spectral study and by thermogravimetry. The curing of interacting blends was monitored on differential scanning calorimeter (DSC). Based on DSC data in situ glass reinforced composites of the resultant blends have been prepared and characterized for mechanical, electrical and chemical properties. Unreinforced blends were characterized by thermogravimetry (TGA).

Influence of Glass Fiber wt% and Silanization on Mechanical Flexural Strength of Reinforced Acrylics

The aim is to evaluate the flexural strength of acrylic resin bars depending on the addiction of glass fibers with or without previous 3-methacryloxypropyl-trimethoxysilane (silane) application. Short fibers (3 mm) were treated and added to an acrylic resin powder, being further mixed with acrylic liquid to create bars (25 × 2 × 2 mm) of 11 experimental groups (N = 10), according to the interaction of experimental factors: weight % of glass fibers: (0.5;1;3;4;6 and 7) and silane application (with silane (S) or without silane (N)). Flexural strength and scanning microscopy evaluation were performed (SEM). Data (MPa) were submitted to ANOVA and Tukey (α = 5%). A significant difference between groups was observed (p = 0.001): S7%(128.85 ± 35.76)a, S6% (119.31 ± 11.97)ab, S4% (116.98 ± 25.23)ab, N4% (107.85 ± 24.88)abc, S1% (96.29 ± 20.65)bc, S0.5% (89.29 ± 7.33)cd, S3% (89.0 ± 11.27)cd, N3% (86.79 ± 17.63)cd, N1% (85.43 ± 16.44)cd, Control (73.29 ± 25.0)de, N0.5% (59.58 ± 19.46)e. For N groups, it was not possible to include more than 4%wt fibers. SEM showed better fiber-resin interaction for S groups, and fractures around fibers on N groups. Previous silane application enables the addiction of greater quantity of glass fibers and better interaction with the acrylic resin resulting in higher flexural strength. Without silane, fibers seem to act as initial crack points due to poor interaction.

水利工程用环氧树脂改性聚氨酯丙烯酸酯性能研究

水利工程金属结构和水工建筑物常遭受腐蚀、高速含沙水流磨蚀破坏,需对其进行便捷有效的防护。利用环氧树脂对聚氨酯丙烯酸酯(PUA)进行改性提高PUA与基体黏结性能,采用紫外光(UV)固化技术制备PUA涂层。研究了环氧树脂改性PUA的化学结构及环氧树脂用量对PUA的力学性能、热稳定性能、耐溶剂性能和抗冲磨性能的影响。结果表明,环氧树脂改性PUA的拉伸强度随着环氧树脂用量增加,呈下降趋势,当加入5%时,PUA拉伸强度为103.0 MPa,材料呈强而脆的特性。环氧树脂加入提升了PUA的拉伸剪切强度,由0.25 MPa增至1.60 MPa。同时,环氧树脂改性PUA具有良好的耐水性能、耐溶剂性能、抗冲磨性能,5%环氧树脂改性PUA抗冲磨强度为800 h/(kg·m^(2))。

丙烯酸硅烷酯柔性自抛光防污涂料制备及性能

以甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸甲氧基乙酯、丙烯酸三异丙基硅酯为单体,制备了丙烯酸硅烷酯基体树脂,将其与韧性树脂(液态聚丁二烯)共同作为成膜共混树脂,并以Cu_(2)O作为主要防污剂组分、吡啶硫酮铜(CuPT)和代森锌(Zineb)为辅助有机防污剂组分,配制了柔性自抛光防污涂料。对丙烯酸硅烷酯基体树脂进行了FTIR表征和玻璃化转变温度(Tg)测定,对成膜共混树脂进行了SEM测试,对柔性自抛光防污涂料进行了柔韧性、附着力、吸水率和防污性能测试。结果表明,丙烯酸硅烷酯基体树脂的Tg=–20.54℃时,具有较好的物理机械性能;韧性树脂可以作为外增塑手段增加丙烯酸硅烷酯基体树脂的柔韧性,当m(丙烯酸硅烷酯基体树脂)∶m(韧性树脂)=7∶3时,成膜共混树脂的相容性最好;柔性自抛光防污涂料柔韧性为1级,在弹性体基材表面附着力达到4.0 MPa;经过60 d测试,吸水率为1.1%~1.2%;浅海浸泡挂板36个月显示出明显的防污效果。

无光耐沾污蒙皮面漆的研制及其应用

介绍了蒙皮涂层耐沾污性的影响因素以及无光蒙皮面漆耐沾污的难点。对比了丙烯酸树脂体系无光、半光、高光漆膜的耐沾污性,并研究了氟碳树脂的添加量对无光漆膜耐沾污性的影响。结果表明:无光丙烯酸树脂体系的漆膜因消光粉添加量高,其表面粗糙度大,导致耐沾污性较差;在丙烯酸树脂体系中加入氟碳树脂,可提高无光漆膜的耐沾污性;且当丙烯酸树脂与氟碳树脂的比例接近1:1时,既能满所需的性能要求,又能降低成本。