Diglycidyl Ether Diacrylate Research Articles

Preparation and evaluation of novel bio-based Bis-GMA-free dental composites with low estrogenic activity

ObjectiveAlthough bisphenol Aglycidyl methacrylate (Bis-GMA) are widely used in the dental composite, its raw materials include the petroleum-based product bisphenol A (BPA) with high estrogenic activity (EA). In this study, two new BPA-free dimethacrylate monomers from bio-based material creosol were synthesized and evaluated. MethodsThe renewable bisphenol monomer 5, 5'-methylenedicreosol (BCF) was prepared from bio-based material creosol. By the human breast cancer cells (MCF-7 cells) proliferation assay, a risk assessment of BCF was performed to determine if BCF possessed reduced EA in comparison to BPA. Then, the novel monomers 5, 5'-methylenedicreosol diglycidyl ether diacrylate (BCF-EA) and 5, 5'-methylenedicreosol diglycidyl ether dimethacrylate (BCF-GMA) were synthesized from BCF with epichlorohydrin and (meth)acrylate. All products were investigated by 1H NMR and FT-IR spectra. The control resin was a mixture based on Bis-GMA and tri(ethyleneglycol) dimethacrylate (TEGDMA) with a weight ratio of 5:5 (5B5T). Similarly, experimental resin matrix was a mixture based on BCF-EA/TEGDMA (5E5T) and BCF-GMA/TEGDMA (5G5T). And their corresponding composites were then prepared with corresponding resin matrices and hybrid SiO2 (5E5TC, 5G5TC and 5B5TC). The properties of these composites were investigated according to the standard or referenced methods. Each sample was evaluated for double bond conversion (DC), shrinkage stress (SS) and volumetric polymerization shrinkage (VS). Water sorption (WS), water solubility (SL), mechanical properties and cytotoxicity were also measured. Results1H NMR and FT-IR spectra confirmed the chemical structure of each monomer. EA test revealed that bio-based bisphenol monomer BCF as the precursor of BCF-EA and BCF-GMA showed lower EA than BPA. Cured resin matrix: Both 5E5T and 5G5T had nearly the same DC (p < 0.05), which was higher than 5B5T (p < 0.05); 5E5T and 5G5T had lower VS, SL and cytotoxicity than 5B5T (p < 0.05); mechanical properties of 5E5T and 5G5T were all better than those of 5B5T (p < 0.05). Cured composite: There was no significant difference in conversion (p < 0.05); 5E5TC and 5G5TC had significantly lower VS (p < 0.05); WS of 5E5TC and 5G5TC were similar (p < 0.05), but higher compared to 5B5TC (p < 0.05); 5E5TC and 5G5TC had the deeper depth of cure (p > 0.05); before water immersion, there was no significant difference in flexural strength between 5E5TC and 5G5TC (p > 0.05), and higher than 5B5TC (p < 0.05); 5E5TC and 5G5TC showed less cytotoxicity than 5B5TC (p < 0.05). SignificanceThe new BPA-free di(meth)acrylates are promising photocurable dental monomers owning to bio-based raw material, high degree of conversion coupled with low curing shrinkage and good mechanical properties. Therefore, BCF-EA and BCF-GMA has a potential to be used as the substitution for Bis-GMA to prepare Bis-GMA-free dental composite.

In Situ Co–O Bond Reinforcement of the Artificial Cathode Electrolyte Interphase in Highly Delithiated LiCoO2 for High-Energy-Density Applications

Highly delithiated LiCoO2 has high specific capacity (>200 mAh g-1); however, its degradation behavior causes it to have poor electrochemical performance and thermal instability. The degradation of highly delithiated LiCoO2 is mainly induced by oxygen vacancy migration and weakening of oxygen-related interactions, which result in pitting corrosion and fault formation on the surface. In this research, a coupling agent, namely, 3-aminopropyltriethoxysilane (APTES), was grafted onto the surface of LiCoO2 to form a cross-linking structure. Through the aza-Michael addition reaction, an oligomer formed from barbituric acid and bisphenol a diglycidyl ether diacrylate were reacted with the cross-linking APTES to form an artificial cathode electrolyte interphase (ACEI). The highly delithiated LiCoO2 containing the ACEI had considerably less degradation on the surface of the bulk material caused by oxygen release. The formation of the O1 phase was prevented in high delithiation and high-temperature operations. This research revealed that the ACEI reinforced the Co-O bond, which is crucial in preventing gas evolution and O1 phase formation. In addition, the ACEI prevents direct contact between the electrolyte and highly active surface of LiCoO2, thereby preventing the formation of a thick and high impedance traditional cathode electrolyte interphase. According to the present results, highly delithiated LiCoO2 containing the ACEI exhibited outstanding cycle retention and capacity at 55 °C as well as low heat capacity release in the fully delithiated state. The ACEI considerably protected and maintained the electrochemical performance of highly delithiated LiCoO2, which is suitable for high-energy-density applications, such as electric vehicles and power tools.

Improvement in the electrochemical stability of Li[Ni0.5Co0.2Mn0.3]O2 as a lithium-ion battery cathode electrode with the surface coating of branched oligomer

Although layered Li[Ni0.5Co0.2Mn0.3]O2 (LNCM 523) is one of the most promising cathode materials for lithium-ion batteries, large capacity losses during charging and discharging, due to poor surface stability, have limited its application. Surface modifications can be effective at improving the electrochemical performance of cathode materials. In this study, an oligomer polymer, named LIVING, was synthesized from bisphenol A diglycidyl ether diacrylate and barbituric acid and then used it as a coating material for LNCM 523 particles. Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, and electrochemical methods were employed to investigate the structure, surface properties, thermal stabilities, and electrochemical properties of the electrodes. Both coated (LIVING@LNCM 523) and uncoated (LNCM 523) electrodes were tested for their battery performance. A cathode material coated with 0.5 wt.% of LIVING (0.5% LIVING@LNCM 523) at a layer thickness of approximately 10 nm showed enhanced cycle stability, with over 80.7% of the capacity retained after 100 cycles at a rate of 0.2C; in comparison, the LNCM 523 electrode retained no more than 66.2% of its capacity under the same conditions. The coated electrode (0.5% LIVING@LNCM 523) also exhibited a better rate capability, retaining about 91% of its initial capacity after applying various current loads, whereas LNCM 523 retained only 79% after applying the same current loads under the same conditions. The improved electrochemical performance of the modified electrode is attributed to the chemical interactions between LNCM 523 and LIVING providing a uniform and stable oligomer layer on the LNCM 523 surface, thereby preventing the LNCM 523 surface from deeper electrolyte ion intercalation and suppressing the growth of interfacial resistance. The coating material (LIVING) appears to have great potential for improving the electrochemical performance of layered structure cathode materials, with promising applications in highly energy demanding lithium-ion batteries.

Study on curing behaviors of epoxy acrylates by UV with and without aromatic component

Two kinds of epoxy acrylates, aromatic BAGEDA (bisphenol A diglycidyl ether diacrylate) and aliphatic BDGEDA (1,4-butanediol diglycidyl ether diacrylate), were prepared from BADGE (bisphenol A diglycidyl ether) and BDDGE (1,4-butanediol diglycidyl ether) respectively by reacting with acrylic acid. Synthesis and change in functional groups were confirmed by FTIR spectra. In the studies of UV curing behaviors by Photo-DSC (differential photocalorimetry), rate constants and conversions under isothermal conditions (T cure =30-80 °C) were determined by exothermic heat flows. Thus, maximum reaction rates of BAGEDA and BDGEDA were 4.06×10-2 s-1 and 5.01×10-2 s-1 respectively. UV curing behaviors were confirmed to follow Kamal equation model. Activation energies were 23.5 kJ/mol (E a1) and 12.0 kJ/mol (E a2) for BAGEDA, and 25.0 kJ/mol (E a1) and 11.3 kJ/mol (E a2) for BDGEDA. In the UV curing reaction of BAGEDA, the maximum reaction rate constants and conversions were increased by increasing reaction temperatures (T cure ), while in that of BDGEDA those were increased until 60 °C followed by a gradual decrease above 60 °C. These phenomena were understood by Gillham’s time-temperature-transformation (TTT) diagram in which curing behavior was determined by the glass transition temperature (T g ) of cured material at each reaction temperature.

Synthesis and properties of a low-viscosity UV-curable oligomer for three-dimensional printing

A novel photosensitive low-viscosity epoxy acrylate resin was synthesized by utilizing polyethylene glycol diglycidyl ether (PEGGE) and acrylic acid (AA) as starting materials. The structure of polyethylene glycol diglycidyl ether diacrylate (PEGGEA) was characterized by Fourier transform infrared spectroscopy (FTIR). 2-Isopropyl thioxanthone (ITX), ethyl 4-(dimethylamino) benzoate (EDAB) and 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone (369) as photoinitiators and trihydroxymethyl propane triacrylate (TMPTA) as monomer were mixed with PEGGEA to prepare a kind of UV-curable resins, which may be utilized to boost the resin curing under UV light. The UV-curing properties and the thermal stability of the prepared resins with different contents of oligomer were investigated using FTIR-attenuated total reflection (ATR) spectroscopy and TGA. The viscosity of the oligomers and the mechanical properties of the cured resins were also studied. The results showed that the content of oligomer will affect the UV-curing properties and the thermal stability of the UV-curing resins. The viscosity of the prepared UV-curing resins was less than 200 mPa s at 25 °C, and the hardness of cured resins was high than 6H, which could meet the requirements for three-dimensional printing (3DP).

Synthesis of a novel UV-curable oligmer 1,4-cyclohexanedimethanol glycidyl ether acrylate and study on its UV-curing properties

A novel UV-curable oligmer 1,4-cyclohexanedimethanol glycidyl ether acrylate (CHDMGEA) was synthesized by utilizing 1,4-cyclohexanedimethanol glycidyl ether (CHDMGE) and acrylic acid (AA) as starting materials, triphenyl phosphine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were that the concentration of triphenyl phosphine was 0.90% of reactants by weight, the concentration of p-hydroxyanisole was 0.20% of reactants by weight, the reaction temperature was 90–100 °C, and the molar ratio of CHDMGE to AA was 0.5:1.1. The experimental results show that CHDMGEA is a kind of good UV-curable oligmer. The impact resistance of the UV-cured films with CHDMGEA as oligmer to prepare UV-curing coating was superior to that of the UV-cured films with bisphenol A diglycidyl ether diacrylate (BPGEA) as oligmer to prepare UV-curing coating.

Non-isothermal degradation of bisphenol A diglycidyl ether diacrylate-based polymers

Non-isothermal degradation kinetics of cured polymer samples of barbituric acid (BTA)/bisphenol A diglycidyl ether diacrylate (EA) and benzoyl peroxide (BPO)/EA was investigated. The sample of BTA/EA exhibited an inferior thermal stability as compared to the BPO/EA counterpart (as the reference sample). The degradation kinetics for both cured polymer samples of BTA/EA and BPO/EA were determined by the model-fitting method with the aid of a deconvolution technique. For the sample of BTA/EA, the complex degradation process was described by the diffusion-controlled and reaction-controlled mechanisms in the first and second steps, respectively. For the sample of BPO/EA, the mechanism responsible for the first step of the degradation process was reaction-controlled. By contrast, the degradation process was described by the nucleation-controlled mechanism, followed by the multi-molecular decay law in the second step. Different degradation kinetics and mechanisms between cured polymer samples of BTA/EA and BPO/EA were attributed to their different crosslinked network structures.

Kinetics of free radical polymerization of bisphenol A diglycidyl ether diacrylate initiated by barbituric acid

Non-isothermal radical polymerization kinetics for barbituric acid (BTA)/epoxy diacrylate (EA) and benzoyl peroxide (BPO)/EA (serving as the reference) in NMP were investigated. The DSC data showed that the activation energy of the polymerization of EA initiated by BTA was much lower than that initiated by BPO. For polymerizations of BTA/EA and BPO/EA except BPO/EA=3/100 (w/w), the reaction mechanism involving nucleation, followed by nucleus growth in the first stage was proposed. For the polymerization of BPO/EA [3/100 (w/w)], the reaction system was adequately described by the instantaneous nucleation and nucleus growth mechanisms in the first stage. Moreover, the nucleation and subsequent growth of microgel nuclei were primarily governed by the propagation reaction and diffusion-controlled termination reaction for the polymerization system of BTA/EA or BPO/EA. In the second stage (in the conversion range 0.75–0.90), the diffusion-controlled propagation and termination reactions governed the development of highly crosslinked macrogel (i.e., macroscopic agglomerate).

Organic/inorganic nanocomposite coating of bisphenol A diglycidyl ether diacrylate containing silica nanoparticles via electron beam curing process

The paper presents the fabrication of organic/inorganic nanocomposite coatings via a solvent free, environment benign-electron beam curing process using Bisphenol A diglycidyl ether diacrylate (BDGDA) as an oligomer, 1,6-Hexandioldiacrylate (HDDA) as a reactive diluent, and SiO2 nanoparticles as inorganic nano-reinforcing component. Silica nanoparticles were modified by 60Co-gamma radiation induced grafting of glycidyl methacrylate (GMA) and 2-hydroxyethyl methacrylate (HEMA), before dispersing them into coating compositions for their better compatibility with coating formulations. Surface modified silica nanoparticles were characterized by FTIR spectroscopy and thermogravimetric analysis (TGA). The rheological behavior of coating formulations was evaluated using Brookfield viscometer; formulations with surface modified SiO2 nanoparticles exhibited pseudoplastic type non-Newtonian behavior. EB cured nanocomposite coatings were characterized by TGA, differential scanning calorimetry (DSC), atomic force microscopy (AFM), scanning electron microscopy (SEM) and contact angle (wettability) measurement. AFM and SEM analysis showed that the dispersion of silica nanoparticles in the coatings improved after surface modification. DSC analysis showed that the modification of SiO2 increased the glass transition temperature (Tg) of the EB cured coatings. Coatings were further analyzed for performance properties, viz. abrasion resistance, gloss at 60° angle, pencil hardness, pendulum hardness, chemical and steam resistance properties, as per standard test methods. It was found that incorporation of silica nanoparticles into coating formulation improves abrasion resistance significantly. Gloss of coating reduced significantly upon addition of silica nanoparticles suggesting that the silica nanoparticles could be used as effective matting agent. Moreover, modification of silica nanoparticles further improved abrasion, pencil hardness and gloss significantly. EB cured nanocomposite coating passed chemical and steam resistance tests and exhibited excellent chemical and stain resistance properties.

4,4'-Thiodibenzenethiol을 이용한 광경화형 에폭시 아크릴레이트 합성과 굴절률에 관한 연구

4,4'-Thiodibenzenethiol을 기반으로 이관능 에폭시 수지인 4,4'-thiodibenzenethiol diglycidyl ether를 직접합성법으로 합성하였다. 합성된 에폭시 수지가 광경화가 가능하도록 acrylic acid와 반응시켜 광경화형 고굴절 이관능 에폭시 아크릴레이트인 4,4'-thiodibenzenethiol diglycidyl ether diacrylate를 합성하였으며 <TEX>$^1H$</TEX> NMR과 FTIR을 이용하여 화학구조를 확인하였다. 이관능 에폭시 아크릴레이트와 함께 반응성 희석제인 2-phenoxythiol ethyl acrylate를 5, 10, 15, 20, 30 wt% 희석하여 점도와 굴절률과의 상관관계를 확인하였으며 광경화 후 경화필름의 굴절률 변화를 고찰 하였다. 반응성 희석제의 농도가 증가함에 따라 경화물의 경화도가 낮아졌으며, 경화도가 클수록 경화 후 굴절률은 높아지는 경향을 확인하였다. UV-curable high refractive index di-functional epoxy acrylate, 4,4'-thiodibenzenethiol diglycidyl ether diacrylate, was synthesized from acrylic acid and 4,4'-thiodibenzenethiol diglycidyl ether that was obtained by reacting 4,4'-thiodibenzenethiol and epichlorohydrin using a direct method (Taffy process). Its chemical structure was identified by <TEX>$^1H$</TEX> NMR and FTIR. After its dilution with a reactive diluent, 2-phenoxythiol ethyl acrylate as 5, 10, 15, 20, and 30 wt% content, the relationship between their viscosity and refractive index was investigated. Their degree of cure decreased with increasing the amount of reactive diluent, and the refractive index of UV-cured film increased with increasing the degree of cure.

Synthesis of a novel UV-curable prepolymer hexanediol diglycidyl ether diacrylate and its cured film tensile property

A novel UV-curable prepolymer hexanediol diglycidyl ether diacrylate (HDGEA) was synthesized by utilizing hexanediol diglycidyl ether (HDGE) and acrylic acid (AA) as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimal synthetic conditions were that the concentration of N, N-dimethylbenzylamine was 0.80 wt% of reactants, the concentration of p-hydroxyanisole was 0.3 wt% of reactants, the reaction temperature was 90–110 °C, and the molar ratio of HDGE to AA was 1: 2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-curing initiator was added to the synthesized HDGEA to prepare a kind of UV-curing coating. The mechanical properties of the UV-cured films were determined, giving 31.87 MPa of tensile strength, 871.88 MPa of Young’s modulus and 6.77% of elongation at tear.

Synthesis of a novel UV-curable prepolymer neopentyl glycol diglycidyl ether diacrylate and its cured film tensile property

A novel UV-curable prepolymer neopentyl glycol diglycidyl ether diacrylate (NPGGEA) was synthesized by using neopentyl glycol diglycidyl ether (NPGGE) and acrylic acid (AA) as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were taken as follows: The concentration of N,N-dimethylbenzylamine, 0.80% of reactants; the concentration of p-hydroxyanisole, 0.3% of reactants; the reaction temperature, 90–110 °C; the molar ratio of NPGGE to AA, 1:2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-cured initiator was added to the synthesized NPGGEA to prepare a kind of UV-cured coating. Mechanical properties of the UV-cured films were determined, giving 28.75 MPa of tensile strength, 923.82 MPa of Young’s modulus and 5.51% of elongation at tear.

Synthesis of a novel UV-curable prepolymer polypropyleneglycol diglycidyl ether diacrylate

A novel UV-curable prepolymer polypropyleneglycol diglycidyl ether diacrylate (PPGGEA) was synthesized by utilizing polypropyleneglycol diglycidyl ether (PPGGE) and acrylic acid (AA) as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were in the following: the concentration of N, N-dimethylbenzylamine was 0.80 wt% of reactants, the concentration of p-hydroxyanisole was 0.3 wt% of reactants, the reaction temperature was 90–110 °C, and the molar ratio of PPGGE to AA was 1:2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-cured initiator was added to the synthesized PPGGEA to prepare a kind of UV-cured coating. The mechanical properties of the UV-cured films were determined, giving 29.99 MPa of tensile strength, 834.27 MPa of the Young’s modulus and 5.66% of elongation at tear.

Coating characteristics of electron beam cured Bisphenol A diglycidyl ether diacrylate-co-aliphatic urethane diacrylate resins

Abstract Electron beam (EB) was used to cure coatings of Bisphenol A diglycidyl ether diacrylate (BDGDA) containing varying proportions of aliphatic urethane diacrylate (AUA). The cured BDGDA-co-AUA polymer coatings were characterized by Fourier transformed infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel fraction and swelling estimation techniques. FTIR study showed that the coating formulations were completely cured at a dose of 420 kGy. The effect of AUA on the end use performance properties of BDGDA coating namely, abrasion resistance, specular gloss at 60° angle, tubular impact resistance, pencil hardness, pendulum hardness, scratch resistance, mar resistance, stain resistance, steam resistance and cigarette burn resistance was also investigated. It was observed that incorporation of urethane acrylate oligomer in the epoxy acrylate formulation improved abrasion resistance, gloss and impact resistance. However, scratch resistance, mar resistance and hardness of the BDGDA coatings decreased due to incorporation of AUA. All coating formulations exhibited excellent stains and steam resistance properties, but showed poor cigarette burn resistance.

Coating characteristics of electron beam cured bisphenol A diglycidyl ether diacrylate resin containing 1,6-hexanediol diacrylate on wood surface

Electron beam curing of bisphenol A diglycidyl ether diacrylate resin (BDGDA) mixed with varying amount of 1,6-hexanediol diacrylate monomer (HDDA) was investigated using low energy DC electron beam accelerator. Cured coating films were analyzed by Fourier transformed infrared spectroscopy (FTIR), gel fraction, swelling ratio and thermogravimetric (TG) techniques. The wood surfaces cured with different coating compositions were tested for their end use performance properties like gloss, pencil hardness, scratch resistance, mar resistance, abrasion resistance, chemical resistance, steam resistance and cigarette burn resistance. FTIR studies indicated that the density of acrylate functionality and degree of curing increased with the HDDA content in the feed mixture. This observation was supported by gel fraction and swelling studies as well. The thermal stability, pencil hardness, mar resistance, abrasion resistance and solvent resistance properties of coating were observed to improve with the incorporation of HDDA. However, there was significant decrease in gloss and scratch resistance at higher HDDA content. The coating showed excellent steam and stain resistance but poor resistance to cigarette burns.