Views: 0 Author: Site Editor Publish Time: 2025-03-05 Origin: Site
In the last issue, we introduced that the most widely used resin in the photocuring industry is epoxy acrylate, and the most used and largest used epoxy acrylate is bisphenol A epoxy acrylate.
Bisphenol A epoxy acrylate is prepared by the reaction of bisphenol A epoxy resin and acrylic acid. Bisphenol A epoxy resin is produced by the reaction of bisphenol A and epichlorohydrin under alkaline conditions. By controlling the ratio of the two raw materials and the reaction conditions, bisphenol A epoxy resins with different polymerization degrees can be obtained. The higher the polymerization degree, the larger the molecular weight and the smaller the epoxy value.
As shown in the figure, the variable n in the general formula represents the degree of polymerization, and the value of n is generally between 0-25; the average value of n of low relative molecular mass epoxy resin is generally less than 2, and its softening point is lower than 50°C; the value of n for medium relative molecular mass epoxy resin is between 2-5, and the softening point is between 50-95°C; Values of n greater than 5 is called high relative molecular mass resin, and the softening point is above 100°C. The value of n of commercial bisphenol A epoxy resin can be between 0-12, but in order to obtain bisphenol A epoxy acrylate with a high curing speed, bisphenol A epoxy resin with a high epoxy content and low viscosity is usually selected, so that more acrylate groups can be introduced. Therefore, in most cases, low relative molecular mass bisphenol A epoxy resin models with n≈0 are used. For example, common domestic models are E-51 (epoxy value is 0.51±0.03eq/100g) or E-44 (epoxy value is 0.44±0.03eq/100g).
The process of ring-opening esterification of epoxy groups in bisphenol A epoxy resin and acrylic acid under the action of catalyst is an exothermic reaction. Generally, the epoxy resin is heated to about 80°C, and a mixture of acrylic acid, catalyst and inhibitor is added dropwise. After most of the reaction is completed, the temperature is gradually raised to 100-120°C to complete the reaction. Samples are taken to test the acid value. After the acid value drops below the target value, the temperature is lowered, and the material is discharged. Since bisphenol A epoxy acrylate has a high viscosity at low temperatures, 20% UV monomer (TPGDA, TMPTA) is usually added to dilute and reduce the viscosity to facilitate later feeding.
In the early stage of the reaction of bisphenol A epoxy acrylate, in order to promote the reaction process, a catalyst is generally added. Commonly used catalysts include tertiary amines and quaternary ammonium salts; such as triethylamine, N,N-dimethylbenzylamine, trimethylbenzyl ammonium chloride, triphenyl phosphine, triphenyl antimony, chromium acetylacetonate, tetraethylammonium bromide, etc. Although triethylamine is cheap and easy to obtain, its catalytic activity is relatively low and the product stability is slightly poor; although quaternary ammonium salts have slightly stronger catalytic activity , their cost is slightly higher; triphenyl phosphine, triphenyl antimony, and chromium acetylacetonate have high catalytic activity, and the product has low viscosity, but the color is darker.
Since the reaction temperature of bisphenol A epoxy acrylate is relatively high, a certain amount of polymerization inhibitor must be added to prevent polymerization of acrylic acid (ester) during the heating process. Commonly used polymerization inhibitors include hydroquinone, methyl hydroquinone, p-methoxyphenol , etc.
The above is the synthesis reaction process of bisphenol A epoxy acrylate.
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In the photo-curing formulation system, apart from UV resins and photoinitiators, UV monomers also serve as a vital component. UV monomers not only adjust the viscosity of the system but also impart or enhance different properties of the cured film, such as enhancing adhesion, improving flexibility, and increasing wear resistance. Therefore, the rational use of various monomers is also an important link in formulation design.
As the name suggests, bifunctional UV monomers are molecules containing two reactive functional groups that participate in photopolymerization reactions. These functional groups are typically acrylates or methacrylates, with acrylates dominating the current market due to their superior reactivity and cost-effectiveness. Compared to their monofunctional counterparts, bifunctional UV monomers offer several advantages: Faster curing speed,Higher crosslinking density in the cured film,Good dilution properties,Reduced volatility and lower odor.
Monofunctional UV monomers refer to those containing only one group capable of participating in the curing reaction per molecule. The types of functional groups include acrylates, methacrylates, vinyls, vinyl ethers, epoxies, etc.
LCD photocuring 3D printing technology, also known as Mask Stereolithography (MSLA), is an emerging additive manufacturing technology. Similar to SLA and DLP technologies, LCD photocuring also solidifies liquid resin via light exposure, but its uniqueness lies in the use of an LCD screen to control the light source. This technology utilizes the imaging principle of liquid crystal displays, where computer programs provide image signals to generate selective transparent regions on the LCD screen. Under UV illumination, the light passing through these transparent areas forms UV image regions, solidifying the liquid resin exposed to them, while areas blocked by the LCD remain uncured. This process is performed layer by layer based on the predefined 3D model, with cured resin layers accumulating to build the final three-dimensional object.
SLA technology mainly uses photosensitive resin as raw material and utilizes the characteristic that liquid photosensitive resin will be rapidly cured under ultraviolet irradiation. Photosensitive resin is generally liquid, and it will immediately cause a polymerization reaction under the irradiation of ultraviolet light with a certain wavelength to complete the curing. SLA focuses ultraviolet light with a specific wavelength and intensity on the surface of the photosensitive resin, so that it solidifies point-by-point and line-by-line, ultimately forming a complete cross-sectional layer. After completing the drawing operation of one layer, the lifting table moves a layer height in the vertical direction, and then another layer is cured. Layers are stacked to form a three-dimensional object, and the formation of the pattern of each layer is controlled by the movement of the laser beam. In theory, the laser beam can move in a large space. Therefore, SLA technology can print large-sized
Digital Light Processing (DLP) came into being over a decade after the emergence of Stereolithography Apparatus (SLA) technology. As a variant of SLA, it bears remarkable similarities to SLA in terms of molding technology, achieving comparable effects through different approaches. This technology is also widely acknowledged in the industry as the second-generation stereolithography technology.
Previously we mentioned that 3D printing can be divided into 7 categories, including material extrusion, binder jetting, powder bed fusion, material jetting, sheet lamination, directed energy deposition, and stereolithography. Below we will introduce these 7 categories in details.
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