• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present disclosure provides a polyurethane-based photosensitive resin, a preparation method and use thereof in 3D printing. The method for preparing a polyurethane-based photosensitive resin is: polyisocyanate and polyol are used as raw materials for prepolymerization to obtain a prepolymer, and a reaction between isocyanate and hydroxyl is performed on the prepolymer and hydroxyl acrylate to obtain a polyurethane-based photosensitive resin; the polyisocyanate is selected from isophorone diisocyanate, toluene diisocyanate, and m-xylylene diisocyanate, the polyol is selected from polyethylene glycol, polypropylene glycol, diethylene glycol, di(2-hydroxypropyl) ether, triethylene glycol, heptapolyethylene glycol, 1,5-pentanediol, and pentaethylene glycol, and hydroxy acrylate is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate.
    公开号:NL2025977A
    申请号:NL2025977
    申请日:2020-07-02
    公开日:2021-08-11
    发明作者:Li Tianduo；Chi Hong
    申请人:Univ Qilu Technology；
    IPC主号:
    专利说明:

    POLYURETHANE-BASED PHOTOSENSITIVE RESIN, PREPARATION METHOD AND USE THEREOF IN 3D PRINTING Field of the Invention The present disclosure pertains to the technical field of 3D printing ink, and relates to the preparation of photosensitive resin, in particular to a polyurethane-based photosensitive resin, a preparation method and use thereof in 3D printing.
    Background of the Invention The disclosure of the information in this background section 1s only intended to promote the overall understanding of the background of the present disclosure, and is not necessarily regarded as acknowledging or in any way implying that this information constitutes the prior art that is known to those skilled in the art.
    The 3D printing, also known as additive manufacturing (AM), has caused a lot of attentions in different research fields, because it allows the use of precisely defined micro-architectures to create complex three-dimensional shapes, thus achieving new functions or improved performances.
    The 3D printing technologies as developed, such as fused deposition modeling (FDM), direct ink writing (DIW), selective laser sintering (SLS), stereolithography (SLA), and digital light processing (DLP) technologies, are considered to be low-cost and high-throughput additive manufacturing technologies, in which DLP printing is based on a local photopolymerization process, which is triggered by ultraviolet radiation and performs in a bath containing liquid monomers, oligomers, and photoinitiators.
    It may produce a variety of highly complex three-dimensional structures, ranging from microscale to mesoscale, having microscale structures and submicron accuracy.
    In the past few years, researchers have made exciting advances in DLP printing technology, such as micro-stereolithography technology that provides micron/submicron printing resolution, high printing speed generated by continuous liquid interfaces, and the 3D features of seven orders of magnitude from nanometer to centimeter.
    However, the development of DLP compatible high-performance multifunctional materials is still relatively limited.
    Commercial UV cured elastomers are suitable for 3D printing technology related to UV curing.
    UV cured materials are mainly based on acrylic and methacrylic resins.
    However, this type of resin still has great limitations.
    Due to the inherent poor performance of these polymers, most of these printed products cannot be used directly as part of equipment, for example in such special fields as aviation, aerospace, and automobile which require high thermal stability, mechanical property, and solvent resistance.
    The limited printable resin severely limits the practical use of revolutionary 3D printing technology.
    For example, the common bisphenol A epoxy acrylate has such defects as high viscosity, poor flexibility, and brittle cured film.
    Secondly, the mechanical adjustability is not high, which is not conducive to adjusting the mechanical property, that is, the Young's modulus is low.
    Summary of the invention As a UV cured oligomer, polyurethane-based photosensitive resin has many advantages, such as high liability of mixing with other resins, good flexibility of the cured films, wide hardness range, good elasticity and wear resistance of its products as the hardness increases, high mechanical strength, good mechanical adjustability, good biocompatibility, adaptability to high-resolution prototype manufacturing and manufacturing of (bio)medical devices, good weather resistance, good processability, mildew resistance and others.
    In order to solve the problems of the prior art, the objective of the present disclosure is to provide a polyurethane-based photosensitive resin, a preparation method and use thereof in 3D printing.
    In order to achieve the above objective, the technical solutions of the present disclosure are: In one aspect, a method for preparing a polyurethane-based photosensitive resin is disclosed, polyisocyanate and polyol are used as raw materials for prepolymerization to obtain a prepolymer, and a reaction between isocyanate and hydroxyl is performed on prepolymer and hydroxyl acrylate to obtain a polyurethane-based photosensitive resin; the polyisocyanate is selected from isophorone diisocyanate, toluene diisocyanate, and m-xylylene diisocyanate; the polyol is selected from polyethylene glycol, polypropylene glycol, diethylene glycol, di(2-hydroxypropyl)ether, triethylene glycol, heptapolyethylene glycol, 1,5-pentanediol, and pentaethylene glycol; and hydroxy acrylate is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. In the present disclosure, polyisocyanate and polyol are first used to prepare a polyurethane prepolymer, and then the isocyanate group at the end of the prepolymer is used to react with the hydroxy acrylate to modify polyurethane. The preparation process is simple, and the ability of polyurethane-based photosensitive resin to copolymerize with acrylate is used, to improve the mechanical property and solvent resistance of 3D printed models. In another aspect, a polyurethane-based photosensitive resin is disclosed, which is obtained by the above preparation method. In a third aspect, use of the above polyurethane-based photosensitive resin in 3D printing is disclosed. It was found by experiments that using the polyurethane-based photosensitive resin of the present disclosure to 3D printing, the printed products have better solvent resistance and better thermal stability. In a fourth aspect, a 3D printing ink is disclosed, comprising the above polyurethane-based photosensitive resins, acrylates, and photoinitiators. The beneficial effects of the present disclosure are:
    1. The process of the preparation method of the present disclosure only requires prepolymerizing into a polyurethane prepolymer, and then performing double bond modification of the polyurethane prepolymer. The preparation process is simple, without adding other chemical reagents, and is easy for industrial production.
    2. The polyurethane-based photosensitive resin prepared by the present disclosure, used as one of the components of the 3D printing ink, can significantly reduce the amount of acrylate used. It has shown by experiments that using the polyurethane-based photosensitive resin of the present disclosure for 3D printing, the printed products have good solvent resistance, and good thermal stability and mechanical property.
    Brief Description of the Drawings The accompanying drawings forming part of the present disclosure are used to provide a further understanding of the present disclosure.
    The exemplary examples and descriptions of the present disclosure are used to explain the present disclosure, and do not constitute an undue limitation on the present disclosure.
    Fig. 1 is an infrared spectrogram of the polyurethane-based photosensitive resin and the prepolymer prepared in Example 1 of the present disclosure; Fig. 2 is a nuclear magnetic hydrogen spectrogram of the polyurethane-based photosensitive resin and the prepolymer prepared in Example 1 of the present disclosure; Fig. 3 is a nuclear magnetic carbon spectrogram of the polyurethane-based photosensitive resin and the prepolymer prepared in Example 1 of the present disclosure; Fig. 4 is picture of a model 3D-printed with the 3D printing ink of Example 1 of the present disclosure; Fig. 5 is a characterization diagram of a tensile test of the model 3D-printed with the 3D printing ink of Example 1 of the present disclosure; Fig. 6 is a characterization diagram of a thermal stability test of the model 3D-printed with the 3D printing ink of Example 1 of the present disclosure; Fig. 7 is a characterization diagram of a water resistance test of the model 3D-printed with the 3D printing ink of Example 1 of the present disclosure; Fig. 8 is a characterization diagram of an alcohol resistance test of the model 3D-printed with the 3D printing ink of Example 1 of the present disclosure.
    Detailed Description of the Embodiments It should be noted that the following detail descriptions are exemplary and are intended to provide further explanations of the present disclosure.
    Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present disclosure belongs.
    It should be noted that the terms used herein are only to describe particular 5 embodiments and are not intended to limit exemplary embodiments according to the present disclosure.
    As used herein, the singular form is also intended to include the plural form, unless clearly indicated in the content.
    Besides, it should also be understood that when the terms “comprising” and/or “including” are used in this specification, they indicate the presence of features, steps, operations, devices, components, and/or combinations thereof.
    The present disclosure proposes a polyurethane-based photosensitive resin, a preparation method and use thereof in 3D printing.
    A typical embodiment of the present disclosure provides a method for preparing a polyurethane-based photosensitive resin, polyisocyanate and polyol are used as raw materials for prepolymerization to obtain a prepolymer, and a reaction between isocyanate and hydroxyl is performed on the prepolymer and hydroxyl acrylate to obtain a polyurethane-based photosensitive resin; the polyisocyanate is selected from isophorone diisocyanate, toluene diisocyanate, and m-xylylene diisocyanate; the polyol is selected from polyethylene glycol (molecular weight 200-800), polypropylene glycol (molecular weight 200-1000), diethylene glycol, di(2-hydroxypropyl) ether, triethylene glycol, heptapolyethylene glycol, 1,5-pentanediol, and pentaethylene glycol; and hydroxy acrylate is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate.
    In one or more examples of this embodiment, the polyisocyanate is toluene-2 4-diisocyanate, the polyol is polypropylene glycol (molecular weight 400), and the hydroxy acrylate is hydroxyethyl acrylate.
    In one or more examples of this embodiment, the prepolymerization process is: heating the polyisocyanate solution, then adding the polyol solution dropwise, performing the heat preservation reaction for a set time, and removing solvent to obtain the prepolymer.
    In these examples, the solvent of the polyisocyanate solution is acetone. In these examples, the solvent of the polyol solution is acetone. In these examples, the temperature is 80 to 85°C by heating, and time of the heat preservation reaction is 3.5 to 4.5h.
    In these examples, after the heat preservation reaction, a part of the solvent is evaporated and removed, then anhydrous ether is added for washing, and then evaporated to obtain a prepolymer.
    In one or more examples of this embodiment, the steps of reacting the prepolymer with the hydroxy acrylate are: heating the prepolymer solution, adding hydroxy acrylate, performing the heat preservation reaction, and removing solvent to obtain a polyurethane-based photosensitive resin.
    In these examples, the temperature is 40 to 50°C by heating, and time of the heat preservation reaction is 14 to 16h. In these examples, the solvent is evaporated and removed after reaction, and then anhydrous ether is added for washing, and then excess anhydrous ether is evaporated to obtain a polyurethane-based photosensitive resin.
    Another embodiment of the present disclosure provides a polyurethane-based photosensitive resin obtained by the above preparation method. The third embodiment of the present disclosure provides use of the above polyurethane-based photosensitive resin in 3D printing. The fourth embodiment of the present disclosure provides a 3D printing ink, comprising the above polyurethane-based photosensitive resins, acrylates, and photoinitiators. In one or more examples of this embodiment, the acrylate is 2-methoxyethyl acrylate, methyl acrylate, butyl acrylate, or isobornyl acrylate. In one or more examples of this embodiment, the photoinitiator is 2-hydroxy-2-methyl-1-phenylacetone (photoinitiator-1173), 1-hydroxycyclohexyl phenyl ketone (photoinitiator-184), 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-acetone (photoinitiator-907), 2,4 6-trimethylbenzoyl-diphenyl phosphine oxide
    (photoinitiator-TPO), 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester (photoinitiator-TPO-L), 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone (photoinitiator-369), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-acetone (photoinitiator-2959), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator-8 19). In order to make those skilled in the art understand the technical solutions of the present disclosure more clearly, the technical solutions of the present disclosure will be described in detail below in conjunction with particular examples and comparative examples.
    Example 1 Preparation of polyurethane prepolymer: 2mmol toluene-2,4-diisocyanate (TDI) and 40mL acetone were added to a flask, heated to 80°C, and stirred continuously at 80°C while Immol polypropylene glycol-400 (PPG-400) (dissolved in 15mL acetone) was added dropwise continuously in the flask, and a heat preservation reaction was performed for 4-6h.
    Excess solvent in the reactants was evaporated to obtain a viscous liquid, and anhydrous ether was added to wash several times to remove unreacted materials, and the solvent was evaporated to obtain the final prepolymerized product.
    Preparation of polyurethane-based photosensitive resin: 1 mmol polyurethane prepolymer was dissolved in 40 mL acetone and sonicated until it was completely dissolved.
    The solution was placed in a flask and the temperature was raised to 45°C. 2 mmol hydroxyethyl acrylate (HA) was added to the flask and stirred for 15 hours while heating.
    Excess solvent was evaporated after reaction, and anhydrous ether was added to wash several times, and anhydrous ether was evaporated to obtain a viscous and transparent polyurethane-based photosensitive resin.
    Preparation of 3D printing ink: 10wt% polyurethane-based photosensitive resin was put into a beaker, and 89wt% 2-methoxyethyl acrylate was added to the beaker, sonicated for a period of time until completely mixed, so the concentration was diluted, and 1wt% photoinitiator-184 was dissolved in the mixed solution, sonicated until the photoinitiator was completely dissolved to obtain the 3D printing ink.
    The other 3D printing inks with 30wt% and 50wt% polyurethane-based photosensitive resin were prepared by the same method, except that 30wt% polyurethane-based photosensitive resin and 69wt% 2-methoxyethyl acrylate as well as 50wt% polyurethane-based photosensitive resin and 49wt% 2-methoxyethyl acrylate were used for preparation.
    Fig. 1 is the infrared spectrogram of the polyurethane-based photosensitive resin and the prepolymer, which shows that the disappearance of the -NCO isocyanate group at 2245cm™ of the synthesized polyurethane-based photosensitive resin compared with the polyurethane prepolymer proves the complete reaction between isocyanate group in the prepolymer with the -OH group in hydroxyethyl acrylate, and the appearance of stretching vibration of C=C double bond at 1640cm™ and the appearance of C=C bending vibration at 810cm™ also prove the appearance of C=C double bond in the polyurethane-based photosensitive resins.
    The synthesis of polyurethane-based photosensitive resins has been demonstrated by above.
    Fig. 2 is 'H NMR of the polyurethane-based photosensitive resin and prepolymer.
    From this figure, it can be concluded that the appearance of the amine vibration peaks at a and bh represents the formation of internal urethane groups, and the appearance of the vibration peak of C=C double bond proves the synthesis of the polyurethane-based photosensitive resin with C=C double bond groups.
    Fig. 3 is PC NMR of the polyurethane-based photosensitive resin and the prepolymer.
    From this figure, it can be concluded that the vibration peaks of C in urethane in the polyurethane prepolymer are at g and h, and the vibration peak of C in NCO 1s at f compared with the nuclear magnetic C spectrum of polyurethane-based photosensitive resin, in which a and b are the vibration peaks of C=C double bond, c is the vibration peak of C in C=O connected to C=C double bond, d e is the vibration peak of C in urethane of the polyurethane-based photosensitive resin.
    The appearance of each vibration peak proves the synthesis of polyurethane-based photosensitive resin with C=C double bond groups.
    The model obtained by 3D printing with the 3D printing ink prepared in this example is shown in Fig. 4, indicating that the 3D printing ink prepared in this example can be used to 3D printing.
    Fig. 5 is the tensile test of the product printed with 3D printing ink. It can be seen from the figure that as the content of polyurethane-based photosensitive resin in the ink increases by 10wt%, 30wt% and 50wt%, the elasticity of the 10wt%, 30wt% and 50wt% products gradually increases, elongation at break increases, and the tensile properties of the material increase.
    Fig. 6 shows the thermal stability test of the products printed with 3D printing ink. It can be seen from the figure that as the content of polyurethane-based photosensitive resin in the ink increases, the thermal performance of the 10wt%, 30wt%, SOwt% products increases, the initial decomposition temperature is 288.5 °C, 296.3°C,
    312.07°C, and the residual carbon content is 1.2%, 3.2%, 29.2%, respectively, which proves the enhanced thermal stability.
    Fig. 7 is the water resistance test of the products printed with 3D printing ink. 10%, 30%, 50% products were put into the container containing deionized water and immersed to observe the changes of the products. There is no significant change in the products at the beginning and after seven days of immersion as shown in the figure, proving that the products have good water resistance.
    Fig. 8 is the alcohol resistance test of the products printed with 3D printing ink. 10%, 30%, 50% products were put into the container containing anhydrous ethanol and immersed to observe the changes of the products. There is no significant change in the products at the beginning and after seven days of immersion as shown in the figure, proving that the products have good alcohol resistance.
    The above contents are only preferred embodiments of the present disclosure, and are not intended to limit the present disclosure. For those skilled in the art, the present disclosure may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present disclosure shall be included in the protection scope of the present disclosure.
    权利要求:
    Claims (15)
    [1]
    A method for preparing a photosensitive resin based on polyurethane, characterized in that polyisocyanate and polyol are used as raw materials for prepolymerization to obtain a prepolymer, and a reaction between isocyanate and hydroxyl is carried out on the prepolymer and hydroxy acrylate to obtain a photosensitive resin based on polyurethane; the polyisocyanate is selected from isophorone diisocyanate, toluene diisocyanate and m-xylylene diisocyanate; the polyol is selected from polyethylene glycol, polypropylene glycol, diethylene glycol, di(2-hydroxypropyl) ether, triethylene glycol, heptapolyethylene glycol, 1,5-pentanediol and pentaethylene glycol; and hydroxy acrylate is selected from hydroxyethyl acrylate, hydroxypropyl acrylate and 4-hydroxybutyl acrylate.
    [2]
    The process for preparing a polyurethane-based photosensitive resin according to claim 1, characterized in that the polyisocyanate is toluene-2-4-diisocyanate 1s, the polyol is polypropylene glycol and the hydroxy acrylate is hydroxyethyl acrylate.
    [3]
    The process for preparing a polyurethane-based photosensitive resin according to claim 1 or 2, characterized in that the prepolymerization process includes: heating a polyisocyanate solution, then adding a polyol solution dropwise, performing a heat preservation reaction for a set time, and removing the solvent to obtain a prepolymer.
    [4]
    The process for preparing a polyurethane-based photosensitive resin according to claim 3, characterized in that the solvent of the polyisocyanate solution is acetone.
    [5]
    The process for preparing a polyurethane-based photosensitive resin according to claim 3 or 4, characterized in that the solvent of the polyol solution is acetone.
    [6]
    The process for preparing a polyurethane-based photosensitive resin according to claim 3, 4 or 5, characterized in that it is heated to 80 to 85°C, the time of the heat preservation reaction being 3.5 to 4.5 o'clock.
    [7]
    The process for preparing a polyurethane-based photosensitive resin according to claim 3, 4, 5 or 6, characterized in that after the heat preservation reaction, part of the solvent is first evaporated, and then anhydrous ether is added for the preparation. washing, and then evaporated to obtain a prepolymer.
    [8]
    The process for preparing a polyurethane-based photosensitive resin according to any one of the preceding claims, characterized in that the steps of reacting the prepolymer with hydroxyacrylate include: heating the prepolymer solution, adding hydroxyacrylate, performing of a further heat preservation reaction, removing the solvent to obtain a polyurethane-based photosensitive resin.
    [9]
    The process for preparing a polyurethane-based photosensitive resin according to claim 8, characterized in that the time of the further heat preservation reaction is 14 to 16 hours.
    [10]
    The process for preparing a polyurethane-based photosensitive resin according to claim 8 or 9, characterized in that the solvent is evaporated and removed after reaction, and then anhydrous ether is added for washing and then an excess of anhydrous ether is added is evaporated to obtain a polyurethane-based photosensitive resin.
    [11]
    A photosensitive resin based on polyurethane, characterized in that it is obtained by the preparation process according to any one of claims 1 to
    10.
    [12]
    Use of the polyurethane-based photosensitive resin according to claim 11 in 3D printing.
    [13]
    A 3D printing ink, characterized in that it contains the polyurethane-based photosensitive resin according to claim 11, one or more acrylates and one or more photoinitiators.
    [14]
    The 3D printing ink according to claim 13, characterized in that the acrylate is 2-methoxyethyl acrylate, methyl acrylate, butyl acrylate or isobornyl acrylate.
    [15]
    The 3D printing ink according to claim 13 or 14, characterized in that the photoinitiator is 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-(4-morpholinyl)-1-[ 4-(methylthio)phenyl]-1-acetone, 2,46-trimethylbenzoyl-diphenylphosphine oxide), 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl ]-1-butanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-acetone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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