WO2023050529A1 - Silicon chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition for photocuring 3d printing and preparation method therefor - Google Patents

Silicon chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition for photocuring 3d printing and preparation method therefor Download PDF

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WO2023050529A1
WO2023050529A1 PCT/CN2021/128717 CN2021128717W WO2023050529A1 WO 2023050529 A1 WO2023050529 A1 WO 2023050529A1 CN 2021128717 W CN2021128717 W CN 2021128717W WO 2023050529 A1 WO2023050529 A1 WO 2023050529A1
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temperature
flexible polyurethane
resistant flexible
resin composition
photosensitive resin
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卓东贤
陈少云
罗永强
陈苗苗
瞿波
王睿
郑燕玉
刘小英
李文杰
黄慧玲
许一昊
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泉州师范学院
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing

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  • the invention belongs to the technical field of chemical industry, and in particular relates to a low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains for photocuring 3D printing and a preparation method thereof.
  • Stereo-curing 3D printing technology has developed rapidly in recent years, and the development of 3D printing materials is one of the three key technologies of 3D printing technology. Material bottlenecks have become the primary problem limiting the development of 3D printing.
  • the market demand for photosensitive resins is becoming more and more diverse, which requires that photosensitive resins should have different systems, different properties, and different application directions.
  • the demand for low-temperature-resistant flexible photosensitive resins is increasing. Therefore, the development of low-temperature-resistant flexible resins that meet the needs will greatly promote the application of light-curing technology. .
  • the main chain structure of silicone materials is polysiloxane structure, and the side chains are connected to other organic groups through silicon atoms. Its chemical properties are relatively stable, and it is used as a medical material in clinical practice and is highly recognized by the medical community. It has a series of excellent properties such as high low temperature resistance, oxidation resistance, softness, permeability, aging resistance, corrosion resistance, and low surface activity. However, the curing speed of the silicone material itself is slow, and its fluidity makes it impossible to guarantee the accuracy of printing, and most silicone materials have poor compatibility with other resins. Polyurethane acrylate has strong photosensitivity, reactivity, high wear resistance, adhesion and other excellent properties.
  • the present invention provides a low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains for photocuring 3D printing with low cost and better mechanical properties and a preparation method thereof.
  • the photosensitive resin composition costs Low, wide applicability, and cold-resistant effect, used in 3D printing technology, effectively solves the problems of expensive 3D printing resin, mechanical properties based on flexible polyurethane photosensitive resin composition, and lays the foundation for the large-scale application of 3D printing technology Base.
  • the low temperature resistant flexible polyurethane photosensitive resin composition containing silicon chains, its raw materials include the following components by weight:
  • the structural formula of the low temperature resistant flexible polyurethane prepolymer containing silicon chains is:
  • R 1 and R 2 are not limited to the listed categories.
  • the preparation method of the low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains for photocuring 3D printing the steps are as follows:
  • said diisocyanate is one or more of toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate;
  • said hydroxy silicone oil has a molecular weight of 20000 (hydroxyl content 0.2 %), 2000 (hydroxyl content: 2%), 1800 (hydroxyl content: 1.8%), 500 (hydroxyl content: 8%), 450 (hydroxyl content: 8.5%), etc.
  • the input ratio of hydroxyl silicone oil and acrylic acid monomer is calculated according to the material ratio of -NCO: -OH 1:1;
  • the urethane acrylate resin is selected from one of aliphatic urethane acrylate oligomers, aromatic urethane acrylate oligomers, polyurethane diacrylate, dimethacrylate urethane resins or its combination.
  • the reactive diluent is selected from propoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, One or a combination of isobornyl acrylate and cyclotrimethylolpropane formal acrylate.
  • the photoinitiator is selected from one of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl benzophenone or a combination thereof.
  • the antioxidant is selected from tetrakis(3,5-di-tert-butyl-4-hydroxy)pentaerythritol phenylpropionate, tris(2,4-di-tert-butyl)phenyl phosphite, N,N One of '-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, 2,6-di-tert-butyl-4-methylphenol, or combination.
  • the low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains provided by the present invention, by photosensitively modifying the silicon chains, inserts them into the structural system of the photosensitive resin, thereby developing a photosensitive resin composition suitable for photocuring 3D Print flexible materials with excellent mechanical properties and low temperature resistance.
  • the low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains has the advantages of simple process and fast curing, which can not only reduce the material usage cost of equipment, but also break the technological monopoly of foreign materials and promote the development of domestic light-cured 3D materials. Rapid development, expanding the scope of application of light-curing 3D printing, especially in the shoe and apparel industry.
  • Figure 1 is a product printed by a desktop-level light-curing 3D printer of the low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains prepared in the embodiment of the present invention.
  • the raw material source that adopts and the abbreviation in embodiment are as follows:
  • Aliphatic urethane acrylate purchased from Sartomer Company, product number CN9010, abbreviated as B-1;
  • Aliphatic urethane acrylate purchased from Sartomer Company, product number CN991, abbreviated as B-2;
  • Hydroxyethyl methacrylate purchased from Aladdin Reagents (Shanghai) Co., Ltd., abbreviated as C-1;
  • Hydroxypropyl methacrylate purchased from Aladdin Reagents (Shanghai) Co., Ltd., abbreviated as C-2;
  • C-3 Cyclotrimethylolpropane formal acrylate
  • Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide purchased from Aladdin Reagents (Shanghai) Co., Ltd., product number photoinitiator XBPO, abbreviated as D-1;
  • 1-Hydroxycyclohexylbenzophenone purchased from Aladdin Reagents (Shanghai) Co., Ltd., product number photoinitiator 184, abbreviated as D-2;
  • 2,6-di-tert-butyl-4-methylphenol purchased from Aladdin Reagents (Shanghai) Co., Ltd., product number antioxidant BHT, abbreviated as E-1;
  • Tetrakis(3,5-di-tert-butyl-4-hydroxy)pentaerythritol phenylpropionate purchased from Guangzhou Kaiyin Chemical Co., Ltd., antioxidant 1010, abbreviated as E-2.
  • Embodiment 1-6 being the preparation of sample 1# ⁇ sample 6#
  • the prepared photosensitive resin composition is introduced into a light-curing 3D printer, and formed by computer modeling, patterning and printing.
  • the photosensitive resin composition was evaluated by curing and observing the appearance of the cured finished product, and the results are shown in Table 2 below.

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Abstract

A silicon chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition for photocuring 3D printing and a preparation method therefor. The composition comprises the following raw materials in parts by weight: 30-80 parts of a silicon chain-containing low-temperature-resistant flexible polyurethane prepolymer, 5-10 parts of polyurethane acrylate resin, 35-70 parts of a reactive diluent, 1.0-5.0 parts of a photoinitiator, and 0.1-1.0 part of an antioxidant. The silicon chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition has higher reaction activity, can be used for conventional SLA, DLP, LCD and other desktop-level 3D printing devices, and moreover, a printed product contains a silicon chain, and is good in low-temperature resistance, small in shrinkage rate, resistant to aging and excellent in mechanical property.

Description

一种用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物及其制备方法A low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains for photocuring 3D printing and its preparation method 技术领域technical field
本发明属于化工技术领域，具体涉及一种用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物及其制备方法。The invention belongs to the technical field of chemical industry, and in particular relates to a low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains for photocuring 3D printing and a preparation method thereof.
背景技术Background technique
光固化3D打印技术近年来发展迅速，3D打印材料的发展是3D打印技术的3大关键技术之一。材料瓶颈已经成为限制3D打印发展的首要问题。市场对光敏树脂的需求越来越多样化，这就要求光敏树脂应该有不同的体系，不同性能，不同应用方向。随着一些医疗模型，生活用品、工艺品设计的发展，对耐低温柔性光敏树脂需求量越来越大，所以研发出符合需要的耐低温柔性树脂对推进光固化技术的应用有很大的促进作用。Stereo-curing 3D printing technology has developed rapidly in recent years, and the development of 3D printing materials is one of the three key technologies of 3D printing technology. Material bottlenecks have become the primary problem limiting the development of 3D printing. The market demand for photosensitive resins is becoming more and more diverse, which requires that photosensitive resins should have different systems, different properties, and different application directions. With the development of some medical models, daily necessities, and handicraft design, the demand for low-temperature-resistant flexible photosensitive resins is increasing. Therefore, the development of low-temperature-resistant flexible resins that meet the needs will greatly promote the application of light-curing technology. .
有机硅材料的主链结构为聚硅氧烷结构，侧链则通过硅原子与其他有机基团相连接，其化学性能相对稳定，在临床中作为医用材料使用，倍受医学界认可。其具有较高的耐低温、抗氧化、柔软性、透过性、耐老化、耐腐蚀、低表面活性等一系列优良性能。但有机硅材料本身固化速度慢，其流动性使其不能保证打印的精确度，并且大数有机硅材料与其他树脂相溶性较差。聚氨酯丙烯酸酯具有较强的光敏性、反应活性以及高耐磨力、黏附性等优良性能。因此，如何将聚氨酯和有机硅材料的优异性能结合起来并应用于光固化3D打印成了研究的热点。如孙芳等人通过在有机硅链段上接入聚氨酯链段合成了具有优异感光性和较好混溶性的光敏有机硅预聚体。J.Y.Cheng等人以聚醚封端的有机硅共聚物、聚丙二醇(Mn＝2000g/mol)、甲苯二异氰酸酯(TDI)为反应原料合成了一系列可进行光固化的多官能团聚氨酯丙烯酸酯预聚物。将预聚物进行光固化，所得固化薄膜具备良好的热稳定性。但是对于含硅链的聚氨酯树脂的柔性、耐低温性都没有相关的研究报道。The main chain structure of silicone materials is polysiloxane structure, and the side chains are connected to other organic groups through silicon atoms. Its chemical properties are relatively stable, and it is used as a medical material in clinical practice and is highly recognized by the medical community. It has a series of excellent properties such as high low temperature resistance, oxidation resistance, softness, permeability, aging resistance, corrosion resistance, and low surface activity. However, the curing speed of the silicone material itself is slow, and its fluidity makes it impossible to guarantee the accuracy of printing, and most silicone materials have poor compatibility with other resins. Polyurethane acrylate has strong photosensitivity, reactivity, high wear resistance, adhesion and other excellent properties. Therefore, how to combine the excellent properties of polyurethane and silicone materials and apply them to light-curing 3D printing has become a research hotspot. For example, Sun Fang and others synthesized a photosensitive silicone prepolymer with excellent photosensitivity and better miscibility by inserting polyurethane segments on the silicone segments. J.Y.Cheng et al synthesized a series of photocurable multifunctional urethane acrylate prepolymers with polyether-terminated silicone copolymers, polypropylene glycol (Mn=2000g/mol), and toluene diisocyanate (TDI) as reaction materials . The prepolymer is photocured, and the resulting cured film has good thermal stability. However, there are no relevant research reports on the flexibility and low temperature resistance of polyurethane resins containing silicon chains.
目前，能用于3D打印的有机硅光敏树脂材料仍较少，丙烯酸有机硅材料的合成方法复杂，固化中存在氧阻聚问题、相容性问题，制品的力学性能较低， 弹性较差；国内关于3D打印用柔性体材料还未真正推出相关产品，并且目前对于3D打印用柔性体材料的研究报道甚少，更不用说3D打印用耐低温柔性体材料。因此，研发兼具良好的柔性、力学性能和耐高低温性能，工艺简单、固化快，适用于光固化3D打印的耐低温柔性体材料，不仅可以降低设备的材料使用费用，还能打破国外材料的技术垄断，促进国内光固化3D材料的快速发展，从而为光固化3D打印在工业领域的广泛发展奠定一定的基础。At present, there are still few silicone photosensitive resin materials that can be used for 3D printing. The synthesis method of acrylic silicone materials is complicated, and there are problems of oxygen inhibition and compatibility during curing. The mechanical properties of the products are low and the elasticity is poor; Domestically, no related products have been launched on flexible body materials for 3D printing, and there are very few research reports on flexible body materials for 3D printing, let alone low temperature resistant flexible body materials for 3D printing. Therefore, the research and development of low-temperature-resistant flexible body materials with good flexibility, mechanical properties and high-low temperature resistance, simple process and fast curing, suitable for light-curing 3D printing, can not only reduce the material cost of equipment, but also break through foreign materials. The technological monopoly of the company promotes the rapid development of domestic light-curing 3D materials, thus laying a certain foundation for the extensive development of light-curing 3D printing in the industrial field.
发明内容Contents of the invention
针对现有的技术情况，本发明提供一种低成本、力学性能较优的用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物及其制备方法，该光敏树脂组合物成本较低、适用性广、具有耐寒效果，用于3D打印技术，有效地解决了3D打印树脂价格昂贵、基于柔性聚氨酯光敏树脂组合物的机械性能等难题，为3D打印技术的大规模应用奠定了基础。In view of the existing technical situation, the present invention provides a low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains for photocuring 3D printing with low cost and better mechanical properties and a preparation method thereof. The photosensitive resin composition costs Low, wide applicability, and cold-resistant effect, used in 3D printing technology, effectively solves the problems of expensive 3D printing resin, mechanical properties based on flexible polyurethane photosensitive resin composition, and lays the foundation for the large-scale application of 3D printing technology Base.
为了实现上述目的，本发明采用的技术方案为：In order to achieve the above object, the technical scheme adopted in the present invention is:
含硅链的耐低温柔性聚氨酯光敏树脂组合物，其原料包括如下重量份的组分：The low temperature resistant flexible polyurethane photosensitive resin composition containing silicon chains, its raw materials include the following components by weight:
Figure PCTCN2021128717-appb-000001
Figure PCTCN2021128717-appb-000001
所述的含硅链的耐低温柔性聚氨酯预聚体的结构式为：The structural formula of the low temperature resistant flexible polyurethane prepolymer containing silicon chains is:
Figure PCTCN2021128717-appb-000002
Figure PCTCN2021128717-appb-000002
Figure PCTCN2021128717-appb-000003
Figure PCTCN2021128717-appb-000003
上式中，R 1，R 2不限于所列的类别。 In the above formula, R 1 and R 2 are not limited to the listed categories.
所述用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物的制备方法，步骤如下：The preparation method of the low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains for photocuring 3D printing, the steps are as follows:
(1)制备含硅链的耐低温柔性聚氨酯光敏预聚体：在装有二元醇的圆底烧瓶中，加入计量的二异氰酸酯，在氮气保护及50～120℃条件下反应0.1～5.0h，再加入计量的羟基硅油，在氮气保护及50～120℃条件下反应0.1～5.0h，得到含硅链及-NCO基团封端的聚氨酯预聚体；所得的含硅链及-NCO基团封端的聚氨酯预聚体再与含羟基、C＝C的丙烯酸单体在氮气保护及40～120℃条件下反应0.1～5.0h，即得含硅链耐低温柔性聚氨酯光敏预聚体；(1) Preparation of low-temperature resistant flexible polyurethane photosensitive prepolymer containing silicon chains: In a round-bottomed flask filled with glycol, add a measured amount of diisocyanate, and react under nitrogen protection and 50-120°C for 0.1-5.0h , then add measured hydroxyl silicone oil, and react for 0.1-5.0h under nitrogen protection and 50-120°C to obtain a polyurethane prepolymer containing silicon chains and -NCO groups terminated; the resulting silicon-containing chains and -NCO groups The blocked polyurethane prepolymer is then reacted with hydroxyl-containing, C=C acrylic monomers under nitrogen protection and 40-120°C for 0.1-5.0 hours to obtain a silicon-containing chain low-temperature resistant flexible polyurethane photosensitive prepolymer;
其中所述的二异氰酸酯为为甲苯二异氰酸酯、对苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种；所述的羟基硅油为分子量20000(羟基含量0.2％)、2000(羟基含量：2％)、1800(羟基含量：1.8％)、500(羟基含量：8％)、450(羟基含量：8.5％)等中的一种或几种；所述的含羟基、C＝C的丙烯酸单体为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯等中的一种或其组合，所述的二异氰酸酯和羟基硅油、丙烯酸单体投入比按-NCO：-OH的物质的量比1:1计算；Wherein said diisocyanate is one or more of toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate; said hydroxy silicone oil has a molecular weight of 20000 (hydroxyl content 0.2 %), 2000 (hydroxyl content: 2%), 1800 (hydroxyl content: 1.8%), 500 (hydroxyl content: 8%), 450 (hydroxyl content: 8.5%), etc.; The acrylic monomer containing hydroxyl group and C=C is one or a combination of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc., the diisocyanate and The input ratio of hydroxyl silicone oil and acrylic acid monomer is calculated according to the material ratio of -NCO: -OH 1:1;
(2)按重量份计，将30～80份含硅链的耐低温柔性聚氨酯光敏预聚体、5～10份聚氨酯丙烯酸酯类树脂、30～70份活性稀释剂、1.0～5.0份光引发剂、0.1～1.0份抗氧化剂混合升温至30～80℃，经搅拌混合均匀后，即得到含硅链的耐低温 柔性聚氨酯光敏树脂组合物。(2) In parts by weight, 30-80 parts of low-temperature-resistant flexible polyurethane photosensitive prepolymer containing silicon chains, 5-10 parts of polyurethane acrylate resin, 30-70 parts of reactive diluent, and 1.0-5.0 parts of photoinitiator agent, 0.1-1.0 parts of antioxidant, mix and heat up to 30-80 DEG C, and after stirring and mixing uniformly, a low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains is obtained.
优选地，所述的聚氨酯丙烯酸酯类树脂选自脂肪族聚氨酯丙烯酸酯齐聚物、芳香族聚氨酯丙烯酸酯齐聚物、聚氨酯二丙烯酸酯、二甲基丙烯酸氨基甲酸酯树脂中的一种或其组合。Preferably, the urethane acrylate resin is selected from one of aliphatic urethane acrylate oligomers, aromatic urethane acrylate oligomers, polyurethane diacrylate, dimethacrylate urethane resins or its combination.
优选地，所述的活性稀释剂选自丙氧化丙三醇三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟乙酯、三羟甲基丙烷三丙烯酸酯、丙烯酸异冰片酯和环三羟甲基丙烷甲缩醛丙烯酸酯的一种或其组合。Preferably, the reactive diluent is selected from propoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, One or a combination of isobornyl acrylate and cyclotrimethylolpropane formal acrylate.
优选地，所述光引发剂选自苯基双(2,4,6-三甲基苯甲酰基)氧化膦、1-羟环己基苯酮中的一种或其组合。Preferably, the photoinitiator is selected from one of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl benzophenone or a combination thereof.
优选地，所述的抗氧化剂选自四(3，5-二叔丁基-4-羟基)苯丙酸季戊四醇酯、三(2，4-二叔丁基)亚磷酸苯酯、N,N’-双-(3-(3，5-二叔丁基-4-羟基苯基)丙酰基)己二胺、2，6-二叔丁基-4-甲基苯酚中的一种或其组合。Preferably, the antioxidant is selected from tetrakis(3,5-di-tert-butyl-4-hydroxy)pentaerythritol phenylpropionate, tris(2,4-di-tert-butyl)phenyl phosphite, N,N One of '-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, 2,6-di-tert-butyl-4-methylphenol, or combination.
本发明的有益效果在于：The beneficial effects of the present invention are:
(1)本发明所提供的含硅链的耐低温柔性聚氨酯光敏树脂组合物，通过对硅链进行光敏性改性，将其接入光敏树脂的结构体系中，从而开发出适用于光固化3D打印优异力学性能和耐低温性能的柔性材料。(1) The low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains provided by the present invention, by photosensitively modifying the silicon chains, inserts them into the structural system of the photosensitive resin, thereby developing a photosensitive resin composition suitable for photocuring 3D Print flexible materials with excellent mechanical properties and low temperature resistance.
(2)该含硅链的耐低温柔性聚氨酯光敏树脂组合物具备工艺简单、固化快等优点，不仅可以降低设备的材料使用费用，还能打破国外材料的技术垄断，促进国内光固化3D材料的快速发展，扩大光固化3D打印的适用范围，特别是在鞋服产业的应用。(2) The low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains has the advantages of simple process and fast curing, which can not only reduce the material usage cost of equipment, but also break the technological monopoly of foreign materials and promote the development of domestic light-cured 3D materials. Rapid development, expanding the scope of application of light-curing 3D printing, especially in the shoe and apparel industry.
附图说明Description of drawings
图1为本发明实施例中制备的含硅链的耐低温柔性聚氨酯光敏树脂组合物用桌面级光固化3D打印机打印出的制品。Figure 1 is a product printed by a desktop-level light-curing 3D printer of the low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains prepared in the embodiment of the present invention.
具体实施方式Detailed ways
实施例中，所采用的原料来源及在实施例中的简写如下所示：In the embodiment, the raw material source that adopts and the abbreviation in embodiment are as follows:
含硅链的耐低温柔性聚氨酯光敏预聚体Low temperature resistant flexible polyurethane photosensitive prepolymer containing silicon chains
在装有60g聚己内酯二醇的圆底烧瓶中，加入9.6g对苯二异氰酸酯，在氮 气保护及100℃条件下反应2h，再加入15.29g羟基硅油(2000分子量)，在氮气保护及80℃条件下反应1h，得到含硅链及-NCO基团封端的聚氨酯预聚体；所得的含硅链及-NCO基团封端的聚氨酯预聚体再与7.8g甲基丙稀酸羟乙酯在氮气保护及80℃条件下反应1h，即得所需的含硅链耐低温柔性聚氨酯光敏预聚体，简写为A-1；In a round-bottomed flask equipped with 60g of polycaprolactone diol, add 9.6g of p-phenylene diisocyanate, react for 2h under nitrogen protection and 100°C, then add 15.29g of hydroxysilicone oil (2000 molecular weight), under nitrogen protection and React for 1 hour at 80°C to obtain a polyurethane prepolymer containing silicon chains and -NCO groups terminated; The ester was reacted under nitrogen protection and 80°C for 1 hour to obtain the required silicon-containing chain low-temperature resistant flexible polyurethane photosensitive prepolymer, which is abbreviated as A-1;
在装有50g聚己二酸乙二醇酯的圆底烧瓶中，加入6g对苯二异氰酸酯，在氮气保护及110℃条件下反应1.5h，再加入15.92g羟基硅油(2000分子量)，在氮气保护及90℃条件下反应2h，得到含硅链及-NCO基团封端的聚氨酯预聚体；所得的含硅链及-NCO基团封端的聚氨酯预聚体再与4.88g甲基丙稀酸羟乙酯在氮气保护及80℃条件下反应1.5h，即得所需的含硅链耐低温柔性聚氨酯光敏预聚体，简写为A-2。In a round-bottomed flask containing 50g of polyethylene adipate, add 6g of p-phenylene diisocyanate, react for 1.5h under nitrogen protection and 110°C, then add 15.92g of hydroxysilicone oil (2000 molecular weight), under nitrogen Protected and reacted at 90°C for 2 hours to obtain a polyurethane prepolymer containing silicon chains and -NCO groups terminated; Hydroxyethyl ester was reacted for 1.5 hours under the protection of nitrogen and 80°C to obtain the desired low temperature resistant flexible polyurethane photosensitive prepolymer containing silicon chains, which is abbreviated as A-2.
聚氨酯丙烯酸酯类树脂polyurethane acrylate resin
脂肪族聚氨酯丙烯酸酯：购自沙多玛公司，产品编号CN9010，简写为B-1；Aliphatic urethane acrylate: purchased from Sartomer Company, product number CN9010, abbreviated as B-1;
脂肪族聚氨酯丙烯酸酯：购自沙多玛公司，产品编号CN991，简写为B-2；Aliphatic urethane acrylate: purchased from Sartomer Company, product number CN991, abbreviated as B-2;
活性稀释剂Active diluent
甲基丙烯酸羟乙酯：购自阿拉丁试剂(上海)有限公司，简写为C-1；Hydroxyethyl methacrylate: purchased from Aladdin Reagents (Shanghai) Co., Ltd., abbreviated as C-1;
甲基丙烯酸羟丙酯：购自阿拉丁试剂(上海)有限公司，简写为C-2；Hydroxypropyl methacrylate: purchased from Aladdin Reagents (Shanghai) Co., Ltd., abbreviated as C-2;
环三羟甲基丙烷甲缩醛丙烯酸酯(CTFA)：购自沙多玛公司，简写为C-3；Cyclotrimethylolpropane formal acrylate (CTFA): purchased from Sartomer Company, abbreviated as C-3;
光引发剂Photoinitiator
苯基双(2，4，6-三甲基苯甲酰基)氧化膦：购自阿拉丁试剂(上海)有限公司，产品编号光引发剂XBPO，简写为D-1；Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide: purchased from Aladdin Reagents (Shanghai) Co., Ltd., product number photoinitiator XBPO, abbreviated as D-1;
1-羟环己基苯酮：购自阿拉丁试剂(上海)有限公司，产品编号光引发剂184，简写为D-2；1-Hydroxycyclohexylbenzophenone: purchased from Aladdin Reagents (Shanghai) Co., Ltd., product number photoinitiator 184, abbreviated as D-2;
抗氧化剂Antioxidants
2，6-二叔丁基-4-甲基苯酚：购自阿拉丁试剂(上海)有限公司，产品编号抗氧化剂BHT，简写为E-1；2,6-di-tert-butyl-4-methylphenol: purchased from Aladdin Reagents (Shanghai) Co., Ltd., product number antioxidant BHT, abbreviated as E-1;
四(3，5-二叔丁基-4-羟基)苯丙酸季戊四醇酯：购自广州凯茵化工有限公 司，抗氧化剂1010，简写为E-2。Tetrakis(3,5-di-tert-butyl-4-hydroxy)pentaerythritol phenylpropionate: purchased from Guangzhou Kaiyin Chemical Co., Ltd., antioxidant 1010, abbreviated as E-2.
实施例1-6(即样品1#～样品6#的制备)Embodiment 1-6 (being the preparation of sample 1#～sample 6#)
将含硅链的耐低温柔性聚氨酯预聚体、聚氨酯丙烯酸酯类树脂、活性稀释剂、光引发剂、抗氧化剂混合升温至30～80℃，经搅拌混合均匀后，即得到耐低温的光固化3D打印柔性体的光敏树脂组合物。样品编号与各组分的种类和配比的关系如表1所示。Mix the low-temperature-resistant flexible polyurethane prepolymer containing silicon chains, polyurethane acrylate resin, reactive diluent, photoinitiator, and antioxidant and heat it up to 30-80°C. After stirring and mixing evenly, the low-temperature-resistant photocuring Photosensitive resin composition for 3D printing flexible body. The relationship between the sample number and the type and proportion of each component is shown in Table 1.
表1Table 1
Figure PCTCN2021128717-appb-000004
Figure PCTCN2021128717-appb-000004
实施例制备的光敏树脂组合物在光固化3D打印机中的应用The application of the photosensitive resin composition prepared by embodiment in photocuring 3D printer
将配制的光敏树脂组合物导入光固化3D打印机中，通过计算机建模、构图及打印后成型。针对上述实施例所制得的产品，通过固化情况及观察固化后成品的外观情况对光敏树脂组合物进行评价，结果如下表2所示。The prepared photosensitive resin composition is introduced into a light-curing 3D printer, and formed by computer modeling, patterning and printing. For the products prepared in the above examples, the photosensitive resin composition was evaluated by curing and observing the appearance of the cured finished product, and the results are shown in Table 2 below.
表2Table 2
Figure PCTCN2021128717-appb-000005
Figure PCTCN2021128717-appb-000005

Claims (8)

  1. 一种用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物，其特征在于，其原料包括如下重量份的组分：A low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains for photocuring 3D printing, characterized in that its raw materials include the following components by weight:
    Figure PCTCN2021128717-appb-100001
    Figure PCTCN2021128717-appb-100001
    所述的含硅链的耐低温柔性聚氨酯预聚体的结构式为：The structural formula of the low temperature resistant flexible polyurethane prepolymer containing silicon chains is:
    Figure PCTCN2021128717-appb-100002
    Figure PCTCN2021128717-appb-100002
    上式中，R 1，R 2，R 3为所列的类别之一。 In the above formula, R 1 , R 2 , and R 3 are one of the listed categories.
  2. 如权利要求1所述的一种用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物的制备方法，其特征在于，包括如下步骤：A method for preparing a silicon chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition for photocuring 3D printing according to claim 1, characterized in that it comprises the following steps:
    (1)制备含硅链的耐低温柔性聚氨酯光敏预聚体；(1) Preparation of low temperature resistant flexible polyurethane photosensitive prepolymer containing silicon chain;
    (2)按重量份计，将30～80份含硅链的耐低温柔性聚氨酯光敏预聚体、5～10份聚氨酯丙烯酸酯类树脂、30～70份活性稀释剂、1.0～5.0份光引发剂、0.1～1.0份抗氧化剂混合升温至30～80℃，经搅拌混合均匀后，即得到含硅链的耐低温柔性聚氨酯光敏树脂组合物。(2) In parts by weight, 30-80 parts of low-temperature-resistant flexible polyurethane photosensitive prepolymer containing silicon chains, 5-10 parts of polyurethane acrylate resin, 30-70 parts of reactive diluent, and 1.0-5.0 parts of photoinitiator agent, 0.1-1.0 parts of antioxidant, mix and heat up to 30-80 DEG C, and after stirring and mixing uniformly, a low-temperature-resistant flexible polyurethane photosensitive resin composition containing silicon chains is obtained.
  3. 根据权利要求2所述的一种用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物的制备方法，其特征在于，所述含硅链的耐低温柔性聚氨酯光敏预聚体的制备方法如下：在装有二元醇的圆底烧瓶中，加入计量的二异氰酸酯，在氮气保护及50～120℃条件下反应0.1～5.0h，再加入计量的羟基硅油，在氮气保护及50～120℃条件下反应0.1～5.0h，得到含硅链及-NCO基团封端的聚氨酯预聚体；所得的含硅链及-NCO基团封端的聚氨酯预聚体再与含羟基、C＝C的丙烯酸单体在氮气保护及40～120℃条件下反应0.1～5.0h，即得含硅链耐低温柔性聚氨酯光敏预聚体；A method for preparing a silicon-chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition for photocuring 3D printing according to claim 2, characterized in that the silicon-containing chain-containing low-temperature flexible polyurethane photosensitive prepolymer The preparation method is as follows: in a round-bottomed flask with glycol, add measured diisocyanate, react for 0.1-5.0h under nitrogen protection and 50-120°C, then add measured hydroxy silicone oil, under nitrogen protection and React at 50-120°C for 0.1-5.0 hours to obtain a polyurethane prepolymer containing silicon chains and -NCO groups terminated; The acrylic acid monomer of =C is reacted for 0.1-5.0 hours under nitrogen protection and 40-120°C to obtain a silicon chain-resistant flexible polyurethane photosensitive prepolymer;
    所述的二异氰酸酯为甲苯二异氰酸酯、对苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种；所述的羟基硅油为分子量20000、2000、1800、500、450的羟基硅油中的一种或几种；所述的含羟基、C＝C的丙烯酸单体为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯等中的一种或其组合，所述的二异氰酸酯和羟基硅油、丙烯酸单体投入比按-NCO：-OH的物质的量比1:1计算。The diisocyanate is one or more of toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate; the hydroxyl silicone oil has a molecular weight of 20000, 2000, 1800, 500 , 450 of one or more of the hydroxy silicone oil; the acrylic acid monomer containing hydroxyl and C=C is hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate One or a combination of esters, etc., the input ratio of the diisocyanate, hydroxyl silicone oil, and acrylic acid monomer is calculated as the material ratio of -NCO: -OH is 1:1.
  4. 根据权利要求2所述的一种用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物的制备方法，其特征在于，所述的聚氨酯丙烯酸酯类树脂选自脂肪族聚氨酯丙烯酸酯齐聚物、芳香族聚氨酯丙烯酸酯齐聚物、聚氨酯二丙烯酸酯、二甲基丙烯酸氨基甲酸酯树脂中的一种或其组合。A method for preparing a silicon chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition for photocuring 3D printing according to claim 2, wherein the polyurethane acrylate resin is selected from aliphatic polyurethane acrylic acid One or a combination of ester oligomers, aromatic urethane acrylate oligomers, polyurethane diacrylate, dimethacrylate urethane resins.
  5. 根据权利要求2所述的一种用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物的制备方法，其特征在于，所述的活性稀释剂选自丙氧化丙三醇三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟乙酯、三羟甲基丙烷三丙烯酸酯、丙烯酸异冰片酯和环三羟甲基丙烷甲缩醛丙烯酸酯的一种或其组合。A method for preparing a silicon-chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition for photocuring 3D printing according to claim 2, wherein the reactive diluent is selected from glycerol triglycerides Acrylates, ethoxylated pentaerythritol tetraacrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, isobornyl acrylate and cyclotrimethylolpropane formal acrylate one or a combination thereof.
  6. 根据权利要求2所述的一种用于光固化3D打印的含硅链的耐低温柔性聚氨酯光敏树脂组合物的制备方法，其特征在于，所述光引发剂选自苯基双(2,4,6-三甲基苯甲酰基)氧化膦、1-羟环己基苯酮中的一种或其组合。A method for preparing a silicon-chain-containing low-temperature flexible polyurethane photosensitive resin composition for photocuring 3D printing according to claim 2, wherein the photoinitiator is selected from the group consisting of phenyl bis(2,4 , one of 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenone or a combination thereof.
  7. 根据权利要求2所述的一种用于光固化3D打印的含硅链的耐低温柔性 聚氨酯光敏树脂组合物的制备方法，其特征在于，所述的抗氧化剂选自四(3，5-二叔丁基-4-羟基)苯丙酸季戊四醇酯、三(2，4-二叔丁基)亚磷酸苯酯、N,N’-双-(3-(3，5-二叔丁基-4-羟基苯基)丙酰基)己二胺、2，6-二叔丁基-4-甲基苯酚中的一种或其组合。A method for preparing a silicon-chain-containing low-temperature-resistant flexible polyurethane photosensitive resin composition for photocuring 3D printing according to claim 2, wherein the antioxidant is selected from the group consisting of tetrakis (3,5-di tert-butyl-4-hydroxy)phenylpropionate pentaerythritol, tris(2,4-di-tert-butyl)phenyl phosphite, N,N'-bis-(3-(3,5-di-tert-butyl- One of 4-hydroxyphenyl)propionyl)hexamethylenediamine, 2,6-di-tert-butyl-4-methylphenol, or a combination thereof.
  8. 根据权利要求2至6任一项所述得制备方法得到的光敏树脂组合物在光固化3D打印中的应用。The application of the photosensitive resin composition obtained by the preparation method according to any one of claims 2 to 6 in photocuring 3D printing.
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