超支化水性光敏树脂的制备及其在3D打印中的应用研究

Preparation of hyperbranched waterborne photosensitive resin and its application in 3D printing

以柠檬酸(CA)和新戊二醇(NPG)合成了一种端羧基超支化聚酯(CHBP)。然后用甲基丙烯酸缩水甘油酯(GMA)对其进行改性,制备超支化水性聚酯丙烯酸酯(WCHBPA),并通过红外和核磁氢谱对其结构进行了表征。通过配方设计得到可水洗3D打印光敏树脂,探究了光引发剂(TPO-L)用量和辐照强度对复配树脂光固化动力学的影响。此外,还研究了超支化水性聚酯丙烯酸酯和丙烯酰吗啉(ACMO)质量比对3D打印样条的力学性能、玻璃化转变温度和热失重的影响。研究结果表明:(1)成功制备了目标产物CHBP和WCHBPA。(2)本研究复配了4种3D打印光敏树脂,黏度适宜,可满足3D打印的基本性能要求,在辐射光强为40 mW/cm^(2)、TPO-L用量为2.0%(质量分数)的条件下,双键转化率达到最高。(3)随着稀释剂(ACMO)含量由30%增加到60%,固化样条的拉伸强度由13.3 MPa逐渐增大到45.6 MPa,冲击强度由2.98 kJ/m^(2)降低至1.53 kJ/m^(2),玻璃化转变温度由92.4℃逐渐增大到151.1℃。(4)通过3D打印得到的制件呈现清晰且精度较好,对制备高性能可水洗3D打印光敏树脂及配方设计具有一定的参考意义。

A carboxyl terminated hyperbranched polyester(CHBP)was synthesized by using citric acid(CA)and neopentyl glycol(NPG),and then it was modified with glycidyl methacrylate(GMA)to prepare hyperbranched waterborne polyester acrylate(WCHBPA).Its structure was characterized by infrared and nuclear magnetic hydrogen spectroscopy.A washable 3D printed photosensitive resin was obtained through formula design,and the effects of the dosage and irradiation intensity of the photoinitiator(TPO-L)on the photopolymerization kinetics of the composite resin were investigated.In addition,the influence of the mass ratio of hyperbranched waterborne polyester acrylate and acryloylmethiolane(ACMO)on the mechanical properties,glass transition temperature,and thermal weight loss of 3D printed splines was also studied.The research results showed that,(1)The target products CHBP and WCHBPA were successfully prepared.(2)In this study,four types of 3D printing photosensitive resins with suitable viscosity were formulated,which could meet the basic requirements of 3D printing.Under the conditions of radiation intensity of 40 mW/cm^(2) and TPO-L dosage of 2.0%(mass fraction),the conversion rate of double bonds reached the highest.(3)As the content of diluent(ACMO)increased from 30%to 60%,the tensile strength of the cured sample gradually increased from 13.3 MPa to 45.6 MPa,the impact strength decreased from 2.98 kJ/m^(2) to 1.53 kJ/m^(2),and the glass transition temperature gradually increased from 92.4℃to 151.1℃.(4)The parts obtained through 3D printing were clear and accurate,which had certain reference significance for the preparation of high-performance washable 3D printing photosensitive resins and formula design.