Synthesis And Properties Of Soybean Oil Based Visible Light Curing Resin For 4D Printing

In recent years,with the rapid development of 3D printing technology,the concept of 4D printing came into being.Compared with traditional 3D printing technology,4D printing adds a time dimension to common 3D printing technology,and enables printed products to be self-assembled,versatile and self-healing.Therefore,the key to4 D printing is using a material with intelligent deformation properties as printing consumable.On the other hand,3D printing technology based on photo-curing mechanism has the characteristics of high printing precision and short printing time.However,most of the commercial photosensitive resins for 4D printing are petroleum-based polymer compounds,which are expensive and can only be used in ultraviolet region,which is difficult for large scale promotion.Compared with UV curing,visible light curing has the characteristics of low cost,high safety and large curing depth.Therefore,it is of great research significance and practical value to develop low-cost 4D printing consumables with shape memory function which can be rapidly solidified in visible light region.Soybean oil is an important and cheap renewable resource.In this thesis,by a simple one-step reaction of epoxy soybean oil and different unsaturated carboxylic acids,a series of soybean oil-based liquid resin prepolymers were obtained.And then,a series of polymer consumables which could be rapidly cured in visible light region and used for 4D printing,were synthesized by introducing appropriate visible light initiator system and modified carboxylate.By using digital light processing(DLP)3D printer,4D printed products with certain mechanical strength and shape memory performance were produced.The main research contents are as follows:(1)By using epoxidized soybean oil as the oil source,acrylic acid as the ring-opening esterification reagent,hydroquinone as inhibitor and triphenylphosphine as catalyst,mixed prepolymer of epoxy soybean oil acrylate and acrylic acid was synthesized by one-step rection.And then,novel epoxidized soybean oil acrylate-acrylic acid(ESOA-AA)4D printing consumables which could be quickly printed under visible light,was obtained by introducing visible light initiator system of camphor quinone and dimethyl amino benzene formaldehyde for the first time.The resulted consumables were printed by DLP 3D printer to form 4D printing products with shape memory performance.The printed product is yellow and transparent solid with good flexibility and thermally induced shape memory performance.By changing the amount of acrylic acid,we obtained a series of resins with tensile strength in therange of 1.2MPa and 9.8MPa,and glass transition temperature in the range of 20? and 75?.(2)By using epoxidized soybean oil as the oil source,methyl acrylic acid as the ring-opening esterification reagent,hydroquinone as inhibitor and triphenylphosphine as catalyst,mixed prepolymer of epoxy soybean oil acrylate and acrylic acid was synthesized by one-step rection.And then,novel epoxidized soybean oil methyl acrylate-methyl acrylic acid(ESOMA-MAA)4D printing consumables which could be quickly printed under visible light,was obtained by introducing visible light initiator system of camphor quinone and dimethyl amino benzene formaldehyde for the first time.The resulted consumables were printed by DLP 3D printer to form 4D printing products with shape memory performance.The printed product is yellow and transparent solid with thermally induced shape memory performance.By changing the amount of acrylic acid,we obtained a series of resins with tensile strength in the range of 2.9 MPa and 49.5 MPa,and glass transition temperature in the range of96 ? and 196 ?.(3)First,by using epoxy soybean oil and a small amount of methyl acrylic acid as raw materials,a low volatility ESOMA-MAA prepolymer was synthesized.And then,by adding a certain amount of triethylene glycol dimethacrylate(TEGDMA)and visible light initiator system of camphor quinone and dimethyl amino benzene formaldehyde,novel epoxidized soybean oil methacrylate-methyl acrylic acid-triethylene glycol dimethacrylate(ESOMA-MAA-TEGDMA)4D printing materials were obtained.The resulted consumables were printed by DLP 3D printer to form 4D printing products with shape memory performance.By changing the amount of TEGDMA,we obtained a series of resins with tensile strength in the range of 2.9 MPa and 7.4 MPa,and glass transition temperature in the range of 70 ? and 86 ?.