阅读说明：本技术 一种适用于光固化成型3d打印技术的新型光敏树脂 (Novel photosensitive resin suitable for photocuring forming 3D printing technology ) 是由 不公告发明人 于 2020-05-19 设计创作，主要内容包括：本发明公开了一种适用于光固化成型3D打印技术的新型光敏树脂,它由以下按重量份配比的原料制成：二官能度丙烯酸酯低聚物(JAZO-401)10-20份、六官能度聚氨酯丙烯酸酯(JAZO-303)10-20份、三缩丙二醇双丙烯酸酯(TPGDA)20-40份、2-羟基-2-甲基-1-苯基-1-丙酮(1173光引发剂,简称HMPF)0.5-2份、废弃木薯渣10-40份。通过此种方案合成一种含两种低聚物的自由基聚合型光敏树脂,其力学性能较单一组分的纯丙烯酸酯树脂有极大的提高,并且可以降低成本,对废弃物进行高值化利用提供了另一种途径；本发明的废弃纤维增强型光敏树脂具有反应活性高,凝胶率高(凝胶含量达到99.22%),力学性能较好(断裂伸长率为4.97%,拉伸强度为28.98 MPa,弹性模量为841.11 MPa),对固化设备及环境要求较低等特点。(The invention discloses a novel photosensitive resin suitable for a photocuring molding 3D printing technology, which is prepared from the following raw materials in parts by weight: 10-20 parts of difunctional acrylate oligomer (JAZO-401), 10-20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20-40 parts of tripropylene glycol diacrylate (TPGDA), 0.5-2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 10-40 parts of waste cassava residue. The free radical polymerization type photosensitive resin containing two oligomers is synthesized by the scheme, the mechanical property of the resin is greatly improved compared with that of pure acrylate resin with a single component, the cost can be reduced, and another way is provided for high-valued utilization of wastes; the waste fiber reinforced photosensitive resin has the characteristics of high reactivity, high gel rate (the gel content reaches 99.22%), good mechanical properties (the elongation at break is 4.97%, the tensile strength is 28.98 MPa, the elastic modulus is 841.11 MPa), low requirements on curing equipment and environment and the like.)

1. A novel photosensitive resin suitable for a photocuring molding 3D printing technology is prepared from the following raw materials in parts by weight: 10-20 parts of difunctional acrylate oligomer (JAZO-401), 10-20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20-40 parts of tripropylene glycol diacrylate (TPGDA), 0.5-2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 10-40 parts of waste cassava residue;

the preparation method comprises the following operation steps:

s1, preprocessing: adding purchased industrial cassava residue into prepared hydrogen peroxide, then putting into an ultrasonic cleaning instrument for cleaning for 30-40min, carrying out auxiliary decolorization, then washing with distilled water (the ratio of fiber to distilled water is 1:100(g/ml)), carrying out suction filtration, and repeating twice; then drying and sieving for later use;

s2, weighing: accurately weighing the diluted 1173 photoinitiator, the pure acrylate oligomer (JAZO-401), the polyurethane acrylate (JAZO-303) and the reactive diluent TPGDA in a fume hood by using an analytical balance, and placing the weighed materials into a container to be protected from light and sealed for later use;

s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer for stirring at a constant temperature of 25 ℃, adding the cassava residue pretreated in the step S1, continuing stirring to obtain colorless transparent liquid, namely the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner for ultrasonic treatment, removing bubbles, and placing in a dark place for later use;

s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;

s5, curing: and (3) placing the mold filled with the liquid photosensitive resin under an ultraviolet lamp for curing, turning off the ultraviolet lamp after curing is finished, and taking out the resin sheet in the mold.

2. The novel photosensitive resin suitable for the photocuring molding 3D printing technology as claimed in claim 1, wherein in the step of pretreating the industrial cassava dregs, the concentration of hydrogen peroxide is 10-15%, the ultrasonic power of an ultrasonic cleaner is 60-150W, the temperature is 50-60 ℃, the drying temperature of an oven is set to 105 ℃, and the industrial cassava dregs are crushed and sieved by a 60-mesh sieve.

3. The novel photosensitive resin suitable for stereolithography 3D printing technology as claimed in claim 1, wherein the concentration of 1173 photoinitiator diluted in step S2 is 3-5%.

4. The novel photosensitive resin suitable for the photocuring molding 3D printing technology as claimed in claim 1, wherein the specific parameters of the step S3 for placing the resin mixture on the digital display constant-temperature magnetic stirrer are as follows: keeping the temperature at 60 ℃ at 200-300rpm, and stirring for 30-60 min; adding the pretreated cassava residues, and continuing stirring at normal temperature at 400rpm for 30-60min and ultrasonic in an ultrasonic cleaner for 30-40 min.

5. The novel photosensitive resin suitable for photocuring molding 3D printing technology as claimed in claim 1, wherein the power of an ultraviolet lamp is 60-80W, the peak wavelength is 310-400nm, the curing irradiation height of the ultraviolet lamp is 10cm, and the curing time is 3-5 min.

Technical Field

The invention belongs to the technical field of 3D printing, and particularly relates to preparation of novel photosensitive resin suitable for a photocuring forming 3D printing technology.

Background

The photocuring molding 3D printing technology takes a computer three-dimensional design model as a blueprint, and by means of a software layering dispersion and numerical control molding system, photosensitive resin materials are irradiated by ultraviolet light to cause photosensitive resin to be polymerized in a radiation mode to form cross-linked polymers, so that solid entity products are manufactured. The photosensitive resin has the characteristics of economy, high efficiency, environmental protection, energy conservation, strong adaptability and the like, and has wide application and wide market in the fields of packaging printing, automobile industry, medical health, aerospace, electronic communication and the like.

At present, the existing photosensitive resin has high cost, and has the problems of low hardness, poor heat resistance, poor mechanical property and the like after photocuring a formed part, and the inherent defects cause that the formed part can not be directly used as a functional part, thereby limiting the application range of photocuring forming materials. The cassava residue contains cellulose, and the cellulose has good toughness, dispersibility and chemical stability and can serve as a reinforcing agent in photosensitive resin modification. In view of the insufficient research on photosensitive resin at present in China, the photosensitive resin is still in the exploration stage in some aspects

Therefore, the photosensitive resin with better performance is prepared by utilizing the existing raw materials, a novel photosensitive resin formula and a preparation process thereof are explored, and the experiences are accumulated for the related research of the photocuring resin in China.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a formula and a preparation process of a novel photosensitive resin suitable for a photocuring molding 3D printing technology, the scheme synthesizes a free radical polymerization type photosensitive resin containing two oligomers, the performance of the photosensitive resin is greatly improved compared with that of a pure acrylate resin with a single component, the cost can be reduced, and another way is provided for high-valued utilization of wastes; the waste fiber reinforced photosensitive resin has the characteristics of high reactivity, high gel rate, good mechanical property, low requirements on curing equipment and environment and the like.

The invention solves the technical problems by the following technical scheme:

the invention relates to a novel photosensitive resin suitable for a photocuring molding 3D printing technology, which is prepared from the following raw materials in parts by weight: 10-20 parts of difunctional acrylate oligomer (JAZO-401), 10-20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20-40 parts of tripropylene glycol diacrylate (TPGDA), 0.5-2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 10-40 parts of waste cassava residue.

The preparation method comprises the following operation steps:

s1, preprocessing: adding the purchased industrial cassava residue into 10-15% hydrogen peroxide, cleaning in an ultrasonic cleaner with ultrasonic power of 60W and temperature of 50-60 deg.C for 30-40min, performing auxiliary decolorization, washing with distilled water, vacuum filtering, and repeating twice. Then putting the mixture into an oven to be dried to constant weight at 105 ℃, crushing the mixture and sieving the crushed mixture with a 60-mesh sieve for later use;

s2, weighing: accurately weighing 1173-5% photoinitiator, pure acrylate oligomer (JAZO-401), polyurethane acrylate (JAZO-303) and TPGDA (reactive diluent) in a ventilated kitchen by using an analytical balance, and placing in a container to be protected from light and sealed for later use;

s3, mixing: placing the resin mixture weighed in the step S2 on a digital display constant temperature magnetic stirrer, stirring for 30-60min at a constant temperature of 60 ℃ and a speed of 200 plus materials and 300rpm, adding the pretreated cassava residues, continuously stirring for 30-60min at a normal temperature and a speed of 300 plus materials and 400rpm, wherein the obtained colorless transparent liquid is the prepared liquid photosensitive resin, placing a medicine bottle containing the liquid photosensitive resin in an ultrasonic cleaner for ultrasonic treatment for 30-40min, removing bubbles, and placing in a dark place for later use;

s4, film formation: adding the resin mixed in the step S3 into a polytetrafluoroethylene mold, wherein the height of the liquid resin is about half of the depth of the mold, the mold is placed on a horizontal table, and a few bubbles in the mixed resin can be blown through by a aurilave;

s5, curing: curing the mold filled with the liquid photosensitive resin under an ultraviolet lamp with power of 80W and peak wavelength of 365nm for 3-5min, wherein the curing irradiation height of the ultraviolet lamp is 10cm, and the resin sheet in the mold is taken out after the curing is finished;

the invention has the following beneficial effects:

(1) the 3D printing photosensitive resin comprises the following components: the oligomer, the photoinitiator, the reactive diluent and the like have low skin irritation, low toxicity and low price, protect the human health to the maximum extent and save the cost;

(2) the invention aims to fully utilize waste cellulose resources and improve the solid loading capacity of cellulose in the 3D printing photosensitive resin;

(2) the 3D printing photosensitive resin contains cellulose components of cassava residues, can improve the mechanical property of a formed part, and obviously improves the tensile strength and Young modulus.

Detailed Description

In the preparation raw materials, difunctional acrylate oligomer (JAZO-401), hexafunctional polyurethane acrylate (JAZO-303) and tripropylene glycol diacrylate (TPGDA) are adopted as main materials, 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and waste cassava residue are adopted as auxiliary agents, and the main materials and the auxiliary agents are prepared from the following raw materials in parts by weight: 10-20 parts of difunctional acrylate oligomer (JAZO-401), 10-20 parts of hexafunctional polyurethane acrylate (JAZO-303), 20-40 parts of tripropylene glycol diacrylate (TPGDA), 0.5-2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173 photoinitiator, HMPF for short) and 10-40 parts of waste cassava residue.

The following are specific embodiments of the present invention: