阅读说明：本技术 一种可降解3d打印树脂 (Degradable 3D printing resin ) 是由 王克敏 章文俊 于 2019-12-03 设计创作，主要内容包括：本发明涉及3D打印材料领域,尤其涉及一种可降解3D打印树脂单体。本发明提供一种可降解3D打印树脂单体,这种可降解3D打印树脂单体分子结构上含有丙烯酸双键和丰富的酸酐基团,现有技术中通常采用PLA、ABS、PLGA、蜡树脂等作为PDMS微流控芯片的阳模,去除阳模的溶剂为酸性、碱性或有机溶液,且阳模去除时间较长,本法所制备的3D打印树脂单体聚合之后可采用DLP光固化3D打印制作PDMS微流控芯片的阳模,实现3D打印复杂三维微通道结构,待PDMS微流控芯片固化成型后,在不破坏PDMS微流控芯片微通道的情况下,作为阳模的3D打印树脂可在温水中快速自行水解。(The invention relates to the field of 3D printing materials, in particular to a degradable 3D printing resin monomer. The invention provides a degradable 3D printing resin monomer, wherein the molecular structure of the degradable 3D printing resin monomer contains acrylic double bonds and rich anhydride groups, PLA, ABS, PLGA, wax resin and the like are generally adopted as a male die of a PDMS microfluidic chip in the prior art, the solvent for removing the male die is acidic, alkaline or organic solution, and the male die removing time is long.)

1. A degradable 3D prints resin monomer which characterized in that: the printing resin is prepared by the stepwise reaction of polyhydric alcohol, succinic anhydride and methacrylic anhydride, the molecular structure of the printing resin contains rich anhydride groups and acrylic double bonds, the printing resin can be used for a male mold of 3D printing PDMS, the molecular weight of the polyhydric alcohol is 120-600, and the viscosity of the degradable 3D printing resin monomer is 800-1000mPa & s.

2. The degradable 3D printing resin monomer according to claim 1, wherein: the polyalcohol is one of PEG-400, PTMG-400, PPG-400, trihydroxy methyl propane and pentaerythritol, and the molecular structure of the degradable 3D printing resin monomer is shown as I, II, III and IV as follows:

wherein R has a molecular structure ofOr ＊ CH₃。

3. The method for preparing the degradable 3D printing resin monomer according to claims 1-2, wherein: the preparation method comprises the following steps:

step (1): dissolving succinic anhydride in toluene, adding polyhydric alcohol and a catalyst according to a certain proportion, wherein the molar ratio of hydroxyl of the polyhydric alcohol to the succinic anhydride is 1:1, the reaction temperature is 80-130 ℃, the using amount of the catalyst is 0.0025 percent of the total mass of the polyhydric alcohol and the succinic anhydride, after the reaction is finished for 20 hours, removing the solvent by reduced pressure distillation, and drying to obtain a polyfunctional group carboxylic acid product I;

step (2): adding the product I into methacrylic anhydride, reacting for 24 hours under the protection of oil bath and nitrogen, wherein the molar ratio of carboxyl of the product I to the methacrylic anhydride is 1:1, the reaction temperature is 60-80 ℃, cooling to room temperature after the reaction is finished, and extracting redundant methacrylic anhydride by using an extracting agent to obtain the degradable 3D printing resin monomer containing acrylic double bonds.

4. The method for preparing the degradable 3D printing resin monomer according to claim 3, wherein the method comprises the following steps: the catalyst in the step (1) is one of p-toluenesulfonic acid, pyridine and dimethylaniline.

5. The method for preparing the degradable 3D printing resin monomer according to claim 3, wherein the method comprises the following steps: the extracting agent in the step (2) is n-hexane or petroleum ether.

6. A preparation method of degradable 3D printing resin is characterized by comprising the following steps:

adding a photoinitiator and a light absorber into the degradable 3D printing resin monomer according to the claims 1-2, wherein the addition amount of the photoinitiator is 0.1-5% of the mass of the degradable 3D printing resin monomer, the amount of the light absorber is 0.01-0.1% of the mass of the degradable 3D printing resin monomer, and uniformly mixing and stirring at room temperature to obtain the degradable 3D printing resin.

7. The method for preparing the degradable 3D printing resin according to claim 6, wherein the method comprises the following steps: the photoinitiator is one of TPO, 819, TTX and EDAB.

8. The method for preparing the degradable 3D printing resin according to claim 6, wherein the method comprises the following steps: the light absorber is one of red pigment Sudan I, carotene and ultraviolet absorber 784.

Technical Field

The invention relates to the field of 3D printing materials, in particular to degradable 3D printing resin.

Background

The microfluidic chip can integrate basic operation units of sample preparation, reaction, separation, detection, cell culture, sorting, lysis and the like, which are involved in the chemical and biological fields, on a chip with an area of only a few square centimeters in a low-cost manner, thereby replacing various functions of a conventional chemical and biological laboratory. The essential feature and the greatest advantage of microfluidic chips are the flexible combination and scale of multiple cell technologies on an integrally controllable micro platform, so microfluidic chips are also often referred to as lab-on-a-chip.

Compared with microfluidic chips made of silicon, glass and quartz materials, the microfluidic chip made of PDMS has the characteristics of good chemical inertness, good biocompatibility, excellent optical performance and easiness in molding and bonding. However, the traditional methods for manufacturing the PDMS microfluidic chip, such as a hot pressing method, a molding method, an injection molding method, a laser ablation method, and the like, are long in time consumption, expensive in equipment, and incapable of realizing personalized processing and manufacturing of complex structures. The 3D printing technology is the most representative of the processing technologies which can realize a complex three-dimensional structure, low cost, individuation and small batch manufacturing at present, the processing process of the three-dimensional structure microfluidic chip can be simplified by utilizing the 3D printing technology, and the integrated preparation of the multi-scale and multi-material microfluidic chip is easy to realize.

The 3D printing method for manufacturing the micro-fluidic chip is divided into a direct method and an indirect method. The indirect method is to print a male die in a 3D mode, then perform die reversing, and finally perform punching and packaging to obtain the microfluidic chip. The micro-fluidic chip is manufactured by an indirect method, and a male die printed by photocuring is difficult to remove, so that a complex three-dimensional micro-channel structure is difficult to realize.

At present, the materials of the positive template of the PDMS microfluidic chip manufactured by the 3D printing method include PLA, ABS, PLGA, wax resin, etc., after the PDMS microfluidic chip is manufactured, a volatile organic solvent such as an acidic solution, an alkaline solution, or acetone is needed to remove the positive template, the solvent for removing the positive template has certain corrosiveness or higher VOC content, and the time for removing the positive template is longer, for example, the down wen et al disclose a method for conveniently processing the special-shaped cross-section microchannel based on the 3D printing sacrificial positive template (the down wen, the fan, the lison et al, the special-shaped cross-section microchannel based on the 3D printing sacrificial positive template [ J ] analytical chemistry, 2019,47(6):838 845.), which specifically discloses that the ABS is used as the positive template for preparing the PDMS microfluidic chip, the obtained PDMS block needs to be immersed in the acetone solution, and multiple times of ultrasonic cleaning are carried out to dissolve the ABS channel positive template embedded in the PDMS, the dissolution time of the micron-scale ABS male mold is long (about 4h), and PDMS curing treatment needs to be carried out for many times in the processing process of the microfluidic chip, so that the whole processing period of the microfluidic chip is as long as 8 h.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: in the prior art, PLA, ABS, PLGA, wax resin and the like are generally used as a male die of the PDMS microfluidic chip, the solvent for removing the male die is acidic, alkaline or organic solution, and the male die removing time is long. The invention provides a degradable 3D printing resin monomer, wherein the degradable 3D printing resin monomer is polymerized to obtain the degradable 3D printing resin, the prepared degradable 3D printing resin can be subjected to DLP photocuring printing to form a male die of a PDMS microfluidic chip, and after the PDMS microfluidic chip is cured and molded, the 3D printing resin serving as the male die can be rapidly and automatically hydrolyzed in warm water under the condition of not damaging a microchannel of the PDMS microfluidic chip.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the invention provides a degradable 3D printing resin monomer which is prepared by the stepwise reaction of polyhydric alcohol, succinic acid and anhydride methacrylic anhydride, the molecular structure of the monomer contains rich anhydride groups and acrylic double bonds, the monomer can be used for a male mold of 3D printing PDMS, and the molecular weight of the polyhydric alcohol is 120-600-;

the polyalcohol is one of polyethylene glycol 400(PEG-400), polytetramethylene glycol 400(PTMG-400), polypropylene glycol 400(PPG-400), trihydroxymethyl propane and pentaerythritol, and the molecular structure of the degradable 3D printing resin monomer is shown as I, II, III and IV:

wherein R has a molecular structure of

Or ＊ CH₃。

The reaction process of the degradable 3D printing resin monomer (taking polyhydric alcohol trihydroxymethyl propane as an example) is as follows:

the specific preparation process of the degradable 3D printing resin monomer is as follows:

step (1): dissolving succinic anhydride in toluene, adding polyhydric alcohol and a catalyst according to a certain proportion, wherein the molar ratio of hydroxyl of the polyhydric alcohol to the succinic anhydride is 1:1, the reaction temperature is 80-130 ℃, the using amount of the catalyst is 0.0025 percent of the total mass of the polyhydric alcohol and the succinic anhydride, after the reaction is finished for 20 hours, removing the solvent by reduced pressure distillation, and drying to obtain a polyfunctional group carboxylic acid product I;

step (2): adding the product I into methacrylic anhydride, reacting for 24 hours under the protection of oil bath and nitrogen, wherein the molar ratio of carboxyl of the product I to the methacrylic anhydride is 1:1, the reaction temperature is 60-80 ℃, cooling to room temperature after the reaction is finished, and extracting redundant methacrylic anhydride by using an extracting agent to obtain a degradable 3D printing resin monomer containing acrylic double bonds;

and (3): the preparation method of the degradable 3D printing resin comprises the following steps:

adding a photoinitiator into the degradable 3D printing resin monomer according to the claims 1-2, wherein the addition amount of the photoinitiator is 0.1-5% of the mass of the degradable 3D printing resin monomer, the amount of the light absorber is 0.01-0.1% of the mass of the degradable 3D printing resin monomer, and uniformly mixing and stirring at room temperature to obtain the degradable 3D printing resin;

preferably, the catalyst in the step (1) is one of p-toluenesulfonic acid, pyridine and dimethylaniline;

preferably, the extractant in the step (2) is n-hexane or petroleum ether;

preferably, the photoinitiator in step (3) is one of TPO, 819, TTX, EDAB.

Preferably, the light absorber is one of red pigment Sudan I, carotene and ultraviolet absorber 784.

The invention has the beneficial effects that:

(1) the degradable 3D printing resin monomer prepared by the invention can be used for 3D printing by an FDM fuse manufacturing technology to form a male die of a PDMS microfluidic chip.

(2) The molecular structure of the degradable 3D printing resin prepared by the invention contains rich anhydride groups, after PDMS is poured and cured, a male die formed by the degradable 3D printing resin can be quickly hydrolyzed only by soaking in warm water and ultrasonic cleaning, an acidic solvent, an alkaline solvent or an organic solvent is not needed, and the process of removing the male die can not cause any damage to the microchannel of the PDMS microfluidic chip.

Drawings

FIG. 1: example 1 preparation of product I¹HNMR hydrogen spectrum.

FIG. 2: example 1 preparation of degradable 3D printing resin monomer¹HNMR hydrogen spectrum.

Detailed Description

The present invention will now be described in further detail with reference to examples.