CN109851727B - Thixotropic photocuring hydrogel and preparation method and application thereof - Google Patents
Thixotropic photocuring hydrogel and preparation method and application thereof Download PDFInfo
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- CN109851727B CN109851727B CN201910010322.7A CN201910010322A CN109851727B CN 109851727 B CN109851727 B CN 109851727B CN 201910010322 A CN201910010322 A CN 201910010322A CN 109851727 B CN109851727 B CN 109851727B
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- 230000009974 thixotropic effect Effects 0.000 title claims abstract description 44
- 239000000017 hydrogel Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000016 photochemical curing Methods 0.000 title description 17
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000000499 gel Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006254 rheological additive Substances 0.000 claims abstract description 14
- 238000010146 3D printing Methods 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- 238000007639 printing Methods 0.000 abstract description 12
- 239000003292 glue Substances 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 238000001723 curing Methods 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 5
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 210000000056 organ Anatomy 0.000 description 2
- 229940089985 polyethylene glycol 700 Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960001631 carbomer Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
本发明公开了一种触变性光固化水凝胶及其制备方法和应用，该制备方法包括如下步骤：将流变调节剂与去离子水充分混合得混合物A；向混合物A中加入丙烯酰胺单体与聚乙二醇二丙烯酸酯充分搅拌的混合物B；向混合物B中添加自由基型光引发剂，充分混合后真空消泡得到无气泡的凝胶；使用紫外光或进紫外光照射消泡后的凝胶，得到固化水凝胶。本发明的触变性光固化水凝胶是一种可以光固化，有触变特性，透明，软体的新型打印介质，可以达打印透明，软体，可光固化的复杂模型；本发明通过赋予水凝胶光固化和触变性的功能，可以让嵌入式3D打印后的复杂实体得以保存，透明软体的属性在医疗手术预判方面有很大潜力。The invention discloses a thixotropic light-cured hydrogel and a preparation method and application thereof. The preparation method comprises the following steps: fully mixing a rheology modifier and deionized water to obtain a mixture A; adding acrylamide monolayer to the mixture A Mixture B, which is fully stirred with polyethylene glycol diacrylate; add a free radical photoinitiator to mixture B, and after thorough mixing, vacuum defoaming to obtain a bubble-free gel; use ultraviolet light or ultraviolet light to defoam After the gel, a cured hydrogel was obtained. The thixotropic light-curing hydrogel of the present invention is a new type of printing medium that can be light-cured, has thixotropic properties, is transparent and soft, and can print complex models that are transparent, soft and light-curable; The functions of glue light curing and thixotropy can save complex entities after embedded 3D printing. The properties of transparent soft bodies have great potential in the prediction of medical operations.
Description
Technical Field
The invention belongs to the technical field of additional manufacturing, and particularly relates to a light-cured hydrogel material with thixotropic property for embedded 3D printing and a preparation method and application thereof.
Background
Embedded 3D printing (Embedded 3D printing) is a relatively novel 3D printing technique that extrudes multiple materials in a gel medium using extremely fine hollow needle tubes. Because the gel medium has certain thixotropic property, the gel medium can be recovered as before in a short time after the needle point is scratched, so that the printed material on the next layer does not influence the material on the previous layer, and the 3D printing process is realized by layer-by-layer accumulation in the thixotropic gel. The advantage of this technique is that it does not require support, and the disadvantage is that only thin walls can be printed, and the mould after printing is difficult to fix. The existing gel for the embedded 3D printing technology has carbomer hydrogel, gelatin and the like with single components, and a medium cannot be solidified after printing, and only has thin-wall characteristics without a solid structure.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problem that a gel medium in common embedded 3D printing is not curable in the prior art, the invention provides the thixotropic photocuring hydrogel which is a novel printing medium which can be photocured, has thixotropic property, is transparent and soft, can print a complex model with high transparency and high elasticity and can be rapidly photocured, and has great potential in material increase manufacturing of organ models and soft models.
The invention also provides a preparation method and application of the thixotropic photocuring hydrogel.
The technical scheme is as follows: in order to achieve the above object, a method for preparing a thixotropic photocurable hydrogel according to the present invention comprises the steps of:
(1) fully mixing a rheology modifier with deionized water to obtain a mixture A;
(2) adding a mixture B of acrylamide monomer and polyethylene glycol diacrylate into the mixture A and fully stirring;
(3) adding a free radical type photoinitiator into the mixture B, fully mixing, and performing vacuum defoaming to obtain bubble-free gel;
(4) irradiating the defoamed gel by using ultraviolet light or ultraviolet light to obtain the cured hydrogel.
Wherein the concentration of the rheological regulator in the step (1) in deionized water is 0.5-2 g/L. Too low a concentration may result in less than desirable thixotropic properties and the material does not heal automatically during printing.
Preferably, the rheology modifier in step (1) is Carbopol940, Carbopol Ultrez 21, Carbopol 980 or fumed silica, and the rheology modifier is neutralized by sodium hydroxide solution during the thorough mixing with deionized water. The pH value of the system is adjusted to 7, so that the system reaches the optimal viscosity.
Preferably, the ratio of the acrylamide monomer to the polyethylene glycol diacrylate in the step (2) is 99-99.9 wt.%, that is, the acrylamide monomer accounts for 99-99.9% of the total mass of the acrylamide monomer and the polyethylene glycol diacrylate; the proportion of the mixture formed by the acrylamide monomer and the polyethylene glycol diacrylate to the mixture A is 20-25 wt.%, namely the mass of the mixture formed by the acrylamide monomer and the polyethylene glycol diacrylate accounts for 20-25% of the total mass of the mixture A and the mixture A. The proportion of polyethylene glycol diacrylate should not be too high, which would lead to brittle systems after curing.
Further, in the step (3), the addition amount of the free radical photoinitiator is 0.01-2% of the mass of the mixture B. The free radical photoinitiator can absorb photons in a wavelength range of 360-450 nm to generate free radicals, the addition amount of the free radical photoinitiator is 0.01-2% of the mass of the mixture B, and the system is whitened when the proportion is too high.
Preferably, the sufficient mixing in step (3) is a long stirring and is a necessary step to allow the photoinitiator to be dispersed in the fluid of thixotropic properties. The photoinitiator is difficult to disperse in the fluid with thixotropic property, and if the stirring is insufficient, the phenomenon of whitening after curing occurs
Preferably, the pressure for vacuum defoaming in the step (3) is 0.5 to 500 Pa.
Further, the wavelength of the ultraviolet light or the ultraviolet light entering the ultraviolet light in the step (4) is 350-460 nm, and the irradiation intensity is 80-100 w. The high intensity radiation can enable the whole system to be cured quickly, and time is saved.
The thixotropic photocuring hydrogel prepared by the preparation method is provided.
The thixotropic photocuring hydrogel prepared by the preparation method disclosed by the invention is applied to embedded 3D printing.
The thixotropic photocuring hydrogel is applied to embedded 3D printing as a medium, and in the embedded 3D printing process, the vacuum defoaming obtained in the step (3) is carried out to obtain bubble-free gel; putting the ink into a transparent container of an embedded printer, wherein the ink extruded by a machine needle point can suspend in a gel medium due to the thixotropic property of gel, and printing is finished layer by layer; and then carrying out ultraviolet curing.
The raw materials in the present invention are all commercially available, and the rheology modifiers Carbopol940, Carbopol Ultrez 21, Carbopol 980, fumed silica are available from Luborun Special chemical Co., Ltd.
The acrylamide monomer and the polyethylene glycol diacrylate are purchased from Shanghai Michelin Biochemical technology Co., Ltd. the polyethylene glycol diacrylate used in the present invention is polyethylene glycol 400 diacrylate (PEG400DA, number average molecular weight 400), and polyethylene glycol 700 diacrylate can also be used.
The free radical photoinitiator TPO was purchased from Shanghai photo chemical Co., Ltd.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the thixotropic photocuring hydrogel prepared by the invention is a novel printing medium which can be photocured, has thixotropic property, is transparent and soft, can print a complex model with high transparency, high elasticity and rapid photocuring in the gel medium, and has great potential in additive manufacturing of organ models and soft models; and the preparation is simple, the use is convenient, and the large-scale industrial production and application can be realized.
The thixotropic property of the thixotropic photocuring hydrogel can enable the printed material to be supported in the gel, layers are not affected with each other, meanwhile, the gel can be photocured into an elastic entity after printing is finished, the printed structure is fixed, and the thixotropic property of the gel enables the printed material to be quickly and automatically healed after being sheared by a printing probe. According to the invention, by endowing hydrogel with functions of photocuring and thixotropy, the embedded 3D printed complex entity can be stored, and the attribute of the transparent software has great potential in the aspect of medical operation prejudgment.
The thixotropic photocuring hydrogel prepared by the invention is neutralized by sodium hydroxide by using a rheological control agent such as Carbopol940, so that the thixotropic property can reach the optimal state; the acrylamide monomer and the polyethylene glycol diacrylate are transparent water-soluble prepolymers which do not react with the rheology modifier, and the whole system is in a transparent state, and the latter adds toughness to the whole system after curing. The raw materials can be fully dispersed by fully mixing for a plurality of times in the whole preparation process, and the whitening after curing is avoided. The vacuum defoaming has the beneficial effects of improving the mixing degree and increasing the transparency degree of the whole formula.
The present invention improves the print media so that the gel media can be fixed by means of photocuring after printing so that complex molds can form an "amber" like structure after curing.
Drawings
FIG. 1 wavelength scan of a cured thixotropic photocurable hydrogel prepared in example 1;
FIG. 2 test chart for breaking strength of thixotropic photocurable hydrogel prepared in example 1.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
(1) Mixing 2g of carbopol940 rheology modifier with 1000mL of deionized water, neutralizing by using a sodium hydroxide solution in the mixing process, measuring the mixture by using a pH meter, and stopping titration when the mixture is completely mixed and becomes neutral to obtain a mixture A;
(2) adding 200g of acrylamide monomer into 700g of the mixture A, slightly mixing, adding 1.25g of polyethylene glycol 400 diacrylate, and continuously mixing for 15 minutes by using a mechanical stirrer to obtain a mixture B;
(3) dripping 0.1g of TPO photoinitiator (liquid, free radical type) into 700g of the mixture B, stirring for 2 hours under the condition of keeping out of the sun by using a mechanical stirrer, and defoaming the obtained mixture under the air pressure of 250Pa in vacuum for later use;
(4) and taking out the printed container, and irradiating the container for 3 minutes at a distance of 5cm by using a near ultraviolet light source of 405nm and 100w for curing to obtain the thixotropic photocuring hydrogel.
Example 2
(1) Mixing 0.5g of carbopol940 rheology modifier with 1000mL of deionized water, neutralizing by using a sodium hydroxide solution in the mixing process, measuring the mixture by using a pH meter, and stopping titration when the mixture is completely mixed and becomes neutral to obtain a mixture A;
(2) adding 250g of acrylamide monomer into 1000g of the mixture A, slightly mixing, adding 1.25g of polyethylene glycol 400 diacrylate, and continuously mixing for 15 minutes by using a mechanical stirrer to obtain a mixture B;
(3) dripping 0.5g of TPO photoinitiator (liquid, free radical type) into 1000g of the mixture B, stirring for 2 hours in a dark condition by using a mechanical stirrer, and defoaming the obtained mixture in vacuum under the air pressure of 0.5Pa for later use;
(4) and taking out the printed container, and irradiating the container for 1 minute at a distance of 5cm by using near ultraviolet light of 460nm and 100w for curing to obtain the thixotropic photocuring hydrogel.
Example 3
(1) Mixing 1g of carbopol940 rheology modifier with 1000mL of deionized water, neutralizing by using a sodium hydroxide solution in the mixing process, measuring the mixture by using a pH meter, and stopping titration when the mixture is completely mixed and becomes neutral to obtain a mixture A;
(2) adding 225g of acrylamide monomer into 905g of the mixture A, slightly mixing, adding 1.25g of polyethylene glycol 400 diacrylate, and continuously mixing for 15 minutes by using a mechanical stirrer to obtain a mixture B;
(3) dripping 0.2g of TPO photoinitiator (liquid, free radical type) into 500g of the mixture B, stirring for 5 hours under the condition of keeping out of the sun by using a mechanical stirrer, and defoaming the obtained mixture in vacuum under the air pressure of 500Pa for later use;
(4) and taking out the printed container, and irradiating the container for 5 minutes at a distance of 5cm by using ultraviolet light of 350nm and 80w for curing to obtain the thixotropic photocuring hydrogel.
Example 4
Example 4 was prepared in the same manner as in example 1, except that the ratio of acrylamide monomer to polyethylene glycol 700 diacrylate in step (2) was 99.9 wt.%; in the step (3), the addition amount of the free radical photoinitiator is 2% of the mass of the mixture B.
Example 5
Example 4 the same procedure as in example 1 was followed, except that in step (1) the rheology modifier Carbopol940 was replaced with Carbopol Ultrez 21, Carbopol 980 or fumed silica, respectively.
Example 6
Application of thixotropic photocuring hydrogel in embedded 3D printing
The preparation method of the embodiment 1 is adopted, the gel obtained in the step (4) is placed into a transparent container of an embedded printer, and the ink extruded by a machine needle point can be suspended in a gel medium due to the thixotropic property of the gel, so that the ink can be printed layer by layer until the printing is finished; the printed container was removed and irradiated using a 405nm, 100w near uv light source for 3 minutes at a distance of 5cm to cure the entire system, during which time the ink was also cured therein.
Test example 1
The thixotropic light-cured hydrogel material prepared in example 1 was subjected to a transparency test, and a cured standard block with a thickness of 1cm was subjected to ultraviolet and visible wavelength scanning by using a spectrophotometer, as can be seen from fig. 1, the sample maintained a transmittance of 50% or more in the visible wavelength band, and the results of examples 2 to 4 were similar, indicating that the thixotropic light-cured hydrogel material prepared in the present invention has a transparent property.
The thixotropic photocurable hydrogel prepared in example 1 was subjected to a tensile strength test, and a dumbbell-shaped standard block (ASTM D412Type A) was tested by using a breaking strength tester, and as can be seen from FIG. 2, the sample was broken when it was stretched by about 12 times, the tensile strength was about 17kPa, and the results of examples 2 to 4 were similar, indicating that the thixotropic photocurable hydrogel prepared in accordance with the present invention has good elasticity.
The thixotropic photocurable hydrogel samples prepared in example 1 were viscosity tested using a rotational viscometer to obtain a viscosity of 49700 mPa.s at 6 rpm and a viscosity drop of 9750 mPa.s at 60 rpm, indicating that the gel became thinner with increasing shear rate, a property which ensures that the extruded ink stays in place during printing.
Claims (5)
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| CN110564009B (en) * | 2019-08-20 | 2021-09-17 | 上普(北京)生物科技有限公司 | Composition for treating skin inflammation |
| CN110628048B (en) * | 2019-10-15 | 2022-03-22 | 常州增材制造研究院有限公司 | Preparation method of conductive hydrogel for 3D printing |
| CN114177356B (en) * | 2021-12-13 | 2023-05-09 | 中国药科大学 | A preparation method and application of printing ink that can be used for photocuring 3D printing |
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| CN107236135A (en) * | 2017-07-07 | 2017-10-10 | 中国科学院理化技术研究所 | Gelatin hydrogel and preparation method and application thereof |
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| CN107614264A (en) * | 2014-12-05 | 2018-01-19 | 佛罗里达大学研究基金会有限公司 | 3D printing using phase change materials as supports |
| CN104721887A (en) * | 2015-02-25 | 2015-06-24 | 湖北工业大学 | Method for preparing polyving akohol/nanosized silica composite hydrogel scaffold through 3D printing |
| CN107236135A (en) * | 2017-07-07 | 2017-10-10 | 中国科学院理化技术研究所 | Gelatin hydrogel and preparation method and application thereof |
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