CN116284566B - A photocurable slurry, organic hydrogel and preparation method thereof for highly elastic wearable strain sensor - Google Patents
A photocurable slurry, organic hydrogel and preparation method thereof for highly elastic wearable strain sensor Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 50
- 239000002002 slurry Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 164
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical group C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 72
- 239000002202 Polyethylene glycol Substances 0.000 claims description 45
- 125000004386 diacrylate group Chemical group 0.000 claims description 45
- 229920001223 polyethylene glycol Polymers 0.000 claims description 45
- 238000000498 ball milling Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000010382 chemical cross-linking Methods 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003848 UV Light-Curing Methods 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 description 55
- 238000000016 photochemical curing Methods 0.000 description 48
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 36
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 238000010146 3D printing Methods 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
- 238000004513 sizing Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
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Abstract
本发明公开了一种可用于高弹性可穿戴应变传感器的光固化浆料、有机水凝胶及其制备方法、应用，属于柔性可穿戴电子器件材料技术领域；本发明的一种可用于高弹性可穿戴应变传感器的光固化浆料、有机水凝胶及其制备方法，通过光固化浆料中组分的合理设置以及有机水凝胶制备手段控制；显著改善有机水凝胶传感器的回弹性能；固化后的有机水凝胶吸水/保水性好，可拉伸，回弹性好，用作可穿戴应变传感器。
The present invention discloses a photocurable slurry, an organic hydrogel and a preparation method and application thereof which can be used for a highly elastic wearable strain sensor, and belongs to the technical field of flexible wearable electronic device materials; the present invention discloses a photocurable slurry, an organic hydrogel and a preparation method thereof which can be used for a highly elastic wearable strain sensor, and controls the components in the photocurable slurry by reasonable arrangement and the preparation method of the organic hydrogel; significantly improves the resilience performance of the organic hydrogel sensor; the cured organic hydrogel has good water absorption/water retention, is stretchable, has good resilience, and is used as a wearable strain sensor.
Description
Technical Field
The invention belongs to the technical field of flexible wearable electronic device materials, and particularly relates to a photo-curing slurry and an organic hydrogel for a high-elasticity wearable strain sensor and a preparation method thereof.
Background
The organic hydrogel strain sensor has good flexibility, can be attached to the skin surface of a human body, has important application in the fields of health monitoring, artificial intelligence, electronic skin and the like, and has the working principle of converting an external mechanical signal into an electrical signal which is easy to process.
However, the traditional organic hydrogel strain sensor has the following defects that 1, the organic hydrogel is easy to dehydrate and affects the stability of the sensor, 2, the organic hydrogel cannot rebound completely, so that obvious hysteresis phenomenon occurs in the using process, the mechanical strength is seriously reduced, the electric signal feedback is inaccurate, and the service life is greatly reduced. In addition to the problems with organic hydrogel performance, the preparation of organic hydrogel strain sensors remains a challenge. The traditional preparation technology has long preparation time and complex procedures, and greatly limits the mass production of the strain sensor. Furthermore, conventional methods can only produce simple structures, such as square, elongated structures, limiting the customisation and wearable applications of strain sensors. Along with the development of the intellectualization and customization of wearable electronic products, the development of organic hydrogel strain sensors with structural diversity is of great importance.
Unlike conventional manufacturing processes, 3D printing forms articles by stacking layers. As one of the most mature 3D printing techniques, photo-curing 3D printing is widely used to produce high precision structures, the curing principle of which is to make a photosensitive resin undergo radical polymerization by irradiating it with ultraviolet light. Although commercial elastic photosensitive resins have good elasticity, they have poor stretchability and cannot meet the demands of strain sensors. Accordingly, development of a photocurable paste for stretchable, highly elastic and wearable strain sensors is urgent.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem of poor usability of flexible wearable electronic device materials in the prior art, the light-cured slurry, the organic hydrogel and the preparation method thereof, which can be used for the high-elasticity wearable strain sensor, are provided, and the technical problems are improved through reasonable arrangement of components in the light-cured slurry and control of the preparation means of the organic hydrogel.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention discloses an organic hydrogel for a high-elasticity wearable strain sensor, which comprises a monomer, a water-retaining agent, a chemical cross-linking agent, a photoinitiator and an ion-conducting filler, wherein the monomer is acryloylmorpholine, and the chemical cross-linking agent is polyethylene glycol diacrylate.
Preferably, the contents of the monomer, the water-retaining agent, the chemical crosslinking agent, the photoinitiator and the ion-conducting filler are respectively as follows:
preferably, the water-retaining agent is one or more of glycerol, ethylene glycol and propylene glycol.
Preferably, the photoinitiator is phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Preferably, the ion-conducting filler is sodium chloride.
Preferably, the organic hydrogel is prepared from a photo-curing paste which can be used for the high-elasticity wearable strain sensor, and the photo-curing paste which can be used for the high-elasticity wearable strain sensor is the photo-curing paste.
The invention relates to a preparation method of an organic hydrogel for a high-elasticity wearable strain sensor, which is characterized in that the organic hydrogel for the high-elasticity wearable strain sensor is prepared by the following steps:
S1, mixing a monomer, a photoinitiator, an ion-conducting filler and a grinding aid, and performing first-stage ball milling after mixing to obtain monomer slurry;
s2, carrying out ultraviolet light curing molding on the photo-curing slurry;
s3, performing ultraviolet light curing and forming, and then performing water absorption to prepare the organic hydrogel for the high-elasticity wearable strain sensor.
Preferably, S1 is placed in a dry environment after the photo-curable paste is prepared, preventing the photo-curable paste from absorbing water.
Preferably, the ultraviolet light wavelength in S2 is 405nm, the layer thickness is 2-100 μm, the ultraviolet light intensity is 2-30mW/cm 2, and the exposure time is 0.1-20S.
Preferably, the water absorption environment in the S3 is that the temperature is 22-27 ℃, the humidity is 40-65%, and the water is absorbed for 12-720 hours.
A strain sensor according to the invention is prepared from the organic hydrogel according to claim 5.
The application of the organic hydrogel for the high-elasticity wearable strain sensor provided by the invention is that the organic hydrogel is used as a material of the strain sensor.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The organic hydrogel for the high-elasticity wearable strain sensor comprises a monomer, a water-retaining agent, a chemical crosslinking agent, a photoinitiator and an ion-conducting filler, wherein the monomer is acryloylmorpholine, the chemical crosslinking agent is polyethylene glycol diacrylate, the water-retaining agent is introduced into the acryloylmorpholine organic hydrogel, so that the saturated vapor pressure of the water-retaining agent is effectively reduced, the water-retaining performance of a subsequent organic hydrogel product is ensured, in addition, the covalent crosslinking point of a polymer in the acryloylmorpholine/water-retaining agent can be increased by introducing the polyethylene glycol diacrylate, the rebound performance of the organic hydrogel sensor is obviously improved, and the cured organic hydrogel is good in water absorption/retention, stretchable and elastic and is used as the wearable strain sensor.
(2) The invention relates to a preparation method of an organic hydrogel for a high-elasticity wearable strain sensor, which is characterized in that S1, a monomer, a photoinitiator, an ion-conducting filler and a grinding aid are mixed, and ball milling is carried out in a first stage after mixing to obtain monomer slurry; adding a water-retaining agent and a chemical cross-linking agent into the monomer slurry after the first-stage ball milling is finished, and then performing the second-stage ball milling, and filtering a grinding aid through the second-stage ball milling to prepare a photo-curing slurry; S2, ultraviolet curing and forming the photo-curing slurry, S3, absorbing water after ultraviolet curing and forming to prepare the organic hydrogel for the high-elasticity wearable strain sensor, wherein in the steps, the monomer, the water-retaining agent, the chemical cross-linking agent, the photoinitiator and the ion-conducting filler are mixed and ball-milled in stages to fully form a photo-curing system, and then the water-retaining agent and the chemical cross-linking agent are locally subjected to water retention and chemical cross-linking around the photo-curing system through ball milling in a second stage, so that the subsequent photo-curing effect is improved, and the problem that the existing photo-curing slurry and the printed organic hydrogel product are easy to dehydrate, poor in rebound resilience and customized to wear is solved.
Drawings
FIG. 1 is a graph of the relative mass change of an acryloylmorpholine, acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured product;
In FIG. 2, (a) acryloylmorpholine/glycerol and (b) acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured articles were photographed for stretch and rebound;
In FIG. 3, (a) acryloylmorpholine/glycerol and (b) acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured articles were cycled 100 times at 100% tensile strain;
FIG. 4 is a graph showing the relative resistance change of an acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured article under different strains;
fig. 5 is a photograph of a 3D printed acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured product having a porous structure and in use.
Detailed Description
The following more detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely illustrative and not limiting of the application's features and characteristics in order to set forth the best mode of carrying out the application and to sufficiently enable those skilled in the art to practice the application. It will be understood that various modifications and changes may be made without departing from the scope of the application as defined by the following claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and if any such modifications and variations are desired to be included within the scope of the application described herein. Furthermore, the background art is intended to illustrate the state of the art and the meaning of the development and is not intended to limit the application or the field of application of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, the terms used herein in this description of the invention are used merely for the purpose of describing particular embodiments and are not intended to limit the invention, and the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention is further described below in connection with specific embodiments.
Example 1
1) Preparation of photo-curing slurry of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
69.3G of acryloylmorpholine, 0.7g of TPO,0.05g of sodium chloride and 300g of zirconia balls are weighed, added into a 250ml zirconia ball mill pot and ball-milled for 10min at the speed of 360r/min, so as to obtain the acryloylmorpholine slurry. Then adding 30g of glycerol and 0.25g of polyethylene glycol diacrylate into a ball milling tank, ball milling for 30min at the speed of 360r/min, filtering zirconia balls by using a strainer to obtain the photo-curing slurry of the acryloylmorpholine/glycerol/polyethylene glycol diacrylate, and storing the photo-curing slurry in a closed container to prevent the photo-curing printing from being affected by water absorption of photosensitive resin. The resin absorbs water to increase the adhesion of the printed product, making it difficult to remove the printed sample from the platform.
2) Preparation of photo-curing 3D printing product of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
And (3) carrying out ultraviolet curing molding on the prepared sizing agent by adopting a photocuring 3D printer. The ultraviolet light wavelength was 405nm, the layer thickness was 20 μm, the ultraviolet light intensity was 5mW/cm 2, and the exposure time was 3s. The printing product with the acryloylmorpholine/glycerol/polyethylene glycol diacrylate is prepared. The product is placed under the condition of room temperature (the temperature is 22-27 ℃ and the humidity is 40-65%) to absorb water for 24 hours, and the acryloylmorpholine/glycerol/polyethylene glycol diacrylate organic hydrogel is obtained.
Example 2
1) Preparation of photo-curing slurry of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
69.3G of acryloylmorpholine, 0.7g of TPO,0.05g of sodium chloride and 300g of zirconia balls are weighed, added into a 250ml zirconia ball mill pot and ball-milled for 10min at the speed of 360r/min, so as to obtain the acryloylmorpholine slurry. Then adding 30g of glycerol and 0.5g of polyethylene glycol diacrylate into a ball milling tank, ball milling for 30min at the speed of 360r/min, filtering zirconia balls by using a strainer to obtain the photo-curing slurry of the acryloylmorpholine/glycerol/polyethylene glycol diacrylate, and storing the photo-curing slurry in a closed container to prevent the photo-curing printing from being affected by water absorption of photosensitive resin. The resin absorbs water to increase the adhesion of the printed product, making it difficult to remove the printed sample from the platform.
2) Preparation of photo-curing 3D printing product of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
And (3) carrying out ultraviolet curing molding on the prepared sizing agent by adopting a photocuring 3D printer. The ultraviolet light wavelength was 405nm, the layer thickness was 20 μm, the ultraviolet light intensity was 5mW/cm 2, and the exposure time was 3s. The printing product with the acryloylmorpholine/glycerol/polyethylene glycol diacrylate is prepared. The product is placed under the condition of room temperature (the temperature is 22-27 ℃ and the humidity is 40-65%) to absorb water for 24 hours, and the acryloylmorpholine/glycerol/polyethylene glycol diacrylate organic hydrogel is obtained.
Example 3
1) Preparation of photo-curing slurry of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
69.3G of acryloylmorpholine, 0.7g of TPO,0.05g of sodium chloride and 300g of zirconia balls are weighed, added into a 250ml zirconia ball mill pot and ball-milled for 10min at the speed of 360r/min, so as to obtain the acryloylmorpholine slurry. Then adding 30g of glycerol and 1g of polyethylene glycol diacrylate into a ball milling tank, ball milling for 30min at the speed of 360r/min, filtering zirconia balls by using a strainer to obtain the photo-curing slurry of the acryloylmorpholine/glycerol/polyethylene glycol diacrylate, and storing the photo-curing slurry in a closed container to prevent the photo-curing printing from being influenced by water absorption of photosensitive resin. The resin absorbs water to increase the adhesion of the printed product, making it difficult to remove the printed sample from the platform.
2) Preparation of photo-curing 3D printing product of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
And (3) carrying out ultraviolet curing molding on the prepared sizing agent by adopting a photocuring 3D printer. The ultraviolet light wavelength was 405nm, the layer thickness was 20 μm, the ultraviolet light intensity was 5mW/cm 2, and the exposure time was 3s. The printing product with the acryloylmorpholine/glycerol/polyethylene glycol diacrylate is prepared. The product is placed under the condition of room temperature (the temperature is 22-27 ℃ and the humidity is 40-65%) to absorb water for 24 hours, and the acryloylmorpholine/glycerol/polyethylene glycol diacrylate organic hydrogel is obtained.
Example 4
1) Preparation of photo-curing slurry of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
69.3G of acryloylmorpholine, 0.7g of TPO,0.05g of sodium chloride and 300g of zirconia balls are weighed, added into a 250ml zirconia ball mill pot and ball-milled for 10min at the speed of 360r/min, so as to obtain the acryloylmorpholine slurry. Then adding 30g of glycerol and 5g of polyethylene glycol diacrylate into a ball milling tank, ball milling for 30min at the speed of 360r/min, filtering zirconia balls by using a strainer to obtain the photo-curing slurry of the acryloylmorpholine/glycerol/polyethylene glycol diacrylate, and storing the photo-curing slurry in a closed container to prevent the photo-curing printing from being influenced by water absorption of photosensitive resin. The resin absorbs water to increase the adhesion of the printed product, making it difficult to remove the printed sample from the platform.
2) Preparation of photo-curing 3D printing product of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
And (3) carrying out ultraviolet curing molding on the prepared sizing agent by adopting a photocuring 3D printer. The ultraviolet light wavelength was 405nm, the layer thickness was 20 μm, the ultraviolet light intensity was 5mW/cm 2, and the exposure time was 3s. The printing product with the acryloylmorpholine/glycerol/polyethylene glycol diacrylate is prepared. The product is placed under the condition of room temperature (the temperature is 22-27 ℃ and the humidity is 40-65%) to absorb water for 24 hours, and the acryloylmorpholine/glycerol/polyethylene glycol diacrylate organic hydrogel is obtained.
Comparative example 1
(1) Preparation of photo-curing acryl morpholine slurry
69.3G of acryloylmorpholine, 0.7g of TPO,0.05g of sodium chloride and 300g of zirconia balls are weighed into a 250ml zirconia ball mill tank, ball milling is carried out for 10min at the speed of 360r/min, and the zirconia balls are filtered by a strainer to obtain the acryloylmorpholine photocuring slurry.
(2) Preparation of Acryloylmorpholine photo-cured 3D printing products
And (3) carrying out ultraviolet curing molding on the prepared sizing agent by adopting a photocuring 3D printer. The ultraviolet light wavelength was 405nm, the layer thickness was 20 μm, the ultraviolet light intensity was 5mW/cm 2, and the exposure time was 3s. And preparing the printing product with the acryloylmorpholine. The product is placed under the condition of room temperature (the temperature is 22-27 ℃ and the humidity is 40-65%) to absorb water for 24 hours, and the acryloylmorpholine organic hydrogel is obtained.
Comparative example 2
1) Preparation of Acryloylmorpholine/glycerol photo-curing slurry
69.3G of acryloylmorpholine, 0.7g of TPO,0.05g of sodium chloride and 300g of zirconia balls are weighed, added into a 250ml zirconia ball mill pot and ball-milled for 10min at the speed of 360r/min, so as to obtain the acryloylmorpholine slurry. Then adding 30g of glycerol into a ball milling tank, ball milling for 30min at the speed of 360r/min, filtering out zirconia balls by using a strainer to obtain the acryloylmorpholine/glycerol photocuring slurry, and storing the slurry in a closed container to prevent the photosensitive resin from absorbing water to influence the photocuring printing. The resin absorbs water to increase the adhesion of the printed product, making it difficult to remove the printed sample from the platform.
2) Preparation of acryloylmorpholine/glycerol photocuring 3D printing product
And (3) carrying out ultraviolet curing molding on the prepared sizing agent by adopting a photocuring 3D printer. The ultraviolet light wavelength was 405nm, the layer thickness was 20 μm, the ultraviolet light intensity was 5mW/cm 2, and the exposure time was 3s. The printed product with acryloylmorpholine/glycerin is prepared. The product is placed under the condition of room temperature (the temperature is 22-27 ℃ and the humidity is 40-65%) to absorb water for 24 hours, and the acryloylmorpholine/glycerol organic hydrogel is obtained.
Index performance verification is performed on the photo-curing slurries prepared in examples 1-4 and comparative examples 1-2, as shown in table 1. As can be seen from Table 1, in several examples, the resin viscosity was less than 60 mPas, which is suitable for use in photo-curing 3D printing.
TABLE 1 photo-curing syrup of acryloylmorpholine/glycerol/polyethylene glycol diacrylate
As shown in figure 1, the pure acryloylmorpholine solidified product is placed under the condition of room temperature, firstly absorbs water and then loses water, and has poor water retention property, and after glycerin is added, the acryloylmorpholine/glycerin and the acryloylmorpholine/glycerin/polyethylene glycol diacrylate solidified product have no obvious water loss phenomenon, thus having good water absorption/water retention property.
For the cured product of acryloylmorpholine/glycerol, the cured product of acryloylmorpholine/glycerol cannot be fully recovered after stretching due to lack of enough chemical crosslinking points (as shown in fig. 2 a), and the introduction of polyethylene glycol diacrylate increases chemical crosslinking (covalent crosslinking points) of acryloylmorpholine. Sufficient covalent crosslinking points ensure that the crosslinked network of the acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured article is not broken under stretching, so that the acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured article can rebound completely (see fig. 2 b). Thus, the residual strain of the acryloylmorpholine/glycerol cured article was gradually increased and the maximum stress was significantly reduced for the cyclic loading-unloading force test of the acryloylmorpholine/glycerol cured article, indicating poor resilience (as in fig. 3 a), and the subsequent stress-strain curve area was substantially unchanged for the acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured article after two cycles of the cyclic loading-unloading force test, indicating excellent resilience and fatigue resistance for the acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured article (as in fig. 3 b).
Since the acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured product has excellent resilience, the cured product can be used as a strain sensor. The resistance of the acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured product changed regularly under different strains and responded repeatedly, indicating potential sensing performance (as shown in fig. 4).
Finally, the 3D printed acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured product has structural design, and the ring with the hole structure can be prepared to be directly worn on the finger. The bending motion of the finger caused the regular change in resistance of the acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured article and repeated responses, indicating that the 3D printed acryloylmorpholine/glycerol/polyethylene glycol diacrylate cured article could be used as a potential wearable organic hydrogel strain sensor (see fig. 5).
The application has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will be understood that various modifications and changes may be made without departing from the scope of the application as defined by the following claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and if any such modifications and variations are desired to be included within the scope of the application described herein. Furthermore, the background art is intended to illustrate the state of the art and the meaning of the development and is not intended to limit the application or the field of application of the application.
More specifically, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments, but includes any and all embodiments that have been modified, omitted, e.g., combined, adapted, and/or substituted between the various embodiments, as would be recognized by those skilled in the art in light of the foregoing detailed description. The limitations in the claims are to be interpreted broadly based on the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control. Where a molar amount, mass, concentration, temperature, time, volume, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1-50 should be understood to include any number, combination of numbers, or subranges selected from 1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49 or 50, and all fractional values between the integers described above, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. Regarding sub-ranges, specifically considered are "nested sub-ranges" that extend from any end point within the range. For example, the nested subranges of exemplary ranges 1-50 can include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.
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| CN111423536A (en) * | 2020-02-29 | 2020-07-17 | 湖南大学 | High-tensile conductive hydrogel for photocuring 3D printing and preparation method thereof |
| CN113717324A (en) * | 2021-09-14 | 2021-11-30 | 中国科学院化学研究所 | Photocurable 3D printing conductive ionic gel, special photosensitive resin thereof and preparation method |
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| CA2468988A1 (en) * | 2001-12-19 | 2003-06-26 | Richard Hoskins | Hydrogel compositions comprising an acryloyl morpholine polymer |
| US11274169B2 (en) * | 2017-05-14 | 2022-03-15 | Collider, Inc. | Synthetic resin composition and method for hybrid manufacturing |
| CN110105502B (en) * | 2019-04-08 | 2020-10-27 | 西安交通大学 | A kind of multifunctional organogel and preparation method thereof |
| CN110108392B (en) * | 2019-04-08 | 2020-10-27 | 西安交通大学 | Application of a multifunctional organogel in sensors |
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| CN113717324A (en) * | 2021-09-14 | 2021-11-30 | 中国科学院化学研究所 | Photocurable 3D printing conductive ionic gel, special photosensitive resin thereof and preparation method |
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