CN115490980B - Gel rate adjustable 3D printing hydrogel ink - Google Patents
Gel rate adjustable 3D printing hydrogel ink Download PDFInfo
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- CN115490980B CN115490980B CN202211216319.9A CN202211216319A CN115490980B CN 115490980 B CN115490980 B CN 115490980B CN 202211216319 A CN202211216319 A CN 202211216319A CN 115490980 B CN115490980 B CN 115490980B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F220/56—Acrylamide; Methacrylamide
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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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
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
Abstract
The invention relates to 3D printing hydrogel ink with adjustable gel rate, and belongs to the technical field of polymer gel. The ink adopts a two-component form, wherein the component A mainly comprises an aqueous solution of Si-N-containing organosiloxane, and the component B mainly comprises an acrylamide monomer or acrylic acid, a cross-linking agent, persulfate and water; alkali metal ions or alkaline earth metal ions are added to the a-component and/or the B-component. The invention provides a novel Si-N-containing organosiloxane/persulfate redox system, wherein alkali metal ions or alkaline earth metal ions are added into the system to catalyze redox reaction, so that quick solidification and molding of hydrogel at room temperature are realized. The gel time of the system can be regulated and controlled by regulating the concentration of alkali metal ions or alkaline earth metal ions, and the method is simple to operate and controllable in gel time.
Description
Technical Field
The invention relates to 3D printing hydrogel ink with adjustable gel rate, and belongs to the technical field of polymer gel.
Background
Biological 3D printing technology is a high-resolution high-precision rapid prototyping technology, and has received a great deal of attention as an emerging research direction. Biological 3D printing techniques are diverse, where micro-extrusion is a powerful method, where the biological ink in a cartridge is extruded through a nozzle under pressure and stacked layer by layer on a platform. Thus, there is a need for bio-inks that not only can be extruded smoothly but also can be set quickly after deposition. Hydrogels are an ideal printable material for micro-extrusion.
The Chinese patent with the publication number of CN113292678B discloses a direct writing 3D printing ionic conductive hydrogel, which comprises polyvinyl alcohol, chitosan, acrylamide, a photoinitiator, a cross-linking agent and water, wherein the three-dimensional hydrogel is required to be cured by ultraviolet light, and the curing time is not adjustable, so that the application of the hydrogel is limited. The Chinese patent with the publication number of CN113308148B discloses a direct writing 3D printing double-network conductive hydrogel, which comprises polyvinyl alcohol, carbon nano tubes, sodium carboxymethylcellulose and water, and is subjected to physical crosslinking and solidification through cyclic freezing and thawing, chemical crosslinking through soaking in hydrochloric acid solution, and is complex in operation.
Disclosure of Invention
The invention aims to provide 3D printing hydrogel ink with adjustable gel rate, which mainly aims to solve the problems of uncontrollable 3D hydrogel gel time and complex operation in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the 3D printing hydrogel ink with adjustable gel rate is as follows:
the 3D printing hydrogel ink with adjustable gel rate adopts a two-component form, wherein the component A mainly comprises an aqueous solution of Si-N-containing organosiloxane, and the component B comprises an acrylamide monomer or acrylic acid, a cross-linking agent, persulfate and water; alkali metal ions or alkaline earth metal ions are added to the a-component and/or the B-component.
The Si-N-containing organosiloxane/persulfate redox system can not only trigger the gel of the 3D printing hydrogel ink at normal temperature, but also generate hydrolysis crosslinking by itself, thereby improving the toughness of the 3D printing hydrogel.
Due to the addition of alkali metal ions or alkaline earth metal ions, the hydrogel is rapidly cured and molded at room temperature. In addition, the introduction of alkali metal ions or alkaline earth metal ions can also lower the freezing point of the hydrogel and improve the freezing resistance of the hydrogel.
Therefore, the hydrogel formed by the hydrogel ink disclosed by the invention is the freeze-resistant hydrogel integrating high strength, high freeze resistance and 3D printing.
Unlike the prior art in which redox systems generate free radicals, the system of the present invention can regulate the gel time of the system by adjusting the concentration of alkali or alkaline earth ions. Therefore, the invention has simple operation and controllable gel time.
PreferablyThe hydrogel is gelled by using Si-N-containing organosiloxane/persulfate as a redox initiation system, and the speed of the gel is adjusted by adding alkali metal ions or alkaline earth metal ions into the system and adjusting the addition amount; the structure of the Si-N containing organosiloxane is as follows:
wherein R is methyl or ethyl.
Preferably, the alkali metal ion or alkaline earth metal ion is used in an amount of 1 to 30wt% based on the total amount of water used in the gel. The higher the mass percentage of alkali metal ions or alkaline earth metal ions, the faster the gel speed of the hydrogel.
Preferably, the alkali metal ion is Na + Or Li (lithium) + The method comprises the steps of carrying out a first treatment on the surface of the The alkaline earth metal ion is Ca 2+ 。
Preferably, the addition amount of the Si-N-containing organosiloxane is 3-7% of the total water consumption during gelation. Wherein the total water consumption during the gel is A, B, and the mass of water in the reaction system is obtained after mixing.
Preferably, the addition amount of the acrylamide monomer or the acrylic acid is 20-40% of the total water consumption during gel.
Preferably, the addition amount of the persulfate is 0.1-0.5% of the total water consumption during gel.
Preferably, the addition amount of the cross-linking agent is 0.005-0.015% of the total water consumption during the gel. The addition of chemical cross-linking agents can further increase the strength of the hydrogel. Further preferably, the crosslinking agent is an N, N' -methylenebisacrylamide crosslinking agent.
Preferably, the A component and the B component are mixed according to a volume ratio of 1:1 are uniformly mixed.
Drawings
FIG. 1 is a schematic illustration of the reaction mechanism of an alkali metal ion doped composite hydrogel;
FIG. 2 is a 3D printed hydrogel ink, (a) precursor solution; (b) 3D printed shapes;
FIG. 3 is a graph of gel time measurements of alkali metal ion or alkaline earth ion doped Si-N/PAAM hydrogels, (a) gel time as a function of alkali metal ion or alkaline earth ion concentration; (b) different shapes of hydrogel printed out;
FIG. 4 is a graph of dynamic rheological behavior of an alkali or alkaline earth ion doped Si-N/PAAM hydrogel; (a) Ca of different concentrations 2+ Doping; (b) Na of different concentrations + Doping;
FIG. 5 shows Ca at various concentrations 2+ And Na (Na) + DSC plot of Si-N/PAAM doped hydrogel;
FIG. 6 is Ca 2+ Macroscopic mechanical behavior diagram of the Si-N/PAAM hydrogel after being frozen for 24 hours at the temperature of minus 20 ℃; (a) is a photograph of a twisted hydrogel; (b) is a photograph of the hydrogel after bending; (c) is a photograph of the hydrogel pressed after freezing.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings and the specific embodiments.
1. Specific embodiment of gel rate adjustable 3D printing hydrogel ink
Example 1
The gel rate adjustable 3D printing hydrogel ink of this example was prepared as follows:
(1) Preparation of Si-N containing organosiloxanes
1, 3-tetramethyl disiloxane and 3-aminopropyl trimethoxysilane in a molar ratio of 1:2 are respectively weighed into a round bottom flask, 3%Karst platinum catalyst is added, and stirring is carried out for 3 hours at room temperature until no bubbles are generated, thus obtaining an organosiloxane product 1, 3-tetramethyl-N1, N3-bis (3- (trimethoxysilyl) propyl) distiloxane-1, 3-diamine (TBPDD).
The reaction equation is shown below:
in other embodiments, the 3-aminopropyl trimethoxysilane can be replaced with 3-aminopropyl triethoxysilane, i.e., the organosiloxane product can be 1, 3-tetramethyl-N1, N3-bis (3- (triethoxysilyl) propyl) distiloxane-1, 3-diamine (TBEPDD).
(2) Preparation of 3D printing hydrogels
The reaction mechanism of the alkali metal ion or alkaline earth metal ion doped composite hydrogel is shown in figure 1.
a. Respectively weighing 10g of deionized water and placing in two beakers;
b. taking one part of the mixture to prepare an aqueous solution containing 10wt% of NaCl, adding 1.25g of TBPDD, fully stirring until the TBPDD is completely dissolved, and marking the mixture as a 3D printing precursor A component;
c. taking the other part, adding 0.025g of ammonium persulfate, 5.0g of acrylamide and 0.001g of N, N' -methylene-propylene cross-linking agent, uniformly stirring, and marking as a component B;
d. the A component and the B component are mixed according to the volume ratio of 1:1 to obtain printable ink, and rapidly gelling at room temperature.
The percentage by weight of NaCl in the aqueous NaCl solution after the A, B components in the step 2 are combined is 5% by weight, and the following examples are described based on the ratio after mixing.
The 3D printing hydrogel ink of the present application corresponds to A, B component in step (2) above, as shown in fig. 2.
Example 2
The gel rate adjustable 3D printing hydrogel ink of this example differs from example 1 in that: in the step (2), the weight percentage of NaCl in the NaCl aqueous solution is 15wt%.
Example 3
The gel rate adjustable 3D printing hydrogel ink of this example differs from example 1 in that: in the step (2), the weight percentage of NaCl in the NaCl aqueous solution is 20wt%.
Example 4
The gel rate adjustable 3D printing hydrogel ink of this example differs from example 1 in that: in the step (2), the weight percentage of NaCl in the NaCl aqueous solution is 25wt%.
Example 5
The gel rate adjustable 3D printing hydrogel ink of this example differs from example 1 in that: in the step (2), the weight percentage of NaCl in the NaCl aqueous solution is 30wt%.
Examples 6 to 10
The gel rate adjustable 3D printing hydrogel ink of this example differs from examples 1-5 in that: in the step (2), the NaCl aqueous solution is replaced by CaCl 2 An aqueous solution.
In other embodiments, the aqueous NaCl solution may also be replaced with an aqueous LiCl solution.
Example 11
The gel rate adjustable 3D printing hydrogel ink of this example differs from example 1 in that: in step (2), acrylamide was replaced with 5.0g of acrylic acid.
2. Comparative example
The gel rate adjustable 3D printing hydrogel ink of this example differs from example 1 in that: in the step (2), no NaCl aqueous solution is added to the component A.
3. Experimental example
Experimental example 1 gel time measurement
This experimental example was observed for the gel times of examples 1-10, and the results are shown in FIG. 3.
As can be seen from FIG. 3a, regardless of whether Na is added to the redox system + Or Ca 2+ The gel time is shortened along with the increase of the ion concentration so as to accelerate the gel of the hydrogel, and Ca is contained in the same ion concentration 2+ Ratio Na + Can promote the gel of hydrogel.
The obtained hydrogel was added with different pigments and 3D printed, the result of which is shown in fig. 3b.
Experimental example 2 rheological behavior test
In this experimental example, the hydrogel precursors of examples 1 to 10 were each subjected to rheological behavior test, using a model HAAKEMARS III rheometer, a geometric parallel plate of 20PiL, and a sample was dropped between the parallel plates at normal temperature, viscosity test was performed, and the frequency sweep was 1Hz, and the results are shown in FIG. 4.
FIG. 4a is a graph of Ca at various concentrations (5 wt%, 7.5wt%, 10wt%, 12.5wt%, 15 wt%) 2+ Viscosity and time of doped silicone/PAAM hydrogels during gelationA relation diagram between the two. At 15wt% Ca 2+ For example, the silicone/PAAM-doped hydrogel solution has a viscosity of 1Pa or less initially, and 15wt% Ca when the time reaches about 260s 2+ The viscosity of the doped silicone/PAAM hydrogel solution began to rise rapidly and then was at rest, a process which indicated that the polymerization of the solution was very rapid. It can also be seen that the first turning point of the viscosity change follows Ca 2+ The increase in the content gradually shifted to the left, indicating that the higher the content of alkali metal ions, the earlier the polymerization took place. Thus, ca 2+ The doped silicone/PAAM hydrogels can be used for 3D printing.
FIG. 4b is Na + The viscosity profile of the silicone/PAAM doped hydrogel over time during the gel process is similar to that of fig. 4a, except for Ca 2+ Gel time of silicone/PAAM doped hydrogels compared to Na + The gel time of the silicone/PAAM doped hydrogel is shorter.
Experimental example 3 freezing resistance test
The hydrogels prepared in examples 1,3, 5 and examples 6, 8, 10 were subjected to low temperature performance test, and the results are shown in fig. 5.
The hydrogels were analyzed using a Differential Scanning Calorimeter (DSC) model Q100 from TA company in the united states, as can be seen from fig. 5 a: with Ca 2+ The concentration is increased, the crystallization temperature of the hydrogel is continuously reduced, and Ca is not contained 2+ The crystallization peak of the organosilicon/PAAM hydrogel formulation appeared at-18℃and contained 15wt% Ca 2+ The crystallization peak of the silicone/PAAM hydrogel of (2) appears at-29 ℃. DSC results show that Ca is doped in the organosilicon/PAAM hydrogel 2+ Is helpful for reducing the solidifying point of the hydrogel and improving the freezing resistance of the hydrogel.
As can be seen from fig. 5 b: 15wt% Na + The doped organosilicon/PAAM hydrogel shows a crystallization peak of water at-29 ℃ and 5wt% -Na + The crystallization peak of the doped silicone/PAAM hydrogel appears at around-19 ℃. This indicates that the hydrogel has not frozen in an environment of-20 ℃ and that the freezing point of the hydrogel decreases with increasing alkali ion concentration.
In this experimental example, the hydrogel prepared in example 5 was subjected to macroscopic mechanical test after being frozen at-20℃for 24 hours, and the results are shown in FIG. 6.
As can be seen from fig. 6a and 6b, the hydrogel prepared by the present invention can be still twisted and bent and stretched after being frozen at-20 ℃ for 24 hours, which indicates that the hydrogel has excellent stretch resistance after being frozen, fig. 6c: the hydrogel was prepared into a cylindrical test sample, which was pressed by hand after freezing, and the sample was restored to its original state after the pressing was completed, indicating that the hydrogel also had excellent rebound performance after freezing.
Claims (9)
1. The 3D printing hydrogel ink with the adjustable gel rate is characterized in that the ink adopts a two-component form, wherein the component A mainly comprises an aqueous solution of Si-N-containing organosiloxane, and the component B mainly comprises an acrylamide monomer or acrylic acid, a cross-linking agent, persulfate and water; alkali metal ions or alkaline earth metal ions are added in the A component and/or the B component;
the structure of the Si-N containing organosiloxane is as follows:
wherein R is methyl or ethyl.
2. The 3D printing hydrogel ink of claim 1, wherein the hydrogel is gelled using Si-N containing organosiloxane/persulfate as the redox initiation system, the gel rate being adjusted by adding alkali or alkaline earth ions to the system and adjusting the amount added.
3. The 3D printing hydrogel ink with adjustable gel rate according to claim 1, wherein the amount of alkali metal ions or alkaline earth metal ions is 1-30wt% of the total water consumption during the gel.
4. The 3D printing hydrogel ink of claim 3, wherein the alkali metal ions are Na + Or Li (lithium) + The method comprises the steps of carrying out a first treatment on the surface of the The saidAlkaline earth metal ions are Ca 2+ 。
5. The 3D printing hydrogel ink with adjustable gel rate according to claim 1, wherein the addition amount of the Si-N containing organosiloxane is 3-7% of the total water consumption during the gel.
6. The 3D printing hydrogel ink with adjustable gel rate according to claim 1, wherein the addition amount of the acrylamide monomer or the acrylic acid is 20-40% of the total water consumption during the gel.
7. The 3D printing hydrogel ink with adjustable gel rate according to claim 6, wherein the persulfate is added in an amount of 0.1-0.5% of the total water consumption during the gel.
8. The 3D printing hydrogel ink with adjustable gel rate according to claim 1, wherein the adding amount of the cross-linking agent is 0.005-0.015% of the total water consumption during the gel.
9. The adjustable gel rate 3D printing hydrogel ink of any one of claims 1-8, wherein the a and B components are in a volume ratio of 1:1 are uniformly mixed.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63199716A (en) * | 1987-02-17 | 1988-08-18 | Shin Etsu Chem Co Ltd | Production of siloxane-modified acrylic polymer |
| US6652634B1 (en) * | 2001-08-03 | 2003-11-25 | Lexmark International, Inc. | Polymeric dispersants used for aqueous pigmented inks for ink-jet printing |
| JP2007106997A (en) * | 2005-09-16 | 2007-04-26 | Ricoh Co Ltd | Ink for recording, and ink cartridge, ink recorded product, inkjet recording device, and inkjet recording method |
| CN109232826A (en) * | 2018-07-18 | 2019-01-18 | 西南石油大学 | A kind of pre-crosslinked gel particle and preparation method thereof of POSS base hydridization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100958736B1 (en) * | 2009-12-07 | 2010-05-18 | 주식회사 삼공사 | Organic-inorganic hybrid transparent hydrogel complex for fire-retardant glass and fire-retardant glass assembly using the same, and the preparation method of said fire-retardant glass assembly |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63199716A (en) * | 1987-02-17 | 1988-08-18 | Shin Etsu Chem Co Ltd | Production of siloxane-modified acrylic polymer |
| US6652634B1 (en) * | 2001-08-03 | 2003-11-25 | Lexmark International, Inc. | Polymeric dispersants used for aqueous pigmented inks for ink-jet printing |
| JP2007106997A (en) * | 2005-09-16 | 2007-04-26 | Ricoh Co Ltd | Ink for recording, and ink cartridge, ink recorded product, inkjet recording device, and inkjet recording method |
| CN109232826A (en) * | 2018-07-18 | 2019-01-18 | 西南石油大学 | A kind of pre-crosslinked gel particle and preparation method thereof of POSS base hydridization |
Non-Patent Citations (2)
| Title |
|---|
| Superstretchable and Processable Silicone Elastomers by Digital Light Processing 3D Printing;Tingting Zhao等;《ACS APPLIED MATERIALS & INTERFACES》;第11卷(第15期);第14391-14398页 * |
| Synthesis of organic-inorganic hybrid hydrogels using rodlike polysiloxane having acrylamido groups as a new cross-linking agent;Yoshiro Kaneko等;《JOURNAL OF MATERIALS CHEMISTRY》;第16卷(第18期);第1746-1750页 * |
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