CN115505241B - Quick-drying 3D printing glue and preparation method thereof - Google Patents
Quick-drying 3D printing glue and preparation method thereof Download PDFInfo
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- CN115505241B CN115505241B CN202211104029.5A CN202211104029A CN115505241B CN 115505241 B CN115505241 B CN 115505241B CN 202211104029 A CN202211104029 A CN 202211104029A CN 115505241 B CN115505241 B CN 115505241B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses quick-drying 3D printing glue and a preparation method thereof, wherein the quick-drying 3D printing glue comprises a component A and a component B, and the component A comprises the following raw materials in parts by weight: 90-110 parts of epoxy resin and 10-15 parts of epoxy toughening agent; the component B comprises the following raw materials in parts by weight: 30-40 parts of curing agent and 10-12 parts of curing accelerator; mixing the component A and the component B, and stirring to obtain quick-drying 3D printing glue; the amino in the curing agent in the component B can be polymerized with the epoxy resin and the epoxy toughening agent to generate a polymer with a three-dimensional network structure, the structure of the epoxy toughening agent is introduced into the polymer, the epoxy toughening agent can be bonded with the epoxy resin in a covalent bond mode, and a stable and uniform disperse phase is formed, so that when the formed polymer is impacted or impacted externally, the fracture surface of the formed polymer can form cracks to absorb fracture energy, and the fracture resistance and the impact resistance of the formed polymer are improved.
Description
Technical Field
The invention relates to the field of 3D printing consumables, in particular to quick-drying 3D printing glue and a preparation method thereof.
Background
The 3D printing technology is also called as a three-dimensional printing technology, namely a 3D printer capable of printing out a real object is adopted, and materials are added layer by layer in a layering processing and stacking forming mode to generate a 3D entity; the 3D printing technology has the most outstanding advantages that objects with any shape can be directly generated from computer graphic data without machining or a die, so that the development period of a product is greatly shortened, the production rate is improved, and the production cost is reduced.
The core of the development of the 3D printing technology is not printing, but is the restriction of the material technology, and the 3D printing technology can be further put into practical use only if the new material technology is developed, and at present, a 3D printer is already used for manufacturing a die, a human skeleton and the like, and can be used for printing relatively simple living goods; the 3D printing consumables are generally divided into several categories; powder consumables for laser sintering molding; photosensitive consumable material for photocuring forming; the molten silk material consumable is used for fusion stacking molding; also paper consumables, plastic spraying consumables and the like.
When 3D printing an article with a powder material, a binder is mixed to print the article with a fixed shape. The existing adhesive for 3D printing has long drying and curing time, and has poor stripping resistance, cracking resistance and impact resistance after the adhesive is cured.
Disclosure of Invention
In order to solve the technical problems, the invention provides quick-drying 3D printing glue and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the quick-drying 3D printing glue comprises a first component and a second component, wherein the first component comprises the following raw materials in parts by weight: 90-110 parts of epoxy resin and 10-15 parts of epoxy toughening agent;
the epoxy toughening agent is prepared by the following steps:
adding absolute ethyl alcohol and absolute methyl alcohol into a three-neck flask to prepare a mixed solvent, stirring at a constant speed and heating to 35-40 ℃, adding deionized water and hydrochloric acid, regulating pH until the pH is 3-4, stirring at a constant speed for 30min, adding a siloxane mixed solution, carrying out hydrolysis reaction for 48h to prepare a reaction solution, then adding a 10% sodium hydroxide aqueous solution by mass fraction to regulate the pH until the system is neutral, distilling under reduced pressure to remove the solvent, washing for three times, drying, filtering, and preparing the epoxy toughening agent, wherein the volume ratio of the absolute ethyl alcohol to the absolute methyl alcohol is 5:1, and the dosage ratio of the mixed solvent, the deionized water and the siloxane mixed solution is 75-90 mL:50-55 mL:6.4-6.6 g.
Through two siloxane hydrolysis reactions, a complex is generated, and the complex is cage-type siloxane with epoxy groups in the structure, and the structure is shown as follows:
further: the siloxane mixed solution is prepared by mixing phenyl triethoxysilane and beta-3, 4-epoxycyclohexyl ethyl trimethoxysilane according to the weight ratio of 4g to 2.4-2.6 g.
Further: the component B comprises the following raw materials in parts by weight: 30-40 parts of curing agent and 10-12 parts of curing accelerator;
the curing accelerator comprises the following steps:
adding beta-cyclodextrin into deionized water, heating to 65 ℃, and uniformly stirring for 30min to obtain a solution a; adding polyethylene glycol 1000 into the solution a, magnetically stirring for 1h, standing for 24h, precipitating, vacuum filtering, washing and vacuum drying the precipitate to obtain a compound, wherein the weight ratio of beta-cyclodextrin to deionized water is controlled to be 1-1.5:100, and the molar ratio of beta-cyclodextrin to polyethylene glycol 1000 is controlled to be 1:2.
The curing accelerator is a mixture of beta-cyclodextrin and polyethylene glycol, the beta-cyclodextrin has a hydrophobic cavity and a large number of hydroxyl groups, the hydroxyl groups can react with epoxy groups to accelerate the curing of epoxy resin, the polyethylene glycol molecules are provided with hydrophobic chain segments and hydrophilic ether bonds, the hydrophobic chain segments replace bound water in the cyclodextrin cavity, and the hydrophilic groups and the hydroxyl groups on the cyclodextrin generate hydrogen bond action to further improve the stability of the prepared compound.
Further: the curing agent is diaminodiphenyl methane.
A preparation method of quick-drying 3D printing glue comprises the following steps:
firstly, preparing a component A;
mixing epoxy resin and epoxy toughening agent, and stirring uniformly to obtain component A;
secondly, preparing a component B;
mixing a curing agent and a curing accelerator, and uniformly stirring to obtain a component B;
and thirdly, mixing the component A and the component B, and stirring to obtain the quick-drying 3D printing glue.
The invention has the beneficial effects that:
the quick-drying 3D printing glue is formed by mixing a first component and a second component, wherein epoxy resin is used as a matrix, an epoxy toughening agent is added into the first component, then the first component is solidified by adding the second component, amino groups in the solidifying agent in the second component can be polymerized with the epoxy resin and the epoxy toughening agent to generate a polymer with a three-dimensional network structure, the structure of the epoxy toughening agent is introduced into the polymer, the epoxy toughening agent can be bonded with the epoxy resin in a covalent bond mode, and a stable and uniform disperse phase is formed, so that cracks can be formed on the section of the formed polymer when the formed polymer is impacted or impacted, and fracture energy is absorbed, thereby improving the cracking resistance and shock resistance of the formed polymer.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The quick-drying 3D printing glue comprises a first component and a second component, wherein the first component comprises the following raw materials in parts by weight: 90 parts of epoxy resin E51 and 10 parts of epoxy toughening agent;
the epoxy toughening agent is prepared by the following steps:
adding absolute ethyl alcohol and absolute methyl alcohol into a three-neck flask to prepare a mixed solvent, stirring at a constant speed and heating to 35 ℃, adding deionized water and hydrochloric acid, regulating the pH until the pH is 3-4, stirring at a constant speed for 30min, adding a siloxane mixed solution, carrying out hydrolysis reaction for 48h to prepare a reaction solution, then adding a 10% sodium hydroxide aqueous solution with mass fraction to regulate the pH until the system is neutral, distilling under reduced pressure to remove the solvent, washing for three times, drying, filtering, and preparing the epoxy toughening agent, wherein the volume ratio of the absolute ethyl alcohol to the absolute methyl alcohol is controlled to be 5:1, and the dosage ratio of the mixed solvent, the deionized water and the siloxane mixed solution is 75mL to 50mL to be 6.4g.
The siloxane mixture is prepared by mixing phenyl triethoxysilane and beta-3, 4-epoxy cyclohexyl ethyl trimethoxysilane according to the weight ratio of 4g to 2.4 g.
The component B comprises the following raw materials in parts by weight: 30 parts of diaminodiphenyl methane and 10 parts of a curing accelerator;
the curing accelerator comprises the following steps:
adding beta-cyclodextrin into deionized water, heating to 65 ℃, and uniformly stirring for 30min to obtain a solution a; adding polyethylene glycol 1000 into the solution a, magnetically stirring for 1h, standing for 24h, precipitating, vacuum filtering, washing and vacuum drying the precipitate to obtain a compound, wherein the weight ratio of beta-cyclodextrin to deionized water is controlled to be 1:100, and the molar ratio of beta-cyclodextrin to polyethylene glycol 1000 is controlled to be 1:2.
Example 2
The quick-drying 3D printing glue comprises a first component and a second component, wherein the first component comprises the following raw materials in parts by weight: 100 parts of epoxy resin E51 and 12 parts of epoxy toughening agent;
the epoxy toughening agent is prepared by the following steps:
adding absolute ethyl alcohol and absolute methyl alcohol into a three-neck flask to prepare a mixed solvent, stirring at a constant speed and heating to 38 ℃, adding deionized water and hydrochloric acid, regulating pH until pH=4, stirring at a constant speed for 30min, adding a siloxane mixed solution, carrying out hydrolysis reaction for 48h to prepare a reaction solution, then adding a 10% sodium hydroxide aqueous solution with mass fraction to regulate pH until the system is neutral, distilling under reduced pressure to remove the solvent, washing for three times, drying, filtering to prepare the epoxy toughening agent, controlling the volume ratio of the absolute ethyl alcohol to the absolute methyl alcohol to be 5:1, and controlling the dosage ratio of the mixed solvent, the deionized water and the siloxane mixed solution to be 80 mL:52 mL:6.5 g.
The siloxane mixture is prepared by mixing phenyl triethoxysilane and beta-3, 4-epoxy cyclohexyl ethyl trimethoxysilane according to the weight ratio of 4g to 2.5 g.
The component B comprises the following raw materials in parts by weight: 35 parts of diaminodiphenyl methane and 11 parts of a curing accelerator;
the curing accelerator comprises the following steps:
adding beta-cyclodextrin into deionized water, heating to 65 ℃, and uniformly stirring for 30min to obtain a solution a; adding polyethylene glycol 1000 into the solution a, magnetically stirring for 1h, standing for 24h, precipitating, vacuum filtering, washing and vacuum drying the precipitate to obtain a compound, wherein the weight ratio of beta-cyclodextrin to deionized water is controlled to be 1.3:100, and the molar ratio of beta-cyclodextrin to polyethylene glycol 1000 is controlled to be 1:2.
Example 3
The quick-drying 3D printing glue comprises a first component and a second component, wherein the first component comprises the following raw materials in parts by weight: 110 parts of epoxy resin E51 and 15 parts of epoxy toughening agent;
the epoxy toughening agent is prepared by the following steps:
adding absolute ethyl alcohol and absolute methyl alcohol into a three-neck flask to prepare a mixed solvent, stirring at a constant speed and heating to 40 ℃, adding deionized water and hydrochloric acid, regulating pH until pH=4, stirring at a constant speed for 30min, adding a siloxane mixed solution, carrying out hydrolysis reaction for 48h to prepare a reaction solution, then adding a 10% sodium hydroxide aqueous solution with mass fraction to regulate pH until the system is neutral, distilling under reduced pressure to remove the solvent, washing for three times, drying, filtering to prepare the epoxy toughening agent, controlling the volume ratio of the absolute ethyl alcohol to the absolute methyl alcohol to be 5:1, and controlling the dosage ratio of the mixed solvent, the deionized water and the siloxane mixed solution to be 90 mL/55 mL/6.6 g.
The siloxane mixture is prepared by mixing phenyl triethoxysilane and beta-3, 4-epoxy cyclohexyl ethyl trimethoxysilane according to the weight ratio of 4g to 2.6 g.
The component B comprises the following raw materials in parts by weight: 40 parts of diaminodiphenyl methane and 12 parts of a curing accelerator;
the curing accelerator comprises the following steps:
adding beta-cyclodextrin into deionized water, heating to 65 ℃, and uniformly stirring for 30min to obtain a solution a; adding polyethylene glycol 1000 into the solution a, magnetically stirring for 1h, standing for 24h, precipitating, vacuum filtering, washing and vacuum drying the precipitate to obtain a compound, wherein the weight ratio of beta-cyclodextrin to deionized water is controlled to be 1.5:100, and the molar ratio of beta-cyclodextrin to polyethylene glycol 1000 is controlled to be 1:2.
Example 4
A preparation method of quick-drying 3D printing glue comprises the following steps:
firstly, preparing a component A;
mixing the epoxy resin prepared in the example 1 with an epoxy toughening agent, and uniformly stirring to prepare a component A;
secondly, preparing a component B;
mixing the curing agent prepared in the example 1 with the curing accelerator, and uniformly stirring to prepare a component B;
and thirdly, mixing the component A and the component B, and stirring to obtain the quick-drying 3D printing glue.
Example 5
A preparation method of quick-drying 3D printing glue comprises the following steps:
firstly, preparing a component A;
mixing the epoxy resin prepared in the example 2 with the epoxy toughening agent, and uniformly stirring to prepare a component A;
secondly, preparing a component B;
mixing the curing agent prepared in the example 2 with the curing accelerator, and uniformly stirring to prepare a component B;
and thirdly, mixing the component A and the component B, and stirring to obtain the quick-drying 3D printing glue.
Example 6
A preparation method of quick-drying 3D printing glue comprises the following steps:
firstly, preparing a component A;
mixing the epoxy resin prepared in the example 3 with the epoxy toughening agent, and uniformly stirring to prepare a component A;
secondly, preparing a component B;
mixing the curing agent prepared in the example 3 with the curing accelerator, and uniformly stirring to prepare a component B;
and thirdly, mixing the component A and the component B, and stirring to obtain the quick-drying 3D printing glue.
Comparative example 1
In this comparative example, no epoxy toughening agent was added as compared to example 4.
Comparative example 2
In this comparative example, no curing accelerator was added as compared with example 4.
Comparative example 3
The comparative example is a two-part epoxy adhesive produced by a commercial company.
The glues prepared in examples 4-6 and comparative examples 1-3 were tested and the results are shown in the following table:
curing time: the glues prepared in examples 4-6 and comparative examples 1-3 were printed with the same 3D printed gypsum-based powder material using zprint4503D printer from 3D systems, usa, in combination with CAD software, to form a 15cmX10cmX cm rectangular parallelepiped article at the same time and in the same environment, and at the same time blow-dried with hot air, the drying cure time was recorded.
From the above table, it can be seen that the glues prepared in examples 4-6 of the present invention are fast curing and have excellent shear and peel strength.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (4)
1. Quick-drying 3D prints glue, including first component and second component, its characterized in that: the component A comprises the following raw materials in parts by weight: 90-110 parts of epoxy resin and 10-15 parts of epoxy toughening agent;
the epoxy toughening agent is prepared by the following steps:
adding absolute ethyl alcohol and absolute methyl alcohol into a three-neck flask to prepare a mixed solvent, stirring at a constant speed and heating to 35-40 ℃, adding deionized water and hydrochloric acid, regulating the pH until the pH is 3-4, stirring at a constant speed for 30min, adding a siloxane mixed solution, carrying out hydrolysis reaction for 48h to prepare a reaction solution, then adding a 10% sodium hydroxide aqueous solution with mass fraction to regulate the pH until the system is neutral, distilling under reduced pressure to remove the solvent, washing for three times, and then drying and filtering to prepare the epoxy toughening agent;
the siloxane mixed solution is formed by mixing phenyl triethoxysilane and beta-3, 4-epoxycyclohexyl ethyl trimethoxysilane according to the weight ratio of 4g to 2.4-2.6 g;
the component B comprises the following raw materials in parts by weight: 30-40 parts of curing agent and 10-12 parts of curing accelerator;
the curing accelerator comprises the following steps:
adding beta-cyclodextrin into deionized water, heating to 65 ℃, and uniformly stirring for 30min to obtain a solution a; adding polyethylene glycol 1000 into the solution a, magnetically stirring for 1h, standing for 24h, precipitating, vacuum filtering, washing and vacuum drying the precipitate to obtain a compound, wherein the weight ratio of beta-cyclodextrin to deionized water is controlled to be 1-1.5:100, and the molar ratio of beta-cyclodextrin to polyethylene glycol 1000 is controlled to be 1:2.
2. The quick-drying 3D printing glue of claim 1, wherein: the volume ratio of the absolute ethyl alcohol to the absolute methyl alcohol is controlled to be 5:1, and the dosage ratio of the mixed solvent, the deionized water and the siloxane mixed solution is 75-90 mL:50-55 mL:6.4-6.6 g.
3. The quick-drying 3D printing glue of claim 1, wherein: the curing agent is diaminodiphenyl methane.
4. The method for preparing quick-drying 3D printing glue according to claim 1, wherein:
the method comprises the following steps:
firstly, preparing a component A;
mixing epoxy resin and epoxy toughening agent, and stirring uniformly to obtain component A;
secondly, preparing a component B;
mixing a curing agent and a curing accelerator, and uniformly stirring to obtain a component B;
and thirdly, mixing the component A and the component B, and stirring to obtain the quick-drying 3D printing glue.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211104029.5A CN115505241B (en) | 2022-09-09 | 2022-09-09 | Quick-drying 3D printing glue and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211104029.5A CN115505241B (en) | 2022-09-09 | 2022-09-09 | Quick-drying 3D printing glue and preparation method thereof |
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| CN115505241A CN115505241A (en) | 2022-12-23 |
| CN115505241B true CN115505241B (en) | 2023-07-18 |
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657986A (en) * | 1984-12-26 | 1987-04-14 | Kanegafuchi Chemical Industry Co., Ltd. | Curable resinous composition comprising epoxy resin and silicon-containing elastomeric polymer |
| JP3216215B2 (en) * | 1992-03-27 | 2001-10-09 | 日本曹達株式会社 | Curable resin composition |
| JP4520003B2 (en) * | 2000-04-14 | 2010-08-04 | 株式会社カネカ | Curable composition |
| US6639025B2 (en) * | 2002-02-01 | 2003-10-28 | Ameron International Corporation | Elastomer-modified epoxy siloxane compositions |
| CN101525466B (en) * | 2009-04-03 | 2012-07-04 | 复旦大学 | Epoxy/organosilicon/inorganic nano-hybrid material, and preparation method and application thereof |
| CN101525467A (en) * | 2009-04-03 | 2009-09-09 | 复旦大学 | Epoxy/organosilicon hybrid material, and preparation method and application thereof |
| JP2011132416A (en) * | 2009-12-25 | 2011-07-07 | Nagase Chemtex Corp | Thermocurable resin composition and organic-inorganic composite resin |
| CN102604327B (en) * | 2012-02-10 | 2014-01-08 | 中科院广州化灌工程有限公司 | Solvent-free epoxy resin as plugging material, and preparation method and application of the solvent-free epoxy resin |
| CN103756260B (en) * | 2014-01-23 | 2016-01-27 | 苏州大学 | A kind of biomass modified thermosetting resin and preparation method thereof |
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