CN111234513A - High-modulus 3D printing epoxy resin and preparation method thereof - Google Patents
High-modulus 3D printing epoxy resin and preparation method thereof Download PDFInfo
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- CN111234513A CN111234513A CN202010214330.6A CN202010214330A CN111234513A CN 111234513 A CN111234513 A CN 111234513A CN 202010214330 A CN202010214330 A CN 202010214330A CN 111234513 A CN111234513 A CN 111234513A
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- epoxy resin
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a high-modulus 3D printing epoxy resin and a preparation method thereof, wherein the epoxy resin comprises the following components in parts by weight: 20-50 parts of alicyclic epoxy resin, 10-30 parts of prepolymer, 8-20 parts of active diluent, 1-20 parts of high-modulus carbon fiber, 5-15 parts of unsaturated polyester resin, 0.5-1 part of ammonium isocyanate, 7-10 parts of polycarbonate and 1-5 parts of diethyl phthalate. According to the invention, the high-modulus carbon fiber with a certain length-diameter ratio is added into the epoxy resin, so that the mechanical property, especially the modulus of the material is obviously improved, and meanwhile, the interface bonding property of the fiber and the resin is good, and no additional surface treatment is needed.
Description
Technical Field
The invention relates to the technical field of 3D epoxy resin, in particular to high-modulus 3D printing epoxy resin and a preparation method thereof.
Background
At present, the resin system for 3D printing is mainly made of thermoplastic materials such as nylon and the like, and the other resin system is solidified and crosslinked resin, wherein the light-cured epoxy resin has the advantages of good environmental resistance and the like and is widely used. However, the traditional 3D printing epoxy resin has the problem of low mechanical properties, and needs to be reinforced and modified, and currently, the modification includes the addition of glass beads, glass fibers and the like. However, for printing of large-sized model parts or using as structural parts, the existing 3D printing epoxy resin still has mechanical properties, and particularly, the modulus of the material is not high enough.
In the research on the epoxy resin composite material for 3D printing, for example, patent document CN 105524425A discloses a heat-conducting epoxy resin composite material for 3D printing, which is composed of epoxy resin, ethanol, β -silicon carbide, oxidized polyethylene wax, methyl cellulose and a silane coupling agent, wherein the modified β -silicon carbide is added into the epoxy resin by utilizing the thermoplastic processability and the fluidity in a molten state of the epoxy resin, so as to enhance the heat-conducting property of the epoxy resin composite material, patent document CN108976714A discloses a one-component epoxy resin modified photosensitive resin composition for 3D printing, which comprises, by mass, 10-30% of the one-component epoxy resin, 24-50% of a bifunctional acrylate prepolymer, 10-30% of a polyfunctional acrylate monomer, 11-30% of an active diluent, and 1.5-4% of a photoinitiator, wherein the one-component epoxy resin is composed of a copolymer containing a liquid epoxy resin compound, a side chain of an epoxy group and a latent epoxy curing agent, and a photocuring molding molded product with good toughness, interlayer bonding force and heat resistance can be obtained after curing molding, but the epoxy resin composition has defects.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-modulus 3D printing epoxy resin and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the invention provides a high-modulus 3D printing epoxy resin which comprises the following components in parts by weight:
preferably, the high modulus carbon fiber is a fiber having a modulus of greater than 200GPa and comprises at least one of polyacrylonitrile-based carbon fiber and pitch-based carbon fiber. More preferably, the high modulus carbon fiber is a carbon fiber having a modulus of 400GPa or more.
Preferably, the high modulus carbon fiber is subjected to powdering treatment, and the diameter of the treated high modulus carbon fiber is 3-10 micrometers, and the length of the treated high modulus carbon fiber is 0.01-0.1 millimeter.
Preferably, the weight part of the high modulus carbon fiber is 5-20 parts.
Preferably, the cycloaliphatic epoxy resin comprises at least one of a rigid cycloaliphatic epoxy resin, a flexible cycloaliphatic epoxy resin.
Preferably, the prepolymer comprises a polyurethane acrylate prepolymer, and the polyurethane acrylate prepolymer comprises the following components in parts by weight: 20-50 parts of polyurethane acrylate monomer and 4-8 parts of photoinitiator.
Preferably, the reactive diluent comprises an oxetane reactive diluent.
The invention also provides a preparation method of the high-modulus 3D printing epoxy resin, which comprises the following steps:
A. mechanically grinding the high-modulus carbon fiber, and performing powdering treatment;
B. b, fully mixing the high-modulus carbon fiber treated in the step A with alicyclic epoxy resin, prepolymer, active diluent, unsaturated polyester resin, ammonium isocyanate, polycarbonate and diethyl phthalate;
C. and C, performing vacuum defoaming treatment on the mixture obtained in the step B to obtain the composite material.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional ceramic powder reinforced or graphene reinforced epoxy resin, the high-modulus carbon fiber with a certain length-diameter ratio is added into the epoxy resin, the mechanical property, particularly the modulus of the material is obviously improved, the traditional resin modulus is 2-3GPa, the resin modulus reinforced by the high-modulus carbon fiber can reach more than 10GPa, the strength reaches more than 180MPa, the elongation at break is as low as less than 3.5%, and the high-modulus carbon fiber reinforced epoxy resin can be used as a structural member. Meanwhile, the carbon fiber adopted by the invention has good interface bonding performance with resin, and additional surface treatment is not needed.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides a high-modulus 3D printing epoxy resin which comprises the following components in parts by weight: 20 parts of rigid alicyclic epoxy resin, 30 parts of polyurethane acrylate prepolymer, 15 parts of oxetane reactive diluent, 10 parts of polyacrylonitrile-based carbon fiber with the modulus of 400GPa, 10 parts of unsaturated polyester resin, 0.5 part of ammonium isocyanate, 8 parts of polycarbonate and 1 part of diethyl phthalate.
The preparation method of the high-modulus 3D printing epoxy resin comprises the following steps:
A. mechanically grinding the polyacrylonitrile-based carbon fiber, and performing powdering treatment; obtaining polyacrylonitrile-based powder carbon fibers with the diameter of 5 micrometers, the average length of 0.02 millimeter and the modulus of 400 GPa;
B. b, fully mixing the polyacrylonitrile-based powder carbon fiber obtained after the treatment of the step A with alicyclic epoxy resin, polyurethane acrylate prepolymer, reactive diluent, unsaturated polyester resin, ammonium isocyanate, polycarbonate and diethyl phthalate;
C. and C, performing vacuum defoaming treatment on the mixture obtained in the step B for 5 hours under the vacuum degree of not less than-0.090 MPa to obtain the composite material.
In the step B, the preparation method of the urethane acrylate prepolymer comprises the following steps: by adopting a conventional method, 20 parts of urethane acrylate monomer and 4 parts of photoinitiator are subjected to prepolymerization reaction at 90-110 ℃ to obtain the acrylic ester.
The 3D printing epoxy resin prepared by the implementation has very good mechanical property, the modulus is increased from 2.3GPa of the initial (the 3D printing epoxy resin prepared without adding high-modulus carbon fiber) to 20GPa, the strength is increased from 40MPa of the initial to more than 200MPa, the elongation at break is reduced from 4.4% of the initial to 2.3%, and the 3D printing epoxy resin can be used for printing large-scale model structural members.
Example 2
The embodiment provides a high-modulus 3D printing epoxy resin which comprises the following components in parts by weight: 35 parts of rigid alicyclic epoxy resin, 10 parts of polyurethane acrylate prepolymer, 20 parts of oxetane reactive diluent, 5 parts of asphalt-based carbon fiber with the modulus reaching 620GPa, 5 parts of unsaturated polyester resin, 1 part of ammonium isocyanate, 10 parts of polycarbonate and 5 parts of diethyl phthalate.
The preparation method of the high-modulus 3D printing epoxy resin comprises the following steps:
A. mechanically grinding the pitch-based carbon fiber, and performing powdering treatment; obtaining the asphalt-based powder carbon fiber with the diameter of 10 microns, the average length of 0.05 mm and the modulus of 620 GPa;
B. b, fully mixing the pitch-based powdered carbon fiber obtained after the treatment of the step A with alicyclic epoxy resin, polyurethane acrylate prepolymer, reactive diluent, unsaturated polyester resin, ammonium isocyanate, polycarbonate and diethyl phthalate;
C. and C, performing vacuum defoaming treatment on the mixture obtained in the step B for 3 hours under the vacuum degree of not less than-0.092 MPa to obtain the composite material.
In the step B, the preparation method of the urethane acrylate prepolymer comprises the following steps: by adopting a conventional method, 50 parts of urethane acrylate monomer and 5 parts of photoinitiator are subjected to prepolymerization reaction at 90-110 ℃ to obtain the acrylic ester.
The 3D printing epoxy resin prepared by the implementation has very good mechanical property, the modulus is increased from 2.0GPa to 12GPa at the beginning (the 3D printing epoxy resin prepared without adding high-modulus carbon fiber), the strength is increased from 32MPa to more than 210MPa at the beginning, the elongation at break is reduced from 4.1% to 3.5% at the beginning, and the 3D printing epoxy resin can be used for printing large-scale model structural parts.
Example 3
The embodiment provides a high-modulus 3D printing epoxy resin which comprises the following components in parts by weight: 50 parts of flexible alicyclic epoxy resin, 20 parts of polyurethane acrylate prepolymer, 8 parts of oxetane reactive diluent, 20 parts of polyacrylonitrile-based powder carbon fiber with the modulus of 540GPa, 15 parts of unsaturated polyester resin, 0.5 part of ammonium isocyanate, 7 parts of polycarbonate and 2 parts of diethyl phthalate.
The preparation method of the high-modulus 3D printing epoxy resin comprises the following steps:
A. mechanically grinding the polyacrylonitrile-based carbon fiber, and performing powdering treatment; obtaining polyacrylonitrile-based powder carbon fibers with the diameter of 7 micrometers, the average length of 0.03 millimeter and the modulus of 540 GPa;
B. b, fully mixing the polyacrylonitrile-based powder carbon fiber obtained after the treatment of the step A with alicyclic epoxy resin, polyurethane acrylate prepolymer, reactive diluent, unsaturated polyester resin, ammonium isocyanate, polycarbonate and diethyl phthalate;
C. and C, performing vacuum defoaming treatment on the mixture obtained in the step B for 12 hours under the vacuum degree of not less than-0.098 MPa, and thus obtaining the composite material.
In the step B, the preparation method of the urethane acrylate prepolymer comprises the following steps: by adopting a conventional method, 40 parts of urethane acrylate monomer and 8 parts of photoinitiator are subjected to prepolymerization reaction at 90-110 ℃ to obtain the acrylic ester.
The 3D printing epoxy resin prepared by the implementation has very good mechanical property, the modulus is increased from 2.0GPa to 25GPa at the beginning (the 3D printing epoxy resin prepared without adding high-modulus carbon fiber), the strength is increased from 36MPa to over 410MPa at the beginning, and the elongation at break is reduced from 4.0% to 1.5% at the beginning, so that the 3D printing epoxy resin can be used for printing large-scale model structural members.
Example 4
The embodiment provides a high-modulus 3D printing epoxy resin, which has substantially the same components and contents as those in embodiment 2, except that: the content of the asphalt-based carbon fiber with the modulus of up to 620GPa is 1 part. The preparation method is the same as that of example 2.
The 3D printing epoxy resin prepared by the implementation has the modulus of 11GPa, the strength of 180MPa and the elongation at break of 3.5%.
Example 5
The embodiment provides a high-modulus 3D printing epoxy resin, which has substantially the same components and contents as those in embodiment 1, except that: the adopted carbon fiber is polyacrylonitrile-based carbon fiber with the modulus reaching 200 GPa. The preparation method is the same as that of example 1.
The 3D printing epoxy resin prepared by the implementation of the method has the modulus of 10GPa, the strength of 185MPa and the elongation at break of 3.5%.
Comparative example 1
This example provides a high modulus 3D printing epoxy resin, with the same components and content as in example 1. The preparation method is basically the same as that of the example 1, and the difference is only that: the polyacrylonitrile-based carbon fiber adopted in the comparative example is not treated in the step A, and is directly treated in the step B with alicyclic epoxy resin, polyurethane acrylate prepolymer, reactive diluent, unsaturated polyester resin, ammonium isocyanate, polycarbonate and diethyl phthalate.
The 3D printing epoxy resin prepared by the comparative example has the modulus of 7GPa, the strength of 145MPa and the elongation at break of 3.6%.
Comparative example 2
The comparative example provides a high modulus 3D printing epoxy resin with the same components and content as example 2. The preparation method is basically the same as that of the example 2, and the difference is only that: in step A, the pitch-based powdered carbon fiber obtained by the powdering treatment of this comparative example had a diameter of 15 μm and an average length of 0.05 mm.
The 3D printing epoxy resin prepared by the above comparative example has a modulus of 8GPa, a strength of 175MPa, and an elongation at break of 3.8%.
Comparative example 3
The comparative example provides a high modulus 3D printing epoxy resin with the same components and content as in example 1. The preparation method is basically the same as that of the example 1, and the difference is only that: in the step A, the polyacrylonitrile-based powdered carbon fiber obtained by performing the powdering treatment on the comparative example has the diameter of 1 micron and the average length of 0.02 mm.
The 3D printing epoxy resin prepared by the comparative example has the modulus of 17GPa, the strength of 155MPa and the elongation at break of 3.2%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The high-modulus 3D printing epoxy resin is characterized by comprising the following components in parts by weight:
2. the high modulus 3D printing epoxy resin according to claim 1, wherein the high modulus carbon fiber is a fiber having a modulus of greater than 200GPa comprising at least one of polyacrylonitrile-based carbon fiber and pitch-based carbon fiber.
3. The high modulus 3D printing epoxy resin according to claim 1, wherein the high modulus carbon fiber is subjected to powdering treatment, and the treated high modulus carbon fiber has a diameter of 3-10 microns and a length of 0.01-0.1 mm.
4. The high modulus 3D printing epoxy resin of claim 1, wherein the cycloaliphatic epoxy resin comprises at least one of a rigid cycloaliphatic epoxy resin, a flexible cycloaliphatic epoxy resin.
5. The high modulus 3D printing epoxy resin according to claim 1, wherein the prepolymer comprises a urethane acrylate prepolymer, and the urethane acrylate prepolymer comprises the following components in parts by weight: 20-50 parts of polyurethane acrylate monomer and 4-8 parts of photoinitiator.
6. The high modulus 3D printing epoxy resin of claim 1, wherein the reactive diluent comprises an oxetane reactive diluent.
7. The preparation method of the high modulus 3D printing epoxy resin according to claim 1, comprising the steps of:
A. grinding the high-modulus carbon fiber, and performing powdering treatment;
B. b, fully mixing the high-modulus carbon fiber treated in the step A with alicyclic epoxy resin, prepolymer, active diluent, unsaturated polyester resin, ammonium isocyanate, polycarbonate and diethyl phthalate;
C. and C, performing vacuum defoaming treatment on the mixture obtained in the step B to obtain the composite material.
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| CN202010214330.6A CN111234513A (en) | 2020-03-24 | 2020-03-24 | High-modulus 3D printing epoxy resin and preparation method thereof |
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| CN202010214330.6A CN111234513A (en) | 2020-03-24 | 2020-03-24 | High-modulus 3D printing epoxy resin and preparation method thereof |
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2020
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Effective date of registration: 20200828 Address after: White Xuexin road Suzhou City, Jiangsu province 215542 Changshou City Shajiabang town No. 8 Applicant after: Suzhou Xingye Aerospace Technology Co.,Ltd. Address before: 201108 No.5 tangjiaku, Yonglian village, Meilong Town, Minhang District, Shanghai Applicant before: Li Fei |
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Application publication date: 20200605 |