CN112048040A - Photocuring 3D printing vinyl star-shaped polycarbonate composite photosensitive resin and preparation method and application thereof - Google Patents
Photocuring 3D printing vinyl star-shaped polycarbonate composite photosensitive resin and preparation method and application thereof Download PDFInfo
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- CN112048040A CN112048040A CN202010876516.8A CN202010876516A CN112048040A CN 112048040 A CN112048040 A CN 112048040A CN 202010876516 A CN202010876516 A CN 202010876516A CN 112048040 A CN112048040 A CN 112048040A
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- photosensitive resin
- printing
- star
- vinyl
- polycarbonate
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- 239000011347 resin Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 34
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 32
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 32
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000010146 3D printing Methods 0.000 title claims abstract description 25
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002861 polymer material Substances 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- -1 vinyl modified hydroxyapatite Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- TYMYJUHDFROXOO-UHFFFAOYSA-N 1,3-bis(prop-2-enoxy)-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COCC=C TYMYJUHDFROXOO-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007943 implant Substances 0.000 abstract description 2
- 238000001727 in vivo Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Classifications
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
-
- 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
-
- 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
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
-
- 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
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a photocuring 3D printing vinyl star polycarbonate composite photosensitive resin, and a preparation method and application thereof. The material comprises the following components in percentage by weight: 30-80% of vinyl star polycarbonate high polymer material, 5-50% of cross-linking agent, 5-30% of photoinitiator, 5-50% of diluent, 0-30% of solvent and 0-60% of filler. The material has good photocuring crosslinking property and high photosensitive activity, is suitable for photocuring three-dimensional forming 3D printing, and can be used for manufacturing medical instruments such as personalized in-vivo implants; the material formed after curing and crosslinking has the characteristics of good biocompatibility and degradability, high mechanical strength and high toughness.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a photocuring 3D printing vinyl star polycarbonate composite photosensitive resin, and a preparation method and application thereof.
Background
The light-cured stereo additive manufacturing technology (SLA) uses liquid photosensitive resin containing unsaturated bonds as raw materials, other materials can be added to form composite materials, ultraviolet laser beams under the control of a computer are used for scanning point by taking each layered section of a computer model as a path, a resin thin layer in a scanned area is cured after photopolymerization or photocrosslinking reaction, after one layer of curing is completed, a workbench is moved in the vertical direction, a layer of new liquid resin is covered on the surface of the previously cured resin, and the three-dimensional prototype is finally obtained after scanning and curing layer by layer. SLA technology has the advantages of high precision, good surface quality, stable performance, high mechanical strength of products and the like, and has the defects that molded products need to be cleaned to remove impurities, the products are possibly deformed, and photosensitive resin is expensive and generally cannot be degraded.
Therefore, the developed vinyl star polycarbonate composite photosensitive resin can be processed by adopting the technologies of photocuring three-dimensional forming additive manufacturing and the like while keeping good biocompatibility and degradability, has good processing performance, has important economic value and wide application range.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a photocuring 3D printing vinyl star polycarbonate composite photosensitive resin, and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
the photocuring 3D printing vinyl star polycarbonate composite photosensitive resin comprises the following components in percentage by weight: 30-80% of vinyl star polycarbonate high polymer material, 5-50% of cross-linking agent, 5-30% of photoinitiator, 5-50% of diluent, 0-30% of solvent and 0-60% of filler, wherein:
the vinyl star polycarbonate high polymer material is selected from the following general formulas in the invention patent with the application number of 201810487155.0:
In formula I: r1、R2Each independently selected from a hydrogen atom, an unsubstituted alkyl group, an aryl group, or an alkyl group bearing at least one hydroxyl group, at least one amino group, at least one carboxyl group, at least one alkoxy group, at least one aryl group, or at least one aryloxy group; r3Selected from a hydrogen atom, an alkyl group or an aryl group;
in formula II: r1、R2Each independently selected from a hydrogen atom, an unsubstituted alkyl group, an aryl group, or an alkyl group bearing at least one hydroxyl group, at least one amino group, at least one carboxyl group, at least one alkoxy group, at least one aryl group, or at least one aryloxy group; r3Selected from a hydrogen atom, an alkyl group or an aryl group;
n in formula I or formula II is a natural number of 1-500000;
the cross-linking agent is selected from any one of pentaerythritol tetraallyl ether and pentaerythritol tetraacrylate;
the filler is selected from any one of vinyl hydroxyapatite or tricalcium phosphate.
The photocuring 3D printing vinyl star-shaped polycarbonate composite photosensitive resin provided by the technical scheme has good photocuring crosslinking property and high photosensitive activity, is suitable for photocuring three-dimensional forming 3D printing, and can be used for manufacturing personalized medical instruments such as in-vivo implants; the material formed after curing and crosslinking has the characteristics of good biocompatibility and degradability, high mechanical strength and high toughness.
The repeated structural unit of the polycarbonate has the characteristic of trimethylene carbonate bond, thereby endowing the photosensitive resin with excellent biocompatibility and biodegradability, good toughness and elasticity and other properties.
The vinyl star polycarbonate high polymer material has good performances such as toughness and elasticity, so that the addition amount of the filler can reach 60 percent.
Preferably, the vinyl star polycarbonate polymer material is:
wherein n is a natural number of 1-500000;
or is that
Wherein n is a natural number of 1-500000;
or is that
Wherein n is a natural number of 1-500000.
Specifically, the vinyl star polycarbonate high polymer material accounts for 30-80% of the composite photosensitive resin by weight percent.
Specifically, the cross-linking agent accounts for 5-50% of the composite photosensitive resin by weight.
Specifically, the filler accounts for 0-60% of the composite photosensitive resin by weight.
Specifically, the photoinitiator is selected from any one or more of 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate; the photoinitiator accounts for 5 to 30 percent of the weight of the composite photosensitive resin.
Specifically, the diluent is N-vinyl pyrrolidone or ethyl fumarate; the diluent accounts for 5 to 50 percent of the weight of the composite photosensitive resin.
Specifically, the solvent is any one of dichloromethane, trichloromethane, carbon tetrachloride or dichloroethane; the solvent accounts for 0 to 30 weight percent of the composite photosensitive resin.
Ultraviolet light (the wavelength is 365nm +/-10 nm, the lamp power is more than or equal to 5w, and the illumination intensity is 400 mw/cm) of the existing photocuring 3D printer2) Under the irradiation, the photocuring 3D printing vinyl star polycarbonate composite photosensitive resin provided by the invention is rapidly crosslinked and cured within 15 seconds. Compared with the similar photocuring 3D printer material, the curing time is further shortened.
The material formed after curing and crosslinking has the characteristics of good biocompatibility and degradability, high mechanical strength and high toughness as shown by experimental results of a test by adopting a universal electronic tester according to national standards GBT29284-2012 and GBT 16886. The mechanical strength and toughness are improved by more than 100% compared with those of photosensitive resin which contains common divinyl crosslinking agent and is not modified by vinyl. Specific performance data and comparative data may be obtained by direct testing using the above or other existing testing methods.
The invention also provides a preparation method of the photocuring 3D printing vinyl star polycarbonate composite photosensitive resin, which comprises the following steps: mixing the above components at room temperature.
The invention also provides application of the photocuring 3D printing vinyl star polycarbonate composite photosensitive resin as a photocuring three-dimensional forming 3D printing material.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
The formula of the photo-curing 3D printing vinyl star polycarbonate composite photosensitive resin (1000 g) is as follows:
example 2
The formula of the photo-cured 3D printing vinyl star polycarbonate composite photosensitive resin (500 g) is as follows:
example 3
The formula of the photo-curing 3D printing vinyl star polycarbonate composite photosensitive resin (200 g) is as follows:
example 4
The formula of the photo-curing 3D printing vinyl star polycarbonate composite photosensitive resin (100 g) is as follows:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The photocuring 3D printing vinyl star polycarbonate composite photosensitive resin is characterized by comprising the following components in percentage by weight: 30-80% of vinyl star polycarbonate high polymer material, 5-50% of cross-linking agent, 5-30% of photoinitiator, 5-50% of diluent, 0-30% of solvent and 0-60% of filler, wherein:
the vinyl star polycarbonate high polymer material has the following general formula:
Formula I or formula II: r1、R2Each independently selected from a hydrogen atom, an unsubstituted alkyl group, an aryl group, or an alkyl group bearing at least one hydroxyl group, at least one amino group, at least one carboxyl group, at least one alkoxy group, at least one aryl group, or at least one aryloxy group; r3Selected from a hydrogen atom, an alkyl group or an aryl group;
n in formula I or formula II is a natural number of 1-500000;
the cross-linking agent is selected from any one of pentaerythritol tetraallyl ether and pentaerythritol tetraacrylate;
the filler is selected from any one of vinyl modified hydroxyapatite or tricalcium phosphate.
2. The photocurable 3D printing vinyl star polycarbonate composite photosensitive resin as claimed in claim 1, wherein the vinyl star polycarbonate high molecular material is:
wherein n is a natural number of 1-500000;
or is that
Wherein n is a natural number of 1-500000;
or is that
Wherein n is a natural number of 1-500000.
3. The photocurable 3D printing vinyl star polycarbonate composite photosensitive resin of claim 1, wherein: the photoinitiator is selected from any one or a mixture of 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate.
4. The photocurable 3D printing vinyl star polycarbonate composite photosensitive resin of claim 1, wherein: the diluent is N-vinyl pyrrolidone or ethyl fumarate.
5. The photocurable 3D printing vinyl star polycarbonate composite photosensitive resin of claim 1, wherein: the solvent is any one of dichloromethane, trichloromethane, carbon tetrachloride or dichloroethane.
6. A method for preparing the photocurable 3D printing vinyl star polycarbonate composite photosensitive resin according to any one of claims 1 to 5, comprising the steps of: mixing the above components at room temperature.
7. Use of the photocurable 3D printing vinyl star polycarbonate composite photosensitive resin according to any one of claims 1 to 5, characterized in that: as a stereolithographic 3D printing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010876516.8A CN112048040A (en) | 2020-08-27 | 2020-08-27 | Photocuring 3D printing vinyl star-shaped polycarbonate composite photosensitive resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010876516.8A CN112048040A (en) | 2020-08-27 | 2020-08-27 | Photocuring 3D printing vinyl star-shaped polycarbonate composite photosensitive resin and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112048040A true CN112048040A (en) | 2020-12-08 |
Family
ID=73599957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010876516.8A Pending CN112048040A (en) | 2020-08-27 | 2020-08-27 | Photocuring 3D printing vinyl star-shaped polycarbonate composite photosensitive resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112048040A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140212532A1 (en) * | 2013-01-28 | 2014-07-31 | Hewlett-Packard Development Company, L.P. | Micro-composite material for three-dimensional printing |
| CN108707226A (en) * | 2018-05-21 | 2018-10-26 | 武汉工程大学 | A kind of vinyl modified star makrolon and its synthetic method |
| CN108948337A (en) * | 2018-05-21 | 2018-12-07 | 武汉工程大学 | A kind of vinyl modified star pla-pcl and its synthetic method |
| CN111378074A (en) * | 2020-04-17 | 2020-07-07 | 阜阳师范大学 | Three-arm acrylate polyurethane 3D printing photosensitive resin and preparation method thereof |
-
2020
- 2020-08-27 CN CN202010876516.8A patent/CN112048040A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140212532A1 (en) * | 2013-01-28 | 2014-07-31 | Hewlett-Packard Development Company, L.P. | Micro-composite material for three-dimensional printing |
| CN108707226A (en) * | 2018-05-21 | 2018-10-26 | 武汉工程大学 | A kind of vinyl modified star makrolon and its synthetic method |
| CN108948337A (en) * | 2018-05-21 | 2018-12-07 | 武汉工程大学 | A kind of vinyl modified star pla-pcl and its synthetic method |
| CN111378074A (en) * | 2020-04-17 | 2020-07-07 | 阜阳师范大学 | Three-arm acrylate polyurethane 3D printing photosensitive resin and preparation method thereof |
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