CN111909320A - Photocuring 3D printing modified polylactic acid composite photosensitive resin and preparation method thereof - Google Patents
Photocuring 3D printing modified polylactic acid composite photosensitive resin and preparation method thereof Download PDFInfo
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- CN111909320A CN111909320A CN202010749582.9A CN202010749582A CN111909320A CN 111909320 A CN111909320 A CN 111909320A CN 202010749582 A CN202010749582 A CN 202010749582A CN 111909320 A CN111909320 A CN 111909320A
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- photosensitive resin
- polylactic acid
- composite photosensitive
- photocuring
- modified polylactic
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- 239000011347 resin Substances 0.000 title claims abstract description 43
- 229920005989 resin Polymers 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 33
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 33
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 25
- 238000010146 3D printing Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000002861 polymer material Substances 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- -1 cyclohexanol hexaacrylate Chemical compound 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- RKCKOWJWQLITLM-UHFFFAOYSA-N P(O)(O)=O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C Chemical compound P(O)(O)=O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C RKCKOWJWQLITLM-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 9
- 238000001723 curing Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000002209 hydrophobic effect 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
- 239000007788 liquid Substances 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
- 238000012360 testing method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005094 computer simulation Methods 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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 modified polylactic acid composite photosensitive resin and a preparation method thereof. The photocuring 3D printing modified polylactic acid composite photosensitive resin comprises the following components in percentage by weight: 20-90% of vinyl polylactic acid high polymer material, 5-79% of cross-linking agent, 1-40% of photoinitiator, 0-60% of diluent, 0-40% of solvent and 0-30% of filler. The photocuring 3D printing modified polylactic acid composite photosensitive resin provided by the invention 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, good hydrophilic/hydrophobic property, 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 modified polylactic acid composite photosensitive resin and a preparation method thereof.
Background
The raw material used by the light-cured three-dimensional additive manufacturing technology (SLA) is liquid photosensitive resin containing unsaturated bonds, and other materials can be added into the liquid photosensitive resin to form a composite material. And scanning ultraviolet laser beams under the control of a computer point by taking each layered section of a computer model as a path, curing after a resin thin layer in a scanned area generates photopolymerization or photocrosslinking reaction, moving a workbench in the vertical direction after one layer is cured, covering a new layer of liquid resin on the surface of the previously cured resin, scanning and curing layer by layer, and finally obtaining the three-dimensional prototype. 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 the currently used photosensitive resin is expensive and generally cannot be degraded.
Therefore, the modified polylactic acid composite photosensitive resin developed by the invention 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 processability, 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 modified polylactic acid composite photosensitive resin and a preparation method thereof.
The technical scheme provided by the invention is as follows:
the photocuring 3D printing modified polylactic acid composite photosensitive resin comprises the following components in percentage by weight: 20-90% of vinyl polylactic acid high polymer material, 5-79% of cross-linking agent, 1-40% of photoinitiator, 0-60% of diluent, 0-40% of solvent and 0-30% of filler, wherein:
the structural general formula of the vinyl polylactic acid high polymer material is as follows:
wherein m, n and l are natural numbers of 1-1000000 respectively;
the cross-linking agent is selected from any one of cyclohexanol hexaallyl ether or cyclohexanol hexaacrylate;
the filler is selected from any one of vinyl modified calcium carbonate and hydroxyapatite nano materials.
The proportion of the diluent, the solvent and the filler is not 0.
The photocuring 3D printing modified polylactic acid 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 in-vivo implants and other medical instruments; the material formed after curing and crosslinking has the characteristics of good biocompatibility and degradability, good hydrophilic/hydrophobic property, high mechanical strength and high toughness.
Preferably, the weight percentage of the vinyl polylactic acid high molecular material in the composite photosensitive resin is 40-79%.
Specifically, the cross-linking agent is selected from any one of cyclohexanol hexaallyl ether or cyclohexanol hexaacrylate, the molecular structure of the cyclohexanol hexaallyl ether or cyclohexanol hexaacrylate contains 6 vinyl groups, and the cyclohexanol hexaallyl ether or cyclohexanol hexaacrylate and the vinyl polylactic acid high polymer material are subjected to effective photo-crosslinking reaction, so that the curing rate and effect are improved, and a good three-dimensional reticular cross-linking structure is formed.
Preferably, the crosslinking agent accounts for 20-50% of the composite photosensitive resin by weight.
Specifically, the filler is selected from any one of vinyl modified calcium carbonate and hydroxyapatite nano materials, the surfaces of the vinyl modified calcium carbonate and the hydroxyapatite nano materials contain a large amount of vinyl groups, and the vinyl modified calcium carbonate and the hydroxyapatite nano materials perform effective photo-crosslinking reaction with a vinyl polylactic acid high polymer material and a crosslinking agent, so that the curing rate and effect are improved, and the formation of a three-dimensional network crosslinking structure is further promoted.
Preferably, the filler accounts for 5-25% of the composite photosensitive resin by weight.
Specifically, the photoinitiator is selected from any one or a mixture of phenyl-2, 4, 6-trimethylbenzoyl lithium phosphonate, 2,4, 6-trimethylbenzoyl ethyl phenyl phosphonate and 1-hydroxycyclohexyl phenyl ketone; the photoinitiator accounts for 2-20% of the composite photosensitive resin by weight.
Specifically, the diluent is N-vinyl pyrrolidone or ethyl fumarate; the weight percentage of the diluent in the composite photosensitive resin is 5-30%.
Specifically, the solvent is selected from any one or more of dichloromethane, trichloromethane, carbon tetrachloride or dichloroethane; the solvent accounts for 5-20% of the composite photosensitive resin by weight.
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, within 10 seconds, the modified polylactic acid composite photosensitive resin provided by the invention is rapidly crosslinked and cured. 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, good hydrophilicity/hydrophobicity, high mechanical strength and high toughness. The mechanical strength and toughness are improved by more than 50% compared with the photosensitive resin which contains a 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 modified polylactic acid composite photosensitive resin, which is characterized by comprising the following steps of: mixing the above components at room temperature.
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 photocuring 3D printing modified polylactic acid composite photosensitive resin (1000 g) is as follows:
example 2
The formula of the photocuring 3D printing modified polylactic acid composite photosensitive resin (500 g) is as follows:
example 3
The formula of the photocuring 3D printing modified polylactic acid composite photosensitive resin (200 g) is as follows:
example 4
The formula of the photocuring 3D printing modified polylactic acid 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 (8)
1. The photocuring 3D printing modified polylactic acid composite photosensitive resin is characterized by comprising the following components in percentage by weight: 20-90% of vinyl polylactic acid high polymer material, 5-79% of cross-linking agent, 1-40% of photoinitiator, 0-60% of diluent, 0-40% of solvent and 0-30% of filler, wherein:
the structural general formula of the vinyl polylactic acid high polymer material is as follows:
wherein m, n and l are natural numbers of 1-1000000 respectively;
the cross-linking agent is selected from any one of cyclohexanol hexaallyl ether or cyclohexanol hexaacrylate;
the filler is selected from any one of vinyl modified calcium carbonate or hydroxyapatite nano materials.
2. The photocurable 3D printing modified polylactic acid composite photosensitive resin according to claim 1, wherein the: the weight percentage of the vinyl polylactic acid high molecular material in the composite photosensitive resin is 40-79%.
3. The photocuring 3D printing modified polylactic acid composite photosensitive resin as claimed in claim 1, wherein: the cross-linking agent accounts for 20-50% of the composite photosensitive resin by weight.
4. The photocuring 3D printing modified polylactic acid composite photosensitive resin as claimed in claim 1, wherein: the filler accounts for 5 to 25 weight percent of the composite photosensitive resin.
5. The photocurable 3D printing modified polylactic acid composite photosensitive resin according to any one of claims 1 to 4, wherein: the photoinitiator is selected from any one or a mixture of more of phenyl-2, 4, 6-trimethyl benzoyl lithium phosphonate, 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate and 1-hydroxycyclohexyl phenyl ketone; the photoinitiator accounts for 2-20% of the composite photosensitive resin by weight.
6. The photocurable 3D printing modified polylactic acid composite photosensitive resin according to any one of claims 1 to 4, wherein: the diluent is N-vinyl pyrrolidone or ethyl fumarate; the weight percentage of the diluent in the composite photosensitive resin is 5-30%.
7. The photocurable 3D printing modified polylactic acid composite photosensitive resin according to any one of claims 1 to 4, wherein: the solvent is selected from any one or more of dichloromethane, trichloromethane, carbon tetrachloride or dichloroethane; the solvent accounts for 5-20% of the composite photosensitive resin by weight.
8. The preparation method of the photocuring 3D printing modified polylactic acid composite photosensitive resin as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps: mixing the above components at room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010749582.9A CN111909320A (en) | 2020-07-30 | 2020-07-30 | Photocuring 3D printing modified polylactic acid composite photosensitive resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010749582.9A CN111909320A (en) | 2020-07-30 | 2020-07-30 | Photocuring 3D printing modified polylactic acid composite photosensitive resin and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN111909320A true CN111909320A (en) | 2020-11-10 |
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|---|---|---|---|
| CN202010749582.9A Pending CN111909320A (en) | 2020-07-30 | 2020-07-30 | Photocuring 3D printing modified polylactic acid composite photosensitive resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174021A (en) * | 2021-03-26 | 2021-07-27 | 四川大学 | Photosensitive bioabsorbable polymer with in-situ anti-cell adhesion function and preparation method thereof |
| CN113999539A (en) * | 2021-10-22 | 2022-02-01 | 李开南 | 3D printing composite material with CT imaging effect and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103941543A (en) * | 2014-03-27 | 2014-07-23 | 沈阳巧时器美科技有限公司 | Photosensitive resin composition based on polylactide polyol, preparation method thereof and photosensitive resin |
| CN104004173A (en) * | 2014-04-25 | 2014-08-27 | 湖北工业大学 | Preparation method of photoactive polylactic acid degradation material |
| CN106750230A (en) * | 2016-12-05 | 2017-05-31 | 武汉嘉三维技术应用有限公司 | A kind of preparation method of the modified polylactic acid material for 3D printing |
| CN107522827A (en) * | 2017-09-20 | 2017-12-29 | 杨军 | A kind of photocuring 3D printing photosensitive resin and its preparation method and application |
| 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 |
| WO2020013765A1 (en) * | 2018-07-11 | 2020-01-16 | Structo Pte Ltd | Methods and composition of a dental model for the manufacture of orthodontic appliances without the use of separator |
| 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
- 2020-07-30 CN CN202010749582.9A patent/CN111909320A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103941543A (en) * | 2014-03-27 | 2014-07-23 | 沈阳巧时器美科技有限公司 | Photosensitive resin composition based on polylactide polyol, preparation method thereof and photosensitive resin |
| CN104004173A (en) * | 2014-04-25 | 2014-08-27 | 湖北工业大学 | Preparation method of photoactive polylactic acid degradation material |
| CN106750230A (en) * | 2016-12-05 | 2017-05-31 | 武汉嘉三维技术应用有限公司 | A kind of preparation method of the modified polylactic acid material for 3D printing |
| CN107522827A (en) * | 2017-09-20 | 2017-12-29 | 杨军 | A kind of photocuring 3D printing photosensitive resin and its preparation method and application |
| 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 |
| WO2020013765A1 (en) * | 2018-07-11 | 2020-01-16 | Structo Pte Ltd | Methods and composition of a dental model for the manufacture of orthodontic appliances without the use of separator |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 刘凡等: "乙烯基改性四臂星形聚乳酸的研究", 《2016年全国高分子材料科学与工程研讨会》, 1 November 2016 (2016-11-01), pages 529 * |
| 杨继全等著: "《异质材料3D打印技术》", 31 March 2019, 华中科技大学出版社, pages: 120 * |
| 陈道义等编著: "《现代网印油墨选择与使用手册》", 上海科学技术出版社, pages: 259 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174021A (en) * | 2021-03-26 | 2021-07-27 | 四川大学 | Photosensitive bioabsorbable polymer with in-situ anti-cell adhesion function and preparation method thereof |
| CN113999539A (en) * | 2021-10-22 | 2022-02-01 | 李开南 | 3D printing composite material with CT imaging effect and preparation method and application thereof |
| CN113999539B (en) * | 2021-10-22 | 2022-09-09 | 李开南 | 3D printing composite material with CT imaging effect and preparation method and application thereof |
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