CN114805702A - SLA high-toughness photosensitive resin for 3D printing and preparation method thereof - Google Patents
SLA high-toughness photosensitive resin for 3D printing and preparation method thereof Download PDFInfo
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- CN114805702A CN114805702A CN202210484538.9A CN202210484538A CN114805702A CN 114805702 A CN114805702 A CN 114805702A CN 202210484538 A CN202210484538 A CN 202210484538A CN 114805702 A CN114805702 A CN 114805702A
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- 229920005989 resin Polymers 0.000 title claims abstract description 65
- 239000011347 resin Substances 0.000 title claims abstract description 65
- 238000010146 3D printing Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 32
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 7
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims description 19
- 150000003077 polyols Chemical class 0.000 claims description 19
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 16
- 238000005886 esterification reaction Methods 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 8
- ZXUJYIQZKNWLQN-UHFFFAOYSA-N [3-(7-oxabicyclo[4.1.0]heptan-3-ylmethyl)-7-oxabicyclo[4.1.0]heptan-3-yl] formate Chemical compound C(=O)OC1(CC2C(CC1)O2)CC1CC2C(CC1)O2 ZXUJYIQZKNWLQN-UHFFFAOYSA-N 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 229920000459 Nitrile rubber Polymers 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 9
- -1 phenyl sulfonium hexafluoroantimonate Chemical compound 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- SCVRCCQFGPWBMC-UHFFFAOYSA-N cyclohexyl-(2-hydroxyphenyl)methanone Chemical compound OC1=CC=CC=C1C(=O)C1CCCCC1 SCVRCCQFGPWBMC-UHFFFAOYSA-N 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000013557 residual solvent Substances 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- 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
- 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
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- 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)
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides SLA high-toughness photosensitive resin for 3D printing, which comprises the following components in percentage by weight: 55-65% of an epoxy resin oligomer, 20-30% of an acrylate oligomer, 4% of a modification additive, 8% of a photoinitiator and 3% of an auxiliary agent, wherein the acrylate oligomer contains polytetrahydrofuran acrylate. The preparation method of the SLA high-toughness photosensitive resin comprises the following steps: fully mixing epoxy resin oligomer, acrylate oligomer, modified additive, photoinitiator and auxiliary agent according to a certain weight percentage; and fully stirring at room temperature for 60-120 minutes to obtain the SLA high-toughness photosensitive resin for 3D printing. The SLA high-toughness photosensitive resin for 3D printing has low viscosity and high product speed, and ensures the rapid formability of 3D printing products; the volume shrinkage change is small after curing, and the dimensional stability of the product is high; stable mechanical property, excellent anti-aging property, simple preparation process and convenient popularization and application.
Description
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to SLA high-toughness photosensitive resin for 3D printing and a preparation method thereof.
Background
The 3D printing manufacturing process is constructed layer by layer with the assistance of a computer, the 3D printing is mainly to design a real space three-dimensional graph by a CAD, the three-dimensional model is processed by layers under the control of the computer, and then each layer is manufactured to form an accumulation manufacturing. Among 3D printing techniques, Stereolithography (SLA) is the most common. It mainly uses laser to irradiate photosensitive resin to cause the resin to radiate and polymerize, forming cross-linked polymer and producing solid material.
However, the performance and cost of the molding material still face many challenges, mainly because the material used in the technology is liquid photosensitive resin, the performance directly affects important indexes such as strength and toughness of the molded part, and further affects the application prospect of the SLA technology, so in recent years, many researches are made on improving the performance of the molding material and reducing the cost, and many effective technological methods are proposed.
At present, most of photosensitive resins have problems in common: after photocuring, the product is brittle, easy to break and poor in processability, so that the application of the product in many fields is limited. Therefore, it is becoming a focus of attention how to develop a photosensitive resin having high toughness.
Polyether polyol is commonly added into a photosensitive resin formula system in the market to improve the flexibility, impact strength and the like of a 3D printing part, the main chain of the polyether polyol molecule is provided with ether bonds, and the polyether polyol is mainly used for forming a soft segment in a polyurethane molecular structure, and although the polyether polyol can improve the flexibility and toughness of PU, the hardness, tensile strength and the like of a material cannot be improved.
Disclosure of Invention
In order to solve the problems, the invention aims to provide an SLA high-toughness photosensitive resin for 3D printing and a preparation method thereof, wherein the resin product has lower viscosity and high forming precision, and a printed product has good stability and excellent toughness; and the preparation method has simple and efficient steps.
In order to achieve the purpose, the invention provides an SLA high-toughness photosensitive resin for 3D printing, which comprises the following components in percentage by weight:
the sum of the percentage compositions of the above components is 100%;
wherein the acrylate oligomer contains polytetrahydrofuran acrylate PTHF-DA.
The polytetrahydrofuran acrylate is obtained by esterification reaction of polytetrahydrofuran polyalcohol and acrylic acid.
The molecular weight of the polytetrahydrofuran polyalcohol is 250-2000.
The molecular weight of the polytetrahydrofuran polyol is 650.
The epoxy resin oligomer is at least one of bisphenol A epoxy resin (DYD-128), 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate (2021P), hydrogenated bisphenol A epoxy resin (HE-2025) and 3-ethyl-3-oxetanylcarbinol (MOX-101).
The acrylate oligomer further comprises at least one of epoxy acrylate (CN104NS), trimethylolpropane triacrylate (SR351NS), ethoxylated trimethylolpropane triacrylate (SR499NS), propoxylated neopentyl glycol diacrylate (SR9003 NS).
The modified additive is core-shell toughened modified resin (EPX-125).
The photoinitiator is a mixture (1176) of diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluoroantimonate and diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluorophosphate and/or hydroxycyclohexyl phenyl ketone (184).
The auxiliary agent comprises one or more of carboxyl-terminated liquid nitrile rubber (CTBN), hydroxyl-terminated liquid nitrile rubber (HTBN) and polyether polyol (LEP 4801).
A method for preparing the SLA high-toughness photosensitive resin for 3D printing comprises the following steps:
(1) fully mixing epoxy resin oligomer, acrylate oligomer, modified additive, photoinitiator and auxiliary agent according to a certain weight percentage;
(2) and fully stirring at room temperature for 60-120 minutes to obtain the SLA high-toughness photosensitive resin for 3D printing.
The invention has the beneficial effects that:
1. the SLA high-toughness photosensitive resin for 3D printing has low viscosity and high product speed, and ensures the rapid formability of 3D printing products; and the volume shrinkage change is small after curing, and the dimensional stability of the product is high.
2. The SLA high-toughness photosensitive resin for 3D printing provided by the invention has the advantages of stable mechanical property, excellent ageing resistance, simple preparation process and convenience in popularization and application.
3. The SLA high-toughness photosensitive resin product for 3D printing has excellent yellowing resistance and high toughness, and can fill the gap of the market for the high-toughness photosensitive resin.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1: SLA high-toughness photosensitive resin for 3D printing and preparation thereof
Preparation of polytetrahydrofuran acrylate: 100g of PTHF250, 63g of acrylic acid, 2.5g of p-hydroxyanisole and 4g of p-toluenesulfonic acid monohydrate are weighed, added into a three-neck flask provided with a water separator, a thermometer, a stirrer and a reflux condenser tube to carry out esterification reaction for 10 hours at 120 ℃, the obtained esterification reactant is subjected to alkali washing and water washing, an organic phase is taken and is subjected to rotary evaporation in a vacuum rotary evaporator until a constant weight is reached, and the organic phase is pumped for 2 hours by using an oil pump to remove residual solvent.
Preparation of photosensitive resin: weighing 10g of prepared polytetrahydrofuran acrylate (PTHF250-DA), 15g of SR351NS (trimethylolpropane triacrylate), 20g of DYD-128 (bisphenol A epoxy resin), 10g of 2021P (3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate), 15g of HE-2025 (hydrogenated bisphenol A epoxy resin), 15g of MOX-101 (3-ethyl-3-oxetanylcarbinol), 3g of LEP4801 (polyether polyol), 4g of EPX-125 (core-shell toughening modified resin), 4g of 1176 (a mixture of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate and diphenyl- (4-phenylthio) phenylsulfonium hexafluoro phosphate), and 4g of 184 (hydroxycyclohexylphenylmethanone), fully mixing, stirring at room temperature for 60-120 minutes until the photoinitiator and the additive are completely dissolved, thus obtaining the SLA high-toughness photosensitive resin for 3D printing.
Example 2: SLA high-toughness photosensitive resin for 3D printing and preparation thereof
Preparation of polytetrahydrofuran acrylate: 100g of PTHF650, 24g of acrylic acid, 1g of p-hydroxyanisole and 1.5g of p-toluenesulfonic acid monohydrate are weighed, added into a three-neck flask provided with a water separator, a thermometer, a stirrer and a reflux condenser tube to carry out esterification reaction for 10 hours at 120 ℃, the obtained esterification reactant is subjected to alkali washing and water washing, an organic phase is taken and is subjected to rotary evaporation in a vacuum rotary evaporator until a constant weight is reached, and the organic phase is pumped for 2 hours by using an oil pump to remove residual solvent.
Preparation of photosensitive resin: weighing 10g of prepared polytetrahydrofuran acrylate (PTHF650-DA), 15g of SR351NS (trimethylolpropane triacrylate), 20g of DYD-128 (bisphenol A epoxy resin), 10g of 2021P (3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate), 15g of HE-2025 (hydrogenated bisphenol A epoxy resin), 15g of MOX-101 (3-ethyl-3-oxetanylcarbinol), 3g of LEP4801 (polyether polyol), 4g of EPX-125 (core-shell toughening modified resin), 4g of 1176 (mixture of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate and diphenyl- (4-phenylthio) phenylsulfonium hexafluoro phosphate), and 4g of 184 (hydroxycyclohexylphenylmethanone), fully mixing, stirring at room temperature for 60-120 minutes until the photoinitiator and the additive are completely dissolved, thus obtaining the SLA high-toughness photosensitive resin for 3D printing.
Example 3: SLA high-toughness photosensitive resin for 3D printing and preparation thereof
Preparation of polytetrahydrofuran acrylate: 100g of PTHF1000, 16g of acrylic acid, 0.6g of p-hydroxyanisole and 1g of p-toluenesulfonic acid monohydrate are weighed, added into a three-neck flask provided with a water separator, a thermometer, a stirrer and a reflux condenser tube to carry out esterification reaction for 9 hours at 120 ℃, the obtained esterification reactant is subjected to alkali washing and water washing, an organic phase is taken and is subjected to rotary evaporation in a vacuum rotary evaporator until reaching a constant weight, and the organic phase is pumped for 2 hours by using an oil pump to remove residual solvent.
Preparation of photosensitive resin: weighing 10g of prepared polytetrahydrofuran acrylate (PTHF1000-DA), 15g of SR351NS (trimethylolpropane triacrylate), 20g of DYD-128 (bisphenol A epoxy resin), 10g of 2021P (3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate), 15g of HE-2025 (hydrogenated bisphenol A epoxy resin), 15g of MOX-101 (3-ethyl-3-oxetanylcarbinol), 3g of LEP4801 (polyether polyol), 4g of EPX-125 (core-shell toughening modified resin), 4g of 1176 (a mixture of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate and diphenyl- (4-phenylthio) phenylsulfonium hexafluoro phosphate), and 4g of 184 (hydroxycyclohexylphenylmethanone), fully mixing, stirring at room temperature for 60-120 minutes until the photoinitiator and the additive are completely dissolved, thus obtaining the SLA high-toughness photosensitive resin for 3D printing.
Example 4: SLA high-toughness photosensitive resin for 3D printing and preparation thereof
Preparation of polytetrahydrofuran acrylate: 100g of PTHF2000, 8g of acrylic acid, 0.3g of p-hydroxyanisole and 0.5g of p-toluenesulfonic acid monohydrate are weighed, added into a three-neck flask provided with a water separator, a thermometer, a stirrer and a reflux condenser tube to carry out esterification reaction for 9h at 120 ℃, the obtained esterification reactant is subjected to alkali washing and water washing, an organic phase is taken out and is subjected to rotary evaporation in a vacuum rotary evaporator until the constant weight is reached, and the mixture is pumped for 2h by using an oil pump to remove residual solvent.
Preparation of photosensitive resin: weighing 10g of prepared polytetrahydrofuran acrylate (PTHF2000-DA), 15g of SR351NS (trimethylolpropane triacrylate), 20g of DYD-128 (bisphenol A epoxy resin), 10g of 2021P (3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate), 15g of HE-2025 (hydrogenated bisphenol A epoxy resin), 15g of MOX-101 (3-ethyl-3-oxetanylcarbinol), 3g of LEP4801 (polyether polyol), 4g of EPX-125 (core-shell toughening modified resin), 4g of 1176 (mixture of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate and diphenyl- (4-phenylthio) phenylsulfonium hexafluoro phosphate), and 4g of 184 (hydroxycyclohexylphenylmethanone), fully mixing, stirring at room temperature for 60-120 minutes until the photoinitiator and the additive are completely dissolved, thus obtaining the SLA high-toughness photosensitive resin for 3D printing.
Example 5: SLA high-toughness photosensitive resin for 3D printing and preparation thereof
Preparation of polytetrahydrofuran acrylate: weighing 120g of PTHF650, 29g of acrylic acid, 1.4g of p-hydroxyanisole and 3.5g of p-toluenesulfonic acid monohydrate, adding the PTHF650, 29g of acrylic acid, 1.4g of p-hydroxyanisole and 3.5g of p-toluenesulfonic acid monohydrate into a three-neck flask provided with a water separator, a thermometer, a stirrer and a reflux condenser, carrying out esterification reaction at 120 ℃ for 10 hours, carrying out alkaline washing and water washing on the obtained esterification reactant, taking an organic phase, carrying out rotary evaporation in a vacuum rotary evaporator until a constant weight is reached, and pumping for 2 hours by using an oil pump to remove residual solvent.
Preparation of photosensitive resin: weighing 5g of prepared polytetrahydrofuran acrylate (PTHF650-DA), 15g of SR351NS (trimethylolpropane triacrylate), 25g of DYD-128 (bisphenol A epoxy resin), 10g of 2021P (3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate), 15g of HE-2025 (hydrogenated bisphenol A epoxy resin), 15g of MOX-101 (3-ethyl-3-oxetanylcarbinol), 3g of LEP4801 (polyether polyol), 4g of EPX-125 (core-shell toughening-modified resin), 4g of 1176 (a mixture of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate and diphenyl- (4-phenylthio) phenylsulfonium hexafluoro phosphate), and 4g of 184 (hydroxycyclohexylphenylmethanone), fully mixing, stirring at room temperature for 60-120 minutes until the photoinitiator and the additive are completely dissolved, thus obtaining the SLA high-toughness photosensitive resin for 3D printing.
Example 6: SLA high-toughness photosensitive resin for 3D printing and preparation thereof
Preparation of polytetrahydrofuran acrylate: 150g of PTHF650, 36g of acrylic acid, 1.7g of p-hydroxyanisole and 4.4g of p-toluenesulfonic acid monohydrate are weighed, added into a three-neck flask provided with a water separator, a thermometer, a stirrer and a reflux condenser tube to carry out esterification reaction for 10 hours at 120 ℃, the obtained esterification reactant is subjected to alkali washing and water washing, an organic phase is taken out and is subjected to rotary evaporation in a vacuum rotary evaporator until a constant weight is reached, and the mixture is pumped for 2 hours by using an oil pump to remove residual solvent.
Preparation of photosensitive resin: weighing 15g of prepared polytetrahydrofuran acrylate (PTHF650-DA), 15g of SR351NS (trimethylolpropane triacrylate), 25g of DYD-128 (bisphenol A epoxy resin), 10g of 2021P (3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate), 10g of HE-2025 (hydrogenated bisphenol A epoxy resin), 10g of MOX-101 (3-ethyl-3-oxetanylcarbinol), 3g of LEP4801 (polyether polyol), 4g of EPX-125 (core-shell toughening modified resin), 4g of 1176 (mixture of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate and diphenyl- (4-phenylthio) phenylsulfonium hexafluoro phosphate), and 4g of 184 (hydroxycyclohexylphenylmethanone), fully mixing, stirring at room temperature for 60-120 minutes until the photoinitiator and the additive are completely dissolved, thus obtaining the SLA high-toughness photosensitive resin for 3D printing.
The mass percentages of the components of the above examples 1-6 are shown in the following table 1:
TABLE 1
The samples produced in the six examples above were subjected to performance tests including, but not limited to, the following: tensile strength (ASTM D638 standard, flexural strength (ASTM D790 standard), hardness (ASTM D2240 standard), elongation at break (ASTM D638 standard), impact strength (ASTM D256 standard), heat distortion temperature (ASTM D648@66PS standard), etc. the corresponding test results are shown in Table 2:
TABLE 2
In the above examples 1 to 4, which are comparative examples, in order to investigate the influence of the polytetrahydrofuran acrylate prepared using polytetrahydrofuran polyols having different molecular weights on the mechanical properties of the finally prepared photosensitive resin, it can be seen from the results of the relevant tests in table 2 that when the polytetrahydrofuran polyol has a molecular weight of 650, the prepared photosensitive resin is more excellent in mechanical properties, the balance between hardness and flexibility is best, and the impact strength is excellent.
In the above examples 2, 5 and 6, which are comparative examples, in order to investigate the influence of using polytetrahydrofuran acrylate with different weight ratios on the mechanical properties of the finally prepared photosensitive resin, it can be seen from the related test results in table 2 that, under the premise that the molecular weight of the polytetrahydrofuran polyol is 650, when the polytetrahydrofuran acrylate accounts for 10% (the total weight of the components), the mechanical properties of the prepared photosensitive resin are more excellent; when the ratio of the polytetrahydrofuran acrylate is less than 10%, the impact strength and the elongation at break of the prepared photosensitive resin are greatly reduced; when the ratio of the polytetrahydrofuran acrylate is more than 10%, the impact strength and elongation at break of the prepared photosensitive resin are reduced.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. The SLA high-toughness photosensitive resin for 3D printing is characterized by comprising the following components in percentage by weight:
55-65% of epoxy resin oligomer
20-30% of acrylate oligomer
4 percent of modified additive
8 percent of photoinitiator
3 percent of auxiliary agent
The sum of the percentage compositions of the above components is 100%;
wherein the acrylate oligomer contains polytetrahydrofuran acrylate.
2. The SLA high toughness photosensitive resin for 3D printing according to claim 1, wherein the polytetrahydrofuran acrylate is obtained by esterification of polytetrahydrofuran polyol and acrylic acid.
3. The SLA high toughness photosensitive resin for 3D printing according to claim 2, wherein the molecular weight of the polytetrahydrofuran polyol is 250-2000.
4. The SLA high toughness photosensitive resin for 3D printing according to claim 3, wherein the molecular weight of the polytetrahydrofuran polyol is 650.
5. The SLA high toughness photosensitive resin for 3D printing according to claim 1, wherein the epoxy resin oligomer is at least one of bisphenol A epoxy resin, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate, hydrogenated bisphenol A epoxy resin, 3-ethyl-3-oxetanylcarbinol.
6. The SLA high toughness photosensitive resin for 3D printing according to claim 1, wherein the acrylate oligomer further comprises at least one of epoxy acrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated neopentyl glycol diacrylate.
7. The SLA high-toughness photosensitive resin for 3D printing according to claim 1, wherein the modification additive is a core-shell toughening modification resin.
8. The SLA high toughness photosensitive resin for 3D printing according to claim 1, wherein the photoinitiator is selected from diphenyl- (4-phenylthio) phenyl sulfonium hexafluoroantimonate, a mixture of diphenyl- (4-phenylthio) phenyl sulfonium hexafluorophosphate and/or hydroxycyclohexyl phenyl ketone.
9. The SLA high toughness photosensitive resin for 3D printing according to claim 1, wherein the auxiliary agent comprises one or more of carboxyl end group liquid nitrile rubber, hydroxyl end group liquid nitrile rubber and polyether polyol.
10. A method for preparing SLA high-toughness photosensitive resin for 3D printing according to any of claims 1-9, comprising the following steps:
(1) fully mixing epoxy resin oligomer, acrylate oligomer, modified additive, photoinitiator and auxiliary agent according to a certain weight percentage;
(2) and fully stirring at room temperature for 60-120 minutes to obtain the SLA high-toughness photosensitive resin for 3D printing.
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| CN1543590A (en) * | 2001-06-21 | 2004-11-03 | Dsm Ip�Ʋ�����˾ | Radiation-curable resin composition and rapid prototyping process using the same |
| WO2012041522A1 (en) * | 2010-10-01 | 2012-04-05 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Device and method for the production of 3d structures in layers, and use thereof |
| CN108329683A (en) * | 2018-02-27 | 2018-07-27 | 中山市精微新材料有限公司 | A kind of 3D printing light-sensitive material and preparation method thereof containing nano-cellulose |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543590A (en) * | 2001-06-21 | 2004-11-03 | Dsm Ip�Ʋ�����˾ | Radiation-curable resin composition and rapid prototyping process using the same |
| WO2012041522A1 (en) * | 2010-10-01 | 2012-04-05 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Device and method for the production of 3d structures in layers, and use thereof |
| CN108329683A (en) * | 2018-02-27 | 2018-07-27 | 中山市精微新材料有限公司 | A kind of 3D printing light-sensitive material and preparation method thereof containing nano-cellulose |
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