CN112250804A - Secondary curing 3D printing resin - Google Patents
Secondary curing 3D printing resin Download PDFInfo
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- CN112250804A CN112250804A CN202011149041.9A CN202011149041A CN112250804A CN 112250804 A CN112250804 A CN 112250804A CN 202011149041 A CN202011149041 A CN 202011149041A CN 112250804 A CN112250804 A CN 112250804A
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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
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Ceramic Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a secondary curing 3D printing resin which comprises a component A, a component B and a photoinitiator, wherein the component A comprises 50-80 parts of isocyanate-terminated prepolymer and 20-50 parts of reactive diluent, the component B comprises 50-80 parts of acrylate prepolymer and 20-50 parts of reactive diluent, and the ultraviolet initiator accounts for 1-5% of the total mass of the resin. The isocyanate groups in the product after the resin is subjected to 3D printing and molding provided by the invention are further reacted under the heating condition to form a double-network structure, so that the mechanical property of the product can be effectively improved, different performance requirements can be met by designing and adjusting the resin formula, the product can be prepared from an elastic material to a tough material simply, and meanwhile, the mixed resin is very stable in the 3D printing process and has a long printing window.
Description
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to a secondary curing 3D printing resin.
Background
For different printing processes, 3D printing technologies can be generally classified into fused deposition modeling, selective laser sintering, and photocuring rapid prototyping. Among them, the photocuring rapid prototyping technology is a 3D printing technology which is the most widely and mature at present. In recent years, with the development of 3D printing technology, DLP/SLA is more and more widely applied, and has advantages that cannot be achieved by traditional processing technology in the processing of customized devices or complex components. But the defects of the required light-cured resin performance limit the further development and industrialization promotion of the technology. At present, the problem of insufficient mechanical properties of the glazing curing resin on the market generally exists.
Therefore, the method has important significance in improving the performance of the light-cured resin while considering the printing performance. CN111592621A discloses a two-component photocuring resin for 3D printing, which is prepared by mixing A, B components and carrying out photocuring, wherein isocyanate groups contained in the components respectively further react with active hydrogen, so that the mechanical property of the photocuring resin is improved. However, after the A, B components in the formula related by the invention patent are mixed, isocyanate contained in the system directly contacts with active hydrogen groups, the 3D printing window time of the resin is short, and the isocyanate and the active hydrogen react in the printing process to cause the whole curing condition, thereby causing printing failure and resin waste. CN111349197B discloses a dual-curing 3D printing photosensitive resin composition, which, like the above patent, also contains several key components of acrylate, isocyanate group-terminated prepolymer, chain extender (active hydrogen), so it also has the problem of short 3D printing window time.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a secondary curing resin, after curing and forming, isocyanate groups contained in a printed product further react under the heating condition, a double-network structure is constructed in the product, the performance of the product is improved, the product with different performance requirements can be obtained by designing and adjusting the formula of the resin, and the problem of short time of a 3D printing window of the resin is solved.
In order to achieve the purpose, the invention adopts the technical scheme that:
the secondary curing 3D printing resin comprises a component A, a component B and a photoinitiator, wherein the component A comprises 50-80 parts of isocyanate-terminated prepolymer and 20-50 parts of reactive diluent, the component B comprises 50-80 parts of acrylate prepolymer and 20-50 parts of reactive diluent, and the ultraviolet initiator accounts for 1-5% of the total mass of the resin.
Preferably, the mixing ratio of the component A to the component B is 1:1, and the photoinitiator is added after the component A and the component B are mixed.
Preferably, the isocyanate group-ended prepolymer is one or a mixture of two of an isocyanate group-ended polyurethane prepolymer and a polyurea prepolymer.
Preferably, the acrylate prepolymer comprises one or more of a polyurethane acrylate prepolymer, an epoxy acrylate prepolymer and a polyester acrylate prepolymer.
Preferably, the reactive diluent in the A component and the B component is one or more of isooctyl acrylate, isodecyl acrylate, ethoxy ethyl acrylate, tetrahydrofuran acrylate, polyethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate.
Preferably, the ultraviolet light initiator is one or more of Irgacure 819, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide and benzoin dimethyl ether.
Preferably, the resin comprises a pigment, the pigment accounts for 0.01-0.5% of the total mass of the resin, and the pigment is one or more of an organic pigment, an ultraviolet curing color paste and a metal complex dye.
Preferably, the preparation method of the isocyanate group-ended prepolymer in the component A is as follows:
1) mixing the dehydrated oligomer polyol or polyamine and polyisocyanate according to the mass ratio of 1 (1.2-2), and stirring and uniformly mixing at 30-70 ℃;
2) adding a catalyst accounting for 0-1% of the total mass of the mixture, and continuously reacting for 1-8 h.
Preferably, the catalyst is one or more of stannous octoate, dibutyltin dilaurate and dioctyltin dilaurate.
Preferably, the polyisocyanate is one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated XDI, hydrogenated MDI, HDI trimer, and HDI biuret.
Preferably, the oligomer polyol or the polyamine is one or more of alkyd polyester polyol, polycaprolactone polyol, polycarbonate polyol, polypropylene oxide polyol, polytetrahydrofuran polyol, polyether polyol and polyether amine.
Preferably, the prepolymer end groups are isocyanate groups.
And (3) after the 3D printing resin is cured by ultraviolet light, carrying out heat treatment in an oven at the temperature of 60-120 ℃ for 3-24h to obtain a 3D printing product.
When the secondary curing 3D printing resin provided by the invention is applied, a printed product contains isocyanate groups, and the isocyanate groups react under the heating condition to form high molecular weight polyurethane, so that a double-network structure is formed with polyacrylate formed in the printing process. The reactions that occur under heating are as follows:
the invention has the advantages that: according to the secondary curing 3D printing resin provided by the invention, the isocyanate group in the product is further reacted under the heating condition after photocuring molding to construct a double-network structure, so that the mechanical property of the product can be effectively improved, different performance requirements can be met by designing and adjusting the resin formula, and the resin can be prepared from an elastic material to a tough material; when the resin system is used, the resin system does not have active hydrogen groups, so that the problems that the resin is integrally cured and fails to be printed due to the reaction between isocyanate groups and the active hydrogen in the resin in the 3D printing process are effectively avoided.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
The isocyanate group-ended prepolymer is prepared as follows:
1) mixing the dehydrated polytetrahydrofuran diol (Mn-1000) and hexamethylene diisocyanate in a mass ratio of 1:1.5, and stirring at 50 ℃;
2) after the mixture is uniformly mixed, slowly dropwise adding dibutyltin dilaurate accounting for 0.2 percent of the total mass of the mixture, and continuously stirring for reaction for 3 hours to obtain the isocyanate-terminated polyurethane prepolymer.
The component A comprises: taking 75 parts of the polyurethane prepolymer, adding 25 parts of isooctyl acrylate, and uniformly stirring for later use;
and B component: 80 parts of commercially available DSM U-80 resin is taken, 10 parts of isooctyl acrylate is added, and the mixture is uniformly stirred for standby.
The A, B components are mixed according to the mass ratio of 1:1, and 3 percent of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide and 0.1 percent of Clariant UV color paste-black N in the total mass of the mixing system are added and stirred uniformly.
Example 2
The isocyanate group-ended prepolymer is prepared as follows:
1) mixing dehydrated polytetrahydrofuran diol (Mn-2000) and hexamethylene diisocyanate in the mass ratio of 1:1.7, and stirring at 50 ℃;
2) after the mixture is uniformly mixed, slowly dropwise adding dibutyltin dilaurate accounting for 0.2 percent of the total mass of the mixture, and continuously stirring for reaction for 5 hours to obtain the isocyanate-terminated polyurethane prepolymer.
The component A comprises: taking 70 parts of the polyurethane prepolymer, adding 30 parts of isodecyl acrylate, and uniformly stirring for later use;
and B component: 80 parts of commercially available DSM U-80 resin is taken, 10 parts of isodecyl acrylate is added, and the mixture is uniformly stirred for standby.
The A, B components are mixed according to the mass ratio of 1:1, 3 percent of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide and 0.1 percent of Clariant UV color paste-black N in the total mass of a mixing system are added, and the mixture is stirred and mixed evenly.
Example 3
The polyurea prepolymer is prepared by the following method:
uniformly mixing the dehydrated polyether amine (Mn-2000) and diphenylmethane diisocyanate in a mass ratio of 1:2, adding no catalyst, and stirring at 60 ℃ for reaction for 4 hours to obtain the isocyanate-terminated polyurea prepolymer.
The component A comprises: taking 70 parts of the polyurea prepolymer, adding 25 parts of isobornyl acrylate, and uniformly stirring for later use;
and B component: taking 70 parts of commercially available DSM U-61 resin, adding 20 parts of isodecyl acrylate, and uniformly stirring for later use.
The A, B components are mixed according to the mass ratio of 1:1, added with Irgacure 819 accounting for 3 percent of the total mass of the mixing system and Sudan III accounting for 0.03 percent of the total mass of the mixing system, and stirred and mixed evenly.
Example 4
The isocyanate group-ended prepolymer is prepared as follows:
1) mixing the dehydrated polytetrahydrofuran diol (Mn-650) and diphenylmethane diisocyanate in a mass ratio of 1:1.4, and stirring at 40 ℃;
2) after the mixture is uniformly mixed, slowly dropwise adding dibutyltin dilaurate accounting for 0.1 percent of the total mass of the mixture, and continuously stirring for reacting for 6 hours to obtain the isocyanate-terminated polyurethane prepolymer.
The component A comprises: taking 75 parts of the polyurethane prepolymer, adding 15 parts of isobornyl acrylate, and uniformly stirring for later use;
and B component: 70 parts of commercially available sartomer CN983 NS resin is taken, 40 parts of isobornyl acrylate is added, and the mixture is stirred uniformly for standby.
The A, B components are mixed according to the mass ratio of 1:1, 2 percent of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide and 0.05 percent of melanin in the total mass of a mixing system are added, and the mixture is stirred and mixed evenly.
After all the samples of the above examples were completely photo-cured, they were further heat treated at 110 ℃ for 12 hours, wherein the samples of examples 1 and 2 were tested according to ASTM D412, and the samples of examples 3 and 4 were tested for properties according to ASTM D638, and the test results are shown in the following table:
the above embodiments are merely preferred embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and any technical solutions belonging to the idea of the present invention should fall within the protection scope of the present invention. Several modifications and variations are possible in light of the above teaching and are to be considered within the scope of the present invention.
Claims (10)
1. The secondary curing 3D printing resin is characterized by comprising a component A, a component B and a photoinitiator, wherein the component A comprises 50-80 parts of isocyanate-terminated prepolymer and 20-50 parts of reactive diluent, the component B comprises 50-80 parts of acrylate prepolymer and 20-50 parts of reactive diluent, and the ultraviolet initiator accounts for 1-5% of the total mass of the resin.
2. The two-shot 3D printing resin of claim 1, wherein the isocyanate-terminated prepolymer is one or a mixture of two of an isocyanate-terminated polyurethane prepolymer or a polyurea prepolymer.
3. The two-cure 3D printing resin of claim 1, wherein the acrylate prepolymer comprises one or more of a polyurethane acrylate prepolymer, an epoxy acrylate prepolymer, and a polyester acrylate prepolymer.
4. The two-shot 3D printing resin as recited in claim 1 wherein the reactive diluent in the a and B components is one or more of isooctyl acrylate, isodecyl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofuranyl acrylate, polyethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate.
5. The two-cure 3D printing resin according to claim 1, wherein the photoinitiator is one or more of Irgacure 819, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, benzoin dimethyl ether.
6. The secondary curing 3D printing resin as claimed in claim 1, wherein the resin comprises a pigment, the pigment accounts for 0.01-0.5% of the total mass of the resin, and the pigment is one or more of an organic pigment, an ultraviolet curing color paste and a metal complex dye.
7. The two-shot 3D printing resin according to claim 1 or 2, wherein the isocyanate-terminated prepolymer in the a-component is prepared by the following method:
1) mixing the dehydrated oligomer polyol or polyamine and polyisocyanate according to the mass ratio of 1 (1.2-2), and stirring and uniformly mixing at 30-70 ℃;
2) adding dibutyltin dilaurate accounting for 0-1% of the total mass of the mixture, and continuously reacting for 1-8 h.
8. The secondary cured 3D printing resin according to claim 7, wherein the polyisocyanate is one or more of hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, xylylene diisocyanate XDI, toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, hydrogenated XDI, hydrogenated MDI, HDI trimer, and HDI biuret.
9. The secondary cured 3D printing resin according to claim 8, wherein the oligomer polyol or polyamine is one or more of a mixture of alkyd polyester polyol, polycaprolactone polyol, polycarbonate polyol, polyoxypropylene polyol, polytetrahydrofuran polyol, co-polyether polyol, and polyetheramine.
10. The secondary curing 3D printing resin as claimed in claim 1, wherein the 3D printing resin is cured by ultraviolet light and then is subjected to heat treatment in an oven at 60-120 ℃ for 3-24h to obtain a 3D printed product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011149041.9A CN112250804A (en) | 2020-10-23 | 2020-10-23 | Secondary curing 3D printing resin |
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| CN202011149041.9A CN112250804A (en) | 2020-10-23 | 2020-10-23 | Secondary curing 3D printing resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072678A (en) * | 2021-02-22 | 2021-07-06 | 浙江大学 | Polyurea acrylate oligomer and preparation method and application method thereof |
| CN114181356A (en) * | 2021-12-09 | 2022-03-15 | 上海交通大学医学院附属第九人民医院 | Photosensitive resin and application thereof and preparation method of dental retainer |
| CN114752109A (en) * | 2022-05-07 | 2022-07-15 | 浙江大学 | Upgrading recycling method of resin containing ester bonds |
| CN115745715A (en) * | 2022-10-28 | 2023-03-07 | 东南大学 | NEPE propellant slurry for 3D printing, preparation method and 3D printing method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072678A (en) * | 2021-02-22 | 2021-07-06 | 浙江大学 | Polyurea acrylate oligomer and preparation method and application method thereof |
| CN114181356A (en) * | 2021-12-09 | 2022-03-15 | 上海交通大学医学院附属第九人民医院 | Photosensitive resin and application thereof and preparation method of dental retainer |
| CN114181356B (en) * | 2021-12-09 | 2023-09-01 | 上海交通大学医学院附属第九人民医院 | Photosensitive resin, application thereof and preparation method of tooth holder |
| CN114752109A (en) * | 2022-05-07 | 2022-07-15 | 浙江大学 | Upgrading recycling method of resin containing ester bonds |
| CN115745715A (en) * | 2022-10-28 | 2023-03-07 | 东南大学 | NEPE propellant slurry for 3D printing, preparation method and 3D printing method |
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