CN107641200B - Thiol-ene photocuring resin for 3D printing and preparation method thereof - Google Patents

Thiol-ene photocuring resin for 3D printing and preparation method thereof Download PDF

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CN107641200B
CN107641200B CN201710857929.XA CN201710857929A CN107641200B CN 107641200 B CN107641200 B CN 107641200B CN 201710857929 A CN201710857929 A CN 201710857929A CN 107641200 B CN107641200 B CN 107641200B
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acrylic resin
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张小敏
陈遒
应慧春
李芳�
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Hangzhou Leyi New Material Technology Co ltd
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C08F283/105Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
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    • C08F2/00Processes of polymerisation
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Abstract

The invention relates to the technical field of 3D printing, in particular to mercaptan-alkene photocuring resin for 3D printing and a preparation method thereof. The thiol-ene photocuring resin for 3D printing is prepared from polythiol, an acrylic resin prepolymer, a reactive diluent, an initiator, an ultraviolet absorbent, a filler and an auxiliary agent. The 3D printing light-cured resin has the advantages that in the presence of a photoinitiator, when printing, polymerizing and molding are carried out, the volume shrinkage of a polymer is reduced due to the chain transfer reaction between double bonds and sulfydryl, oxygen-free polymerization inhibition is realized, the crosslinking degree and the reaction speed can be controlled according to different vinyl monomers, a small amount of photoinitiator is used, and the like. According to the invention, through introducing thiol-ene click chemical reaction into the 3D printing resin, the curing time can be shortened, the toughness and hardness of the 3D printing material can be improved, the production efficiency is improved, and the energy utilization rate is greatly improved.

Description

Thiol-ene photocuring resin for 3D printing and preparation method thereof
Technical Field
The invention relates to the technical field of 3D printing, in particular to mercaptan-alkene photocuring resin for 3D printing and a preparation method thereof.
Background
Thiol-ene click chemistry describes the chemical reaction process visually as simple, efficient, practical as clicking a mouse, and is characterized by: (1) the reaction raw materials are easy to obtain, and the monomer has wide application range; (2) the method has high thermodynamic driving force and high reaction speed; (3) the reaction condition is simple and mild, and is hardly influenced by external environment (oxygen, water and the like); (4) no solvent is needed or the used solvent is easy to separate; (5) the yield is high, and the regularity of the product is good; (6) the product separation and purification method is simple. Click chemistry can utilize a series of efficient and reliable and selective C-S bond forming reactions to realize atomic connection, and carry out modular preparation of novel high-performance and functional polymers, so that the click chemistry has wide application as a connecting tool in the fields of organic synthesis, material science, molecular biology, biotechnology, high molecular synthesis and the like.
3D prints and is honored as the industrial revolution once more that overturns traditional manufacturing, and 3D printing technique utilizes the computer, turns into simple two-dimensional plane model with three-dimensional solid model, through computer control shaping procedure, finally obtains the manufacturing technology of the forming part of complicated shape. At present, dozens of rapid forming technologies exist, wherein the photocuring rapid forming technology is the earliest rapid forming technology, photosensitive resin is used as a material, and the characteristics of the resin directly influence the performance of a workpiece, the manufacturing time, the final precision of the part and the like. Currently, photosensitive resins are classified into 3 types: radical photosensitive resin, cationic photosensitive resin, and hybrid photosensitive resin. The traditional photosensitive resins can generate volume shrinkage in the photopolymerization process, directly affect the performance of a workpiece, cause the reduction of the properties such as adhesive force, hardness and the like, prolong the manufacturing time, affect the precision of the workpiece and cause serious oxygen inhibition.
Aiming at the technical problems in the prior art, providing a photosensitive resin material with new performance is a problem to be solved urgently.
Disclosure of Invention
In order to solve the problems in the prior art, the present invention provides a novel photosensitive resin for 3D printing technology: the thiol-ene photosensitive resin for 3D printing is prepared from polythiol, an acrylic resin prepolymer, a reactive diluent, an initiator, an ultraviolet absorbent, a filler and an auxiliary agent.
In a preferred embodiment, the thiol-ene photocurable resin is prepared according to the following mixture ratio:
Figure BDA0001413487490000021
the thiol-ene photocurable resin of the present invention includes at least one polythiol. The polythiol is an organic molecule containing at least two mercapto groups and having the general formula R- (S-H)n1Wherein R is an organic moiety having a valence n1, and n1 is at least 2.
The polythiol can be polymerized or crosslinked with the acrylate by irradiation with light in the presence of an initiator. The polythiol can include 2 or more thiol groups.
An illustrative example of a polythiol having 2 or more mercapto groups in the molecule is represented by the following formulae (1) (2) (3) (4):
Figure BDA0001413487490000031
compounds containing 2 or more thiol groups in the molecule are: 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 8-octanedithiol, 2, 3-butanedithiol, 1, 9-nonanedithiol, 2,2 '- (1, 2-ethanediylbenzoyloxy) bisethanethiol, pentaerythritol tetrakis (3-mercaptopropionate), mercaptosilicone oils, isophthalylthiol, 1, 4-benzenedimethylmercaptan, 4-methyl-1, 2-dimercaptobenzene, 4, 4' -thiobisthiophenol, 2,4, 6-trimercaptotriazine, pentaerythritol tetrakis (3-mercaptobutyrate). Such compounds may be used alone or in combination of two or more.
The functionality of the polythiol, the type and number of R groups, and the degree of crosslinking, hardness and flexibility of the material can be adjusted.
For example, when preparing high hardness, high stiffness materials, the preferred R groups are aryl, alkyl, N-alkylcarbamoyl. Preferred polythiols include m-benzenedithiol, 1, 4-benzenedimethylthiol, 4, 4' -thiobisthiophenol, 4-methyl-1, 2-dimercaptobenzene, 2,4, 6-trimercaptotriazine, and the like.
In the preparation of highly flexible, high toughness materials, the preferred R groups are polyether groups, alkoxy groups, straight chain alkyl groups, siloxane groups. Preferred polythiols include, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 8-octanedithiol, 2, 3-butanedithiol, 1, 9-nonanedithiol, 2,2' - (1, 2-ethanediylberoxy) bisethanethiol, pentaerythritol tetrakis (3-mercaptopropionate), mercaptosilicone oils, pentaerythritol tetrakis (3-mercaptobutyrate), and the like.
The thiol-ene photosensitive resin preferably includes at least one polythiol, and about 5 to 30 parts by weight, more preferably about 10 to 20 parts by weight, of the polythiol, relative to the total weight of the composition.
The thiol-ene photocurable resin of the present invention includes at least one acrylic oligomer. The acrylic resin prepolymer in the thiol-ene light-cured resin forms the main component of the light-cured resin system, and the performance of the acrylic resin prepolymer greatly determines the main performance of the cured material. Generally, a prepolymer has a large molecular weight, and when cured, the volume shrinkage is small, and the curing speed is high, but the prepolymer has a large molecular weight, and the viscosity is high, so that more monomer dilution is required, and the high viscosity of the system affects the forming accuracy and forming efficiency of the 3D printing technology. Therefore, the choice of the prepolymer and its content is particularly important. The acrylic resin oligomer in the thiol-ene photosensitive resin comprises one or more of epoxy acrylic resin, polyester acrylic resin, polyurethane acrylic resin, unsaturated polyester, organic silicon acrylate prepolymer and polyether acrylic resin.
In the present invention, when a high-hardness, high-rigidity material is produced, epoxy acrylic resin, polyester acrylic resin and unsaturated polyester are preferable. In the preparation of a high-flexibility and high-toughness material, polyurethane acrylic resin, silicone acrylic resin and polyether acrylic resin are preferred.
The thiol-ene photosensitive resin preferably includes at least one acrylic oligomer in an amount of about 10 to about 60 parts by weight, more preferably about 20 to about 50 parts by weight, relative to the total weight of the composition.
The thiol-ene photocurable resin of the present invention includes at least one reactive diluent. Preferably, the reactive diluent is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, caprolactone acrylate, isodecyl acrylate, polyethylene glycol monoacrylate, 2-phenoxyethyl methacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, dicyclopentadiene (meth) acrylate, triethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, pentachlorophenyl (meth) acrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate, dipentaerythritol tetraacrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, in an amount of about 5 to 40 parts by weight, more preferably about 10 to 35 parts by weight, relative to the total weight of the composition.
The thiol-ene photocurable resin of the present invention contains an initiator including one or more of benzoin dimethyl ether (DMAP), 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6, -trimethylbenzoyl) phenylphosphine oxide 2, 4-diethylthioxanthone, benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1, and 4-benzoyl-4' -methyldiphenylsulfide. About 0.1 to 10 parts by weight, more preferably about 0.5 to 6 parts by weight, based on the total weight of the composition.
The thiol-ene photosensitive resin of the present invention includes at least one ultraviolet absorber. The curing depth of the 3D photosensitive resin can be adjusted through the using amount of the ultraviolet absorber, so that the precision of the resin curing material is adjusted. The ultraviolet absorbent comprises one or more of 2-hydroxy-4-n-neoxy benzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole and bis (2,2,6, 6-pentamethyl-4-piperidyl) sebacate. About 0.01 to about 1 part by weight, more preferably about 0.1 to about 0.5 part by weight, relative to the total weight of the composition.
The mercaptan-alkene light-cured resin comprises a filler, preferably comprises one or more of superfine calcium carbonate, superfine silicon dioxide, talcum powder and nano core-shell rubber. About 0.5 to 8 parts by weight, more preferably about 1 to 5 parts by weight, based on the total weight of the composition.
The auxiliary agent contained in the thiol-ene photocurable resin of the present invention preferably includes one or more of a coupling agent, a polymerization inhibitor, a leveling agent, a defoaming agent, a fluorescent brightener, a wetting dispersant or a pigment, and the coupling agent is preferably KH-560 or KH-570. The pigment comprises an inorganic pigment and an organic pigment, wherein the inorganic pigment is one of titanium white, lithopone, lead chrome yellow and iron blue; the organic pigment is one of red powder, azo yellow, phthalocyanine blue and quinacridone. The auxiliary agent is preferably 0.1 to 3 parts by weight, and more preferably 0.2 to 4 parts by weight.
The invention introduces a new polymerization mechanism in the 3D printing photosensitive resin: thiol-ene click chemistry has the advantages of high reaction speed, no oxygen inhibition and no solvent, and the crosslinking degree, hardness and flexibility of the material can be adjusted through different functionalities and substituent groups R.
Correspondingly, the invention also provides a preparation method of the thiol-ene photocuring resin for 3D printing, which comprises the following steps: and mixing the polythiol, the acrylate prepolymer, the reactive diluent, the initiator, the ultraviolet absorbent, the filler and the auxiliary agent, and stirring at 20-60 ℃ for 30-120 minutes to obtain the thiol-ene photocuring 3D printing material. Wherein the stirring temperature is preferably 30-50 ℃, and more preferably 30-40 ℃; the stirring time is preferably 40 to 100 minutes, and more preferably 50 to 90 minutes.
The thiol-ene photocuring resin for 3D printing introduces thiol-ene click chemistry into 3D photocuring printing, has simple, convenient and efficient thiol-ene click chemistry, produces no or harmless by-products in the reaction process, is easy to apply, can be rapidly carried out at room temperature, can accurately control the reaction by selecting an exposure area and time, is applied to the field of 3D photocuring printing, provides a novel 3D photocuring reaction mode, and can control the hardness, strength and toughness of materials by selecting and proportioning the types of polythiol and acrylate.
For further understanding of the present invention, the following embodiments are provided to illustrate the technical solutions of the present invention in detail, and the scope of the present invention is not limited by the following embodiments.
Detailed Description
The raw materials adopted in the embodiment of the invention are all commercially available.
Example 1
The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 13 percent of 1, 4-benzenedimethylmercaptan, 12 percent of pentaerythritol tetrakis (3-mercaptopropionate), 15 percent of epoxy acrylate, 21 percent of polyester acrylate, 20 percent of dicyclopentadiene (methyl) acrylate, 10 percent of hydroxyethyl acrylate, 3 percent of benzoin dimethyl ether, 5 percent of nano silicon dioxide, 0.1 percent of 2-hydroxy-4-methoxybenzophenone, 0.2 percent of defoaming agent, 0.3 percent of wetting dispersant, 0.2 percent of flatting agent and 0.2 percent of KH-560 coupling agent. Stirring temperature is 25 ℃, and stirring time is 90 min.
Example 2
The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 20% of mercapto silicone oil, 6% of tetra (3-mercaptobutanoic acid) pentaerythritol ester, 15% of polyether acrylic resin, 15% of polyurethane acrylic resin, 30% of 1, 6-hexanediol diacrylate, 5% of benzoin dimethyl ether, 8% of nano core-shell rubber, 0.1% of 2-hydroxy-4-methoxybenzophenone, 0.3% of defoaming agent, 0.3% of wetting dispersant and 0.3% of flatting agent. Stirring at 30 deg.C for 60 min.
Example 3
The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 10% of 4, 4' -thiobisthiophenol, 12.85% of 2,4, 6-trimercapto triazine, 20% of polyester acrylate, 15% of epoxy acrylate, 15% of dipentaerythritol tetraacrylate, 20% of 2-phenoxyethyl methacrylate, 4% of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2% of superfine calcium carbonate, 0.2% of 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 0.3% of defoaming agent, 0.3% of wetting dispersant, 0.3% of flatting agent and 0.05% of fluorescent whitening agent. Stirring temperature is 40 ℃, and stirring time is 90 min.
Example 4
The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 20% of pentaerythritol tetra (3-mercaptopropionate), 8% of polyurethane acrylate, 10% of epoxy acrylate, 20% of polyester acrylate, 15.7% of triethylene glycol diacrylate, 18% of dipentaerythritol tetraacrylate, 1% of 4-benzoyl-4' -methyl diphenyl sulfide, 3% of benzoin dimethyl ether, 3% of nano silicon dioxide, 0.2% of 2-hydroxy-4-methoxy benzophenone, 0.3% of defoaming agent, 0.3% of wetting dispersant, 0.3% of flatting agent and 0.2% of titanium white. Stirring at 30 deg.C for 100 min.
The following table 1 shows thiol-ene photocurable resins obtained by changing the component ratios according to the method of example 1:
Figure BDA0001413487490000091
the properties of the photocurable resins prepared in examples 1-9 of the present invention were measured, respectively, and the results are shown in table 2.
Table 2 results of measuring properties of thiol-ene 3D printing photocurable resins prepared in examples 1 to 9
Figure BDA0001413487490000101
From the test results given in the table above it can be seen that:
the product prepared from the thiol-ene photocuring resin obtained in the example 1 has the characteristics of high strength and high hardness.
The thiol-ene photocurable resin obtained in example 2 is characterized by high toughness, low viscosity, high flexibility, soft touch and high impact strength.
The product prepared from the thiol-ene photocuring resin obtained in the embodiment 3 has the characteristics of high hardness, high strength, excellent toughness and impact strength, and good comprehensive performance.
The thiol-ene photocurable resin obtained in example 4 can be used to prepare articles with high toughness, high impact, and excellent hardness and impact strength.
The thiol-ene photocurable resin obtained in example 5 has a higher resin viscosity due to a higher epoxy acrylate resin content. The articles prepared from the resin are characterized by high strength and high stiffness, have acceptable impact strength, but are inferior to examples 1-4.
The thiol-ene photocurable resin obtained in example 6 contains a higher proportion of reactive diluent, the viscosity of the resin is lower, but the higher proportion of monomer results in a great reduction in the strength of the material. Meanwhile, because the content of the ultraviolet absorbent is higher, the hardness of the product prepared by the resin is reduced.
The thiol-ene photocuring resin obtained in example 7 has a higher proportion of polythiol, and beyond the preferable range, the resin can be used for preparing products with higher crosslinking degree, and polymers contain more ester bond groups, and have high hardness and high strength, but lower toughness and impact strength.
The thiol-ene photocuring resin obtained in example 8 has a low polythiol proportion, is lower than the preferred range, and can be used for preparing products with low crosslinking degree and low material strength and hardness.
The thiol-ene photocurable resin obtained in example 9 has a high ratio of acrylic oligomer, and if the ratio is outside the preferable range, the viscosity of the resin is high, which is not favorable for printing and molding, and has a large influence on the accuracy of the cured resin.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (2)

1. The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 20% of mercapto silicone oil, 6% of tetra (3-mercaptobutanoic acid) pentaerythritol ester, 15% of polyether acrylic resin, 15% of polyurethane acrylic resin, 30% of 1, 6-hexanediol diacrylate, 5% of benzoin dimethyl ether, 8% of nano core-shell rubber, 0.1% of 2-hydroxy-4-methoxybenzophenone, 0.3% of defoaming agent, 0.3% of wetting dispersant and 0.3% of flatting agent.
2. A preparation method of thiol-ene photocuring resin for 3D printing is characterized by comprising the following steps:
mixing the polythiol, the acrylic resin prepolymer, the reactive diluent, the initiator, the ultraviolet absorber, the filler and the auxiliary agent in the mass ratio, and stirring at a high speed for 30-120 minutes at 20-50 ℃ to obtain the thiol-ene photocuring resin for 3D printing.
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