CN112480329A - Light-cured resin model material based on DLP (digital light processing) type 3D printing and preparation method thereof - Google Patents

Light-cured resin model material based on DLP (digital light processing) type 3D printing and preparation method thereof Download PDF

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CN112480329A
CN112480329A CN202011432253.8A CN202011432253A CN112480329A CN 112480329 A CN112480329 A CN 112480329A CN 202011432253 A CN202011432253 A CN 202011432253A CN 112480329 A CN112480329 A CN 112480329A
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printing
preparing
dlp
model material
graphene
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徐勇军
蔡卓弟
谭世芝
陈天熙
尹辉斌
杨宇
刘鉴
陈炎丰
肖永辉
谭学城
郭浩民
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Dongguan University of Technology
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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
    • C08F283/01—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
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

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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)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to the technical field of 3D printing jewelry casting, in particular to a DLP-based 3D printing photocureable resin model material, which comprises the following components: modified matrix resin: 40-65%; bifunctional reactive diluent: 30-50%; photoinitiator (2): 3 to 9 percent; auxiliary agent: 0.5 to 1 percent. The invention provides a DLP (digital light processing) type 3D printing-based photocureable resin model material which is low in material viscosity, good in shrinkage, high in printing precision, high in toughness and excellent in mechanical property; the invention also provides a preparation method of the DLP-based 3D printing photocureable resin model material, which has the advantages of simple preparation, mild reaction conditions and easily obtained raw materials, is a material widely used in the market, is favorable for industrialized production and manufacturing, and further reduces the production cost.

Description

Light-cured resin model material based on DLP (digital light processing) type 3D printing and preparation method thereof
Technical Field
The invention relates to the technical field of 3D printing jewelry casting, in particular to a DLP (digital light processing) -based 3D printing photocuring resin model material and a preparation method thereof.
Background
The 3D printing technology has the advantages of greatly shortening the product development period, improving the production efficiency and the like because parts in any shapes can be directly generated from computer graphic data without machining or dies, is called as an important part of the third industrial revolution, has the advantages of high forming speed and high precision in the DLP type photocuring printing technology, and is suitable for printing small-size precise casting components such as individuation and a small amount of jewelry.
But at present, the 3D printer and the light-cured resin raw material market are basically monopolized abroad, so that the manufacturing cost is high, while the domestic 3D printing light-cured resin model material for casting the jewelry model has poor forming effect, high viscosity, low printing precision and insufficient toughness, so that the subsequent processing technology for casting the jewelry model becomes more complicated.
Therefore, in view of the above problems, a 3D printing photocurable resin model material which has the same overall performance as that of the model material in foreign countries but is relatively cheaper is researched, and has a high market potential in China.
Disclosure of Invention
In order to solve the technical problems, the invention provides a DLP-based 3D printing photocuring resin model material which is low in material viscosity, good in shrinkage, high in printing precision, high in toughness and excellent in mechanical property.
The invention also provides a preparation method of the DLP-based 3D printing photocureable resin model material, which has the advantages of simple preparation, mild reaction conditions and easily obtained raw materials, is a material widely used in the market, is favorable for industrialized production and manufacturing, and further reduces the production cost.
The invention adopts the following technical scheme:
a model material of light-cured resin based on DLP type 3D printing comprises the following components: modified matrix resin: 40-65%; bifunctional reactive diluent: 30-50%; photoinitiator (2): 3 to 9 percent; auxiliary agent: 0.5 to 1 percent.
The technical proposal is further improved in that the difunctional reactive diluent is two or more of 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diethoxy diacrylate and polyethylene glycol (400) dimethacrylate.
In a further improvement of the above technical solution, the photoinitiator is a mixture of a cationic photoinitiator and a free radical photoinitiator, and the cationic photoinitiator is one or more of diphenyl iodonium hexafluorophosphate, 4 '-dimethyl diphenyl iodonium hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyl iodonium hexafluoro-ate, diphenyl- (4-phenylsulfide) phenyl sulfonium hexafluoro-ate, and η 6-isopropylbenzene cyclopentadienyl iron (II) hexafluorophosphate; the free radical photoinitiator is one or more of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, p-chlorobenzophenone, ethyl p-dimethylaminobenzoate and 2, 4-diethyl thiazolone.
The technical scheme is further improved in that the auxiliary agent comprises a polymerization inhibitor and an organic dye, wherein the polymerization inhibitor is one of diethylhydroxylamine, p-tert-butylcatechol, hydroquinone and p-hydroxyanisole; the organic dye is one of curcumin, eosin Y, gardenia blue and fluorescent whitening powder.
A preparation method of a DLP (digital light processing) -based 3D printing photocureable resin model material comprises the following steps:
preparing polyester acrylate: weighing a certain proportion of dibasic acid, dihydric alcohol and a catalyst in a four-opening beaker, stirring until the dibasic acid, the dihydric alcohol and the catalyst are completely dissolved, adding acrylic acid and a polymerization inhibitor, and continuously reacting for a period of time to obtain the polyester acrylate;
preparing graphene modified polyester acrylate: weighing a certain mass of graphene in a clean round-bottom flask, mixing the prepared polyester acrylate with the graphene, stirring for 15 minutes by using a high-speed dispersion machine under the condition of 6000r/min to ensure that the graphene is fully and uniformly mixed, and sealing for later use in a dark place;
preparing modified matrix resin: preparing modified matrix resin from the prepared graphene modified polyester acrylate and epoxy resin according to the proportion (1-2): 1;
preparing a light-cured resin model material: under the condition of room temperature, sequentially adding the modified matrix resin, the photoinitiator, the reactive diluent and the auxiliary agent into a round-bottom flask according to the mass ratio, stirring the mixture by using an electric stirrer until the mixture is uniformly mixed, pouring the mixture into a container for sealing, placing the container into an ultrasonic cleaning instrument for oscillation, taking out the mixture, standing and defoaming the mixture, and obtaining the photocuring resin model material.
The technical scheme is further improved in that in the step of preparing the polyester acrylate, the dibasic acid is one of isophthalic acid, adipic acid, azelaic acid, sebacic acid and phthalic anhydride; the dihydric alcohol is one of ethylene glycol, propylene glycol, 1, 4-butanediol and 1, 2-butanediol; the polymerization inhibitor is any one of diethylhydroxylamine, p-tert-butylcatechol, hydroquinone and p-hydroxyanisole; the catalyst is p-toluenesulfonic acid.
The technical scheme is further improved in that in the step of preparing the polyester acrylate, the specific steps of the preparation are as follows:
weighing a certain proportion of dibasic acid, dihydric alcohol and p-toluenesulfonic acid in a four-opening beaker, heating under the condition of nitrogen, and stirring until the dibasic acid, the dihydric alcohol and the p-toluenesulfonic acid are completely dissolved; heating to 130 ℃, refluxing for 2 hours, and separating water;
cooling to 100 ℃, adding p-tert-butyl catechol and acrylic acid, continuously heating to 150 ℃, refluxing for 1.5 hours, dividing water, cooling and discharging after no water is distilled out, thus obtaining the polyester acrylate.
The technical proposal is further improved in that in the step of preparing the graphene modified polyester acrylate, the specific surface area of the graphene is 180-280m2(iv) at least 50% of the graphene has a particle size of less than 10 μm.
In the step of preparing the modified matrix resin, the epoxy resin is one or two of alicyclic epoxy resin 2021P and bisphenol a epoxy resin E55.
In the step of preparing the light-cured resin model material, the stirring time of the electric stirrer is about 1.5 hours, and the oscillation time in the ultrasonic cleaning instrument is about 1.5 hours.
The invention has the beneficial effects that:
the graphene is a two-dimensional flaky inorganic nano material and has an ideal two-dimensional crystal structure, and the structure of the C-C bond enables the graphene to have a plurality of excellent properties, such as excellent mechanical properties, excellent heat conductivity and the like; the polyester acrylate has the advantages of low price, low odor, low irritation, low viscosity and good flexibility; after the graphene is modified, the viscosity of the matrix resin is further reduced, the graphene dispersed in the matrix resin also strengthens the tensile strength of the matrix resin, improves the toughness of the resin, increases the fastest decomposition temperature of the resin, reduces the maximum decomposition rate, and improves the thermal stability of the resin, so that the mechanical properties such as the thermal stability, the toughness and the like of the light-cured resin model material are improved, and the viscosity of the light-cured resin model material is reduced.
Ultraviolet curing can be divided into two categories of free radical type and cationic type according to the curing mechanism, and the free radical curing has the advantages of high curing speed, large volume shrinkage and poor forming precision. The invention has the advantages of small shrinkage of cation photocuring volume, long service life of active intermediate, post-curing and the like, but the curing speed is low, the absorption spectrum of a cation photoinitiator is not matched with a UV curing light source, and in order to exert the respective advantages of a free radical and a cation photocuring system and make up the defects, the invention adopts a hybrid polymer system to generate good synergistic effect, the hybrid curing system has various optional monomers and prepolymers, the viscosity and the performance of a cured product can be better adjusted through different proportions of the monomers and the prepolymers, and compared with a single curing system, the photocuring time and the shrinkage rate of a photocuring resin model material can be reduced.
Meanwhile, the preparation method is simple, the reaction condition is mild, the raw materials are easily available, and the raw materials are widely used materials in the market, so that the industrial production and manufacturing are facilitated, and the production cost is further reduced.
Detailed Description
The invention will be further described with reference to preferred embodiments.
Example 1:
the preparation process of the graphene polyester acrylate comprises the following steps: in a four-necked flask equipped with an electric jacket, an electric stirrer, and a reflux condenser, 50 parts of a dibasic acid, 40 parts of a dihydric alcohol, and 1 part of p-toluenesulfonic acid were weighed, heated under nitrogen, and stirred until completely dissolved. Heating to 130 ℃ for refluxing for 2 hours, dividing water, cooling to 100 ℃, adding 1 part of p-tert-butylcatechol and 8 parts of acrylic acid, continuously heating to 150 ℃ for refluxing for 1.5 hours, dividing water, cooling and discharging when no water is distilled out to obtain the polyester acrylate, weighing 2 per mill of graphene in a clean round-bottom flask, mixing the prepared polyester acrylate with the graphene, stirring for 15 minutes by using a high-speed dispersion machine under the condition of 6000r/min to fully mix the obtained mixture uniformly, and sealing the obtained mixture in a dark place for later use.
In this example, 40 parts of graphene-modified polyester acrylate, 25 parts of bisphenol a epoxy resin E55, 20 parts of 1, 4-butanediol diglycidyl ether, 11.5 parts of tripropylene glycol diacrylate, 2 parts of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 1 part of diphenyl iodonium hexafluorophosphate, 0.45 part of p-tert-butyl catechol, and 0.05 part of gardenia blue organic dye are weighed by mass percentage for use. Under the condition of room temperature, adding the modified matrix resin, the photoinitiator, the reactive diluent and the auxiliary agent into a round-bottom flask in sequence according to the mass ratio, stirring for 1.5 hours by using an electric stirrer until the materials are uniformly mixed, pouring the materials into a container for sealing, then placing the container into an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out the materials, and standing and defoaming the materials to obtain the photocuring resin model material.
Example 2:
the preparation process of the graphene polyester acrylate comprises the following steps: in a four-necked flask equipped with an electric jacket, an electric stirrer, and a reflux condenser, 45 parts of a dibasic acid, 40 parts of a dihydric alcohol, and 0.8 part of p-toluenesulfonic acid were weighed, heated under nitrogen, and stirred until completely dissolved. Heating to 130 ℃ for refluxing for 2 hours, dividing water, cooling to 100 ℃, adding 0.7 part of p-tert-butylcatechol and 13.5 parts of acrylic acid, continuing heating to 150 ℃ for refluxing for 1.5 hours, dividing water, cooling and discharging after anhydrous distillation to obtain the polyester acrylate, weighing 3 per mill of graphene in a clean round-bottom flask, mixing the prepared polyester acrylate with the graphene, stirring for 15 minutes by a high-speed dispersion machine under the condition of 6000r/min to ensure that the graphene is fully and uniformly mixed, and sealing in the dark for later use.
In this example, 30 parts of graphene-modified polyester acrylate, 25 parts of cycloaliphatic epoxy resin 2021P, 21 parts of 1, 4-butanediol diglycidyl ether, 17 parts of polyethylene glycol (400) dimethacrylate, 4 parts of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2.4 parts of diphenyliodonium hexafluorophosphate, 0.55 part of hydroquinone, and 0.05 part of eosin Y organic dye were weighed out in percentage by mass for use. Under the condition of room temperature, adding the modified matrix resin, the photoinitiator, the reactive diluent and the auxiliary agent into a round-bottom flask in sequence according to the mass ratio, stirring for 1.5 hours by using an electric stirrer until the materials are uniformly mixed, pouring the materials into a container for sealing, then placing the container into an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out the materials, and standing and defoaming the materials to obtain the photocuring resin model material.
Example 3:
the preparation process of the graphene polyester acrylate comprises the following steps: in a four-necked flask equipped with an electric jacket, an electric stirrer, and a reflux condenser, 48 parts of a dibasic acid, 37 parts of a dihydric alcohol, and 0.5 part of p-toluenesulfonic acid were weighed, heated under nitrogen, and stirred until completely dissolved. Heating to 130 ℃ for refluxing for 2 hours, dividing water, cooling to 100 ℃, adding 0.5 part of p-tert-butylcatechol and 14 parts of acrylic acid, continuously heating to 150 ℃ for refluxing for 1.5 hours, dividing water, cooling and discharging when no water is distilled out to obtain the polyester acrylate, weighing 4 per thousand of graphene in a clean round-bottom flask, mixing the prepared polyester acrylate with the graphene, stirring for 15 minutes by using a high-speed dispersion machine under the condition of 6000r/min to ensure that the graphene is fully and uniformly mixed, and sealing in the dark for later use.
In the preparation of the photo-curing resin model material described in this embodiment, 30 parts of graphene-modified polyester acrylate, 20 parts of bisphenol a epoxy resin E55, 25 parts of polypropylene glycol diglycidyl ether, 17.2 parts of tripropylene glycol diacrylate, 4.5 parts of ethyl p-dimethylaminobenzoate, 2.5 parts of diphenyl iodonium hexafluorophosphate, 0.75 part of p-tert-butyl catechol, and 0.05 part of curcumin organic dye are weighed by mass percentage for use. Under the condition of room temperature, adding the modified matrix resin, the photoinitiator, the reactive diluent and the auxiliary agent into a round-bottom flask in sequence according to the mass ratio, stirring for 1.5 hours by using an electric stirrer until the materials are uniformly mixed, pouring the materials into a container for sealing, then placing the container into an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out the materials, and standing and defoaming the materials to obtain the photocuring resin model material.
Example 4:
the preparation process of the graphene polyester acrylate comprises the following steps: in a four-necked flask equipped with an electric jacket, an electric stirrer, and a reflux condenser, 48 parts of a dibasic acid, 42 parts of a diol, and 0.6 part of p-toluenesulfonic acid were weighed, heated under nitrogen, and stirred until completely dissolved. Heating to 130 ℃ for refluxing for 2 hours, dividing water, cooling to 100 ℃, adding 0.4 part of p-tert-butylcatechol and 9 parts of acrylic acid, continuously heating to 150 ℃ for refluxing for 1.5 hours, dividing water, cooling and discharging when no water is distilled out to obtain the polyester acrylate, weighing 3 per thousand of graphene in a clean round-bottom flask, mixing the prepared polyester acrylate with the graphene, stirring for 15 minutes by using a high-speed dispersion machine under the condition of 6000r/min to ensure that the graphene is fully and uniformly mixed, and sealing in the dark for later use.
In this example, 20 parts of graphene-modified polyester acrylate, 20 parts of alicyclic epoxy resin 2021P, 25 parts of polypropylene glycol diglycidyl ether, 25 parts of polyethylene glycol (400) dimethacrylate, 5.5 parts of ethyl P-dimethylaminobenzoate, 3.5 parts of 4,4' -dimethyldiphenyliodonium salt hexafluorophosphate, 0.95 part of hydroquinone, and 0.05 part of fluorescent whitening organic dye are weighed by mass percentage for use. Under the condition of room temperature, adding the modified matrix resin, the photoinitiator, the reactive diluent and the auxiliary agent into a round-bottom flask in sequence according to the mass ratio, stirring for 1.5 hours by using an electric stirrer until the materials are uniformly mixed, pouring the materials into a container for sealing, then placing the container into an ultrasonic cleaning instrument for shaking for 1.5 hours, taking out the materials, and standing and defoaming the materials to obtain the photocuring resin model material.
The results of the performance tests of the photo-curable resin molding materials prepared in examples 1 to 4 above are shown in the following table:
Figure BDA0002826897150000071
the above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The model material is characterized by comprising the following components in parts by weight: modified matrix resin: 40-65%; bifunctional reactive diluent: 30-50%; photoinitiator (2): 3 to 9 percent; auxiliary agent: 0.5 to 1 percent.
2. The DLP based 3D printing photocurable resin modeling material of claim 1, wherein the difunctional reactive diluent is two or more of 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diethoxy diacrylate, polyethylene glycol (400) dimethacrylate.
3. The DLP-based 3D printing photocurable resin modeling material of claim 1, wherein the photoinitiator is a cationic photoinitiator intermixed with a free-radical photoinitiator, the cationic photoinitiator being one or more of diphenyliodonium hexafluorophosphate, 4 '-dimethyldiphenyliodonium hexafluorophosphate, 4-isobutylphenyl-4' -methylphenyliodohexafluoro-nate, diphenyl- (4-phenylsulfide) phenylsulfonium hexafluoro-ate, η 6-cumeneferrocenium (II) hexafluorophosphate; the free radical photoinitiator is one or more of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, p-chlorobenzophenone, ethyl p-dimethylaminobenzoate and 2, 4-diethyl thiazolone.
4. The DLP-based 3D printing photocurable resin model material as claimed in claim 1, wherein the auxiliary agent comprises a polymerization inhibitor and an organic dye, wherein the polymerization inhibitor is one of diethylhydroxylamine, p-tert-butylcatechol, hydroquinone and p-hydroxyanisole; the organic dye is one of curcumin, eosin Y, gardenia blue and fluorescent whitening powder.
5. A preparation method of a DLP (digital light processing) -based 3D printing photocureable resin model material is characterized by comprising the following steps:
preparing polyester acrylate: weighing a certain proportion of dibasic acid, dihydric alcohol and a catalyst in a four-opening beaker, stirring until the dibasic acid, the dihydric alcohol and the catalyst are completely dissolved, adding acrylic acid and a polymerization inhibitor, and continuously reacting for a period of time to obtain the polyester acrylate;
preparing graphene modified polyester acrylate: weighing a certain mass of graphene in a clean round-bottom flask, mixing the prepared polyester acrylate with the graphene, stirring for 15 minutes by using a high-speed dispersion machine under the condition of 6000r/min to ensure that the graphene is fully and uniformly mixed, and sealing for later use in a dark place;
preparing modified matrix resin: preparing modified matrix resin from the prepared graphene modified polyester acrylate and epoxy resin according to the proportion (1-2): 1;
preparing a light-cured resin model material: under the condition of room temperature, sequentially adding the modified matrix resin, the photoinitiator, the reactive diluent and the auxiliary agent into a round-bottom flask according to the mass ratio, stirring the mixture by using an electric stirrer until the mixture is uniformly mixed, pouring the mixture into a container for sealing, placing the container into an ultrasonic cleaning instrument for oscillation, taking out the mixture, standing and defoaming the mixture, and obtaining the photocuring resin model material.
6. The method for preparing the DLP type 3D printing light-cured resin model material according to claim 5, wherein in the step of preparing the polyester acrylate, the dibasic acid is one of isophthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride; the dihydric alcohol is one of ethylene glycol, propylene glycol, 1, 4-butanediol and 1, 2-butanediol; the polymerization inhibitor is any one of diethylhydroxylamine, p-tert-butylcatechol, hydroquinone and p-hydroxyanisole; the catalyst is p-toluenesulfonic acid.
7. The preparation method of the DLP type 3D printing based light-cured resin model material according to claim 6, wherein in the step of preparing the polyester acrylate, the specific steps of preparation are as follows:
weighing a certain proportion of dibasic acid, dihydric alcohol and p-toluenesulfonic acid in a four-opening beaker, heating under the condition of nitrogen, and stirring until the dibasic acid, the dihydric alcohol and the p-toluenesulfonic acid are completely dissolved; heating to 130 ℃, refluxing for 2 hours, and separating water;
cooling to 100 ℃, adding p-tert-butyl catechol and acrylic acid, continuously heating to 150 ℃, refluxing for 1.5 hours, dividing water, cooling and discharging after no water is distilled out, thus obtaining the polyester acrylate.
8. The method for preparing the DLP type 3D printing-based light-cured resin model material as claimed in claim 5, wherein in the step of preparing the graphene-modified polyester acrylate, the specific surface area of the graphene is 180-280m2(iv) at least 50% of the graphene has a particle size of less than 10 μm.
9. The method for preparing DLP type 3D printing based photocurable resin model material according to claim 5, wherein in the step of preparing modified matrix resin, the epoxy resin is one or two of alicyclic epoxy resin 2021P and bisphenol A type epoxy resin E55.
10. The method for preparing the light-curable resin mold material based on the DLP type 3D printing according to claim 5, wherein in the step of preparing the light-curable resin mold material, the electric stirrer stirs for about 1.5 hours, and the ultrasonic cleaning device shakes for about 1.5 hours.
CN202011432253.8A 2020-12-09 2020-12-09 Light-cured resin model material based on DLP (digital light processing) type 3D printing and preparation method thereof Pending CN112480329A (en)

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CN115612040A (en) * 2022-09-23 2023-01-17 共享新材料(山东)有限公司 Photosensitive resin and preparation method thereof
CN115894773A (en) * 2022-12-07 2023-04-04 郑州德派医疗器械有限公司 Light-cured 3D printing resin for dentistry and preparation method thereof

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Application publication date: 20210312