CN113698544A - High-temperature-resistance 3D (three-dimensional) molding composite material and preparation method thereof - Google Patents

High-temperature-resistance 3D (three-dimensional) molding composite material and preparation method thereof Download PDF

Info

Publication number
CN113698544A
CN113698544A CN202111201816.7A CN202111201816A CN113698544A CN 113698544 A CN113698544 A CN 113698544A CN 202111201816 A CN202111201816 A CN 202111201816A CN 113698544 A CN113698544 A CN 113698544A
Authority
CN
China
Prior art keywords
parts
acrylate
composite material
epoxy acrylate
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111201816.7A
Other languages
Chinese (zh)
Inventor
周双留
陈磊
徐炜
高凡琛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Rich Opto Technology Co ltd
Original Assignee
Jiangsu Rich Opto Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Rich Opto Technology Co ltd filed Critical Jiangsu Rich Opto Technology Co ltd
Priority to CN202111201816.7A priority Critical patent/CN113698544A/en
Publication of CN113698544A publication Critical patent/CN113698544A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—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
    • 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
    • C08F2/46—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
    • C08F283/10—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
    • C08F283/105—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 on to unsaturated 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention relates to the technical field of 3D forming additive manufacturing, and discloses a high-temperature-resistant 3D forming composite material which comprises the following raw materials in parts by weight: 30-50 parts of polyurethane acrylate, 10-30 parts of epoxy acrylate, 10-30 parts of hyperbranched acrylate, 30-50 parts of functional reactive diluent monomer, 1-5 parts of photoinitiator, 0-1 part of ultraviolet absorber, 0-1 part of pigment and 1-10 parts of filler, wherein the polyurethane acrylate is 30-40 parts of aliphatic polyurethane acrylate, and the epoxy acrylate is phenolic epoxy acrylate. The high-temperature-resistant composite material based on the 3D forming technology is prepared by pre-dividing polyurethane acrylate with high crosslinking density, epoxy acrylate and hyperbranched acrylate prepolymer and a high-glass-transition-temperature diluent monomer into liquid and powder according to a certain proportion, and mixing the liquid and the solid-phase nano powder into a multi-phase mixed system in a high-speed dispersion mode, wherein the temperature-resistant HDT of the material can reach 180 ℃, and the 3D forming precision is improved.

Description

High-temperature-resistance 3D (three-dimensional) molding composite material and preparation method thereof
Technical Field
The invention relates to the technical field of 3D forming additive manufacturing, in particular to a high-temperature-resistant 3D forming composite material and a preparation method thereof.
Background
The 3D molding is also known in academia as additive manufacturing, wherein the photocuring molding is a process of curing under the action of a light source (ultraviolet light and laser), belongs to chemical curing, and is a result of photoinitiated chemical reaction, the photocuring material is based on single-phase photosensitive resin, the polymerization and crosslinking processes of the cured material are performed through unsaturated double bonds, and HDT is hardly higher than 120 ℃ in temperature resistance.
The composite material is a mixture and can be mainly divided into two categories of structural composite materials and functional composite materials, wherein the hybrid composite material is formed by mixing two or more than two reinforcing phase materials in a matrix phase material, compared with a common single reinforcing phase composite material, the impact strength, the strength toughness, the temperature resistance and the like of the composite material are obviously improved, and in order to improve the high temperature resistance of the composite material prepared by a 3D forming technology, the application aims to provide the high temperature resistance 3D forming composite material and the preparation method thereof.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-temperature-resistant 3D forming composite material and a preparation method thereof, which have the advantage of high temperature resistance and solve the problems that the polymerization and crosslinking processes of the traditional cured material are carried out through unsaturated double bonds, and HDT is hardly higher than 120 ℃ in temperature resistance.
(II) technical scheme
In order to realize the purpose of high temperature resistance, the invention provides the following technical scheme: a high-temperature-resistant 3D molding composite material comprises the following raw materials in parts by weight: 30-50 parts of polyurethane acrylate, 10-30 parts of epoxy acrylate, 10-30 parts of hyperbranched acrylate, 30-50 parts of functional reactive diluent monomer, 1-5 parts of photoinitiator, 0-1 part of ultraviolet absorbent, 0-1 part of pigment and 1-10 parts of filler.
Preferably, the urethane acrylate is one or more of aliphatic urethane acrylate and aromatic urethane acrylate, the epoxy acrylate is one or more of bisphenol A epoxy acrylate, novolac epoxy acrylate and modified epoxy acrylate, the functional reactive diluent monomer is one or more of ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane triacrylate, cyclotrimethylolpropane formal acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, acryloylmorpholine and tris (2-hydroxyethyl) isocyanurate triacrylate, and the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 2, 6 (trimethylbenzoyl) diphenylphosphine oxide, The ultraviolet absorber is one or more of 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol) and 2-hydroxy-4-n-octoxybenzophenone, the pigment is one or more of titanium dioxide and iron oxide black, the filler is one or more of nano silicon micropowder, nano aluminum trioxide powder and nano zirconium dioxide powder, and the hyperbranched acrylic ester is thioether polyester acrylate.
Preferably, the urethane acrylate is aliphatic urethane acrylate, and the epoxy acrylate is novolac epoxy acrylate.
Preferably, the functional reactive diluent monomer comprises 10-20 parts of acryloyl morpholine and 20-30 parts of tris (2-hydroxyethyl) isocyanurate triacrylate.
Preferably, the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide.
Preferably, the ultraviolet absorber is 2, 2' -methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol).
Preferably, the pigment is titanium dioxide.
Preferably, the filler is nano silicon micropowder or nano zirconium dioxide powder.
The invention provides a preparation method of a high-temperature-resistant 3D molding composite material, which comprises the following steps:
s1, weighing polyurethane acrylate, epoxy acrylate, hyperbranched acrylate, a functional reactive diluent monomer, a photoinitiator and an ultraviolet absorbent in proportion, and stirring and pre-dispersing on an independent suspension stirrer at 400 rpm/min;
s2, heating the pre-dispersion prepared in the step to 60-65 ℃ in a water bath, keeping the temperature constant, adding the pigment and the nano powder filler into the pre-dispersion in batches according to a proportion under the high-speed dispersion state of 3000 plus 5000rpm/min, and stirring and dispersing at a high speed for 30-60min to prepare the high-temperature-resistant 3D forming composite material.
(III) advantageous effects
Compared with the prior art, the invention provides a high-temperature-resistant 3D molding composite material and a preparation method thereof, and the high-temperature-resistant 3D molding composite material has the following beneficial effects:
the high-temperature-resistant 3D forming composite material and the preparation method thereof are characterized in that a prepolymer of polyurethane acrylate, epoxy acrylate and hyperbranched acrylate with high crosslinking density and a high-glass transition temperature diluent monomer are pre-divided into liquid and powder according to a certain proportion, and then the liquid and the solid-phase nano powder are mixed into a multi-phase mixed system in a high-speed dispersion mode to prepare the high-temperature-resistant composite material based on the 3D forming technology, wherein the temperature-resistant HDT of the material can reach 180 ℃, and the 3D forming precision is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows: a high-temperature-resistant 3D molding composite material comprises the following raw materials in parts by weight: 30 parts of polyurethane acrylate, 10 parts of epoxy acrylate, 10 parts of hyperbranched acrylate, 50 parts of functional reactive diluent monomer, 5 parts of photoinitiator, 1 part of ultraviolet absorbent, 1 part of pigment and 5 parts of filler.
Wherein, the urethane acrylate is one or a mixture of aliphatic urethane acrylate and aromatic urethane acrylate, the epoxy acrylate is one or a mixture of bisphenol A epoxy acrylate, novolac epoxy acrylate and modified epoxy acrylate, the functional active diluent monomer is one or a mixture of ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane triacrylate, cyclotrimethylolpropane formal acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, acryloylmorpholine and tris (2-hydroxyethyl) isocyanurate triacrylate, and the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, bis 2,4,6 (trimethylbenzoyl) phenylphosphine oxide, bis (2, 4,6 (trimethylbenzoyl) phenylphosphine oxide, poly (p-phenylene oxide), poly (p-phenylene oxide, p-p, p-p, p-p, p-p, p-p, p-p, p-p, p-p, p, One or more compositions of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-phenyl acetone-1, the ultraviolet absorbent is one of 2, 2' -methylene bis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethyl butyl) phenol) and 2-hydroxy-4-n-octoxy benzophenone, the pigment is one or more compositions of titanium dioxide and iron oxide black, the filler is one or more compositions of nano silica micropowder, nano alumina powder and nano zirconium dioxide powder, and the hyperbranched acrylic ester is thioether hyperbranched polyester acrylate.
Specifically, the ultraviolet absorbent is 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol), the pigment is titanium dioxide, and the filler is nano glass fiber powder.
A preparation method of a high temperature-resistant 3D molding composite material comprises the following steps:
s1, weighing 30 parts of aliphatic polyurethane acrylate, 10 parts of novolac epoxy acrylate, 10 parts of thioether hyperbranched acrylate, 20 parts of functional active diluent monomer acryloyl, 30 parts of aliphatic polyurethane acrylate, 5 parts of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, and 1 part of ultraviolet absorbent 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol according to a proportion, and stirring and pre-dispersing on an independent suspension stirrer at 400 rpm/min;
s2, heating the pre-dispersion prepared in the step to 60-65 ℃ in a water bath, keeping the temperature constant, adding 1 part of pigment titanium dioxide and 5 parts of filler nano glass fiber powder into the pre-dispersion in batches according to a proportion under the high-speed dispersion state of 3000 plus 5000rpm/min, stirring at a high speed for dispersion for 30-60min to prepare the high-temperature-resistant 3D forming composite material, and then printing and forming on an LCD type 3D printer.
Example two: a high-temperature-resistant 3D molding composite material comprises the following raw materials in parts by weight: 30 parts of polyurethane acrylate, 10 parts of epoxy acrylate, 10 parts of hyperbranched acrylate, 50 parts of functional reactive diluent monomer, 5 parts of photoinitiator, 1 part of ultraviolet absorbent, 1 part of pigment and 5 parts of filler.
Wherein, the urethane acrylate is one or a mixture of aliphatic urethane acrylate and aromatic urethane acrylate, the epoxy acrylate is one or a mixture of bisphenol A epoxy acrylate, novolac epoxy acrylate and modified epoxy acrylate, the functional active diluent monomer is one or a mixture of ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane triacrylate, cyclotrimethylolpropane formal acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, acryloylmorpholine and tris (2-hydroxyethyl) isocyanurate triacrylate, and the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, bis 2,4,6 (trimethylbenzoyl) phenylphosphine oxide, bis (2, 4,6 (trimethylbenzoyl) phenylphosphine oxide, poly (p-phenylene oxide), poly (p-phenylene oxide, p-p, p-p, p-p, p-p, p-p, p-p, p-p, p-p, p, One or more compositions of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-phenyl acetone-1, the ultraviolet absorbent is one of 2, 2' -methylene bis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethyl butyl) phenol) and 2-hydroxy-4-n-octoxy benzophenone, the pigment is one or more compositions of titanium dioxide and iron oxide black, the filler is one or more compositions of nano silica micropowder, nano alumina powder and nano zirconium dioxide powder, and the hyperbranched acrylic ester is thioether hyperbranched polyester acrylate.
Specifically, the ultraviolet absorbent is 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol), the pigment is titanium dioxide, and the filler is nano aluminum oxide powder.
A preparation method of a high temperature-resistant 3D molding composite material comprises the following steps:
s1, weighing 30 parts of aliphatic polyurethane acrylate, 10 parts of novolac epoxy acrylate, 10 parts of thioether hyperbranched acrylate, 20 parts of functional active diluent monomer acryloyl, 30 parts of aliphatic polyurethane acrylate, 5 parts of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, and 1 part of ultraviolet absorbent 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol according to a proportion, and stirring and pre-dispersing on an independent suspension stirrer at 400 rpm/min;
s2, heating the pre-dispersion prepared in the step to 60-65 ℃ in a water bath, keeping the temperature constant, adding 1 part of pigment titanium dioxide and 5 parts of filler nano-alumina powder into the pre-dispersion in batches according to a proportion under the high-speed dispersion state of 3000 plus 5000rpm/min, stirring at a high speed for dispersion for 30-60min to prepare the high-temperature-resistant 3D forming composite material, and then printing and forming on an LCD type 3D printer.
Example three: a high-temperature-resistant 3D molding composite material comprises the following raw materials in parts by weight: 30 parts of polyurethane acrylate, 10 parts of epoxy acrylate, 10 parts of hyperbranched acrylate, 50 parts of functional reactive diluent monomer, 5 parts of photoinitiator, 1 part of ultraviolet absorbent, 1 part of pigment and 5 parts of filler.
Wherein, the urethane acrylate is one or a mixture of aliphatic urethane acrylate and aromatic urethane acrylate, the epoxy acrylate is one or a mixture of bisphenol A epoxy acrylate, novolac epoxy acrylate and modified epoxy acrylate, the functional active diluent monomer is one or a mixture of ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane triacrylate, cyclotrimethylolpropane formal acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, acryloylmorpholine and tris (2-hydroxyethyl) isocyanurate triacrylate, and the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, bis 2,4,6 (trimethylbenzoyl) phenylphosphine oxide, bis (2, 4,6 (trimethylbenzoyl) phenylphosphine oxide, poly (p-phenylene oxide), poly (p-phenylene oxide, p-p, p-p, p-p, p-p, p-p, p-p, p-p, p-p, p, One or more compositions of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-phenyl acetone-1, the ultraviolet absorbent is one of 2, 2' -methylene bis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethyl butyl) phenol) and 2-hydroxy-4-n-octoxy benzophenone, the pigment is one or more compositions of titanium dioxide and iron oxide black, the filler is one or more compositions of nano silica micropowder, nano alumina powder and nano zirconium dioxide powder, and the hyperbranched acrylic ester is thioether hyperbranched polyester acrylate.
Specifically, the ultraviolet absorbent is 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol), the pigment is titanium dioxide, and the filler is nano zirconium dioxide powder.
A preparation method of a high temperature-resistant 3D molding composite material comprises the following steps:
s1, weighing 30 parts of aliphatic polyurethane acrylate, 10 parts of novolac epoxy acrylate, 10 parts of thioether hyperbranched acrylate, 20 parts of functional active diluent monomer acryloyl, 30 parts of aliphatic polyurethane acrylate, 5 parts of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, and 1 part of ultraviolet absorbent 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol according to a proportion, and stirring and pre-dispersing on an independent suspension stirrer at 400 rpm/min;
s2, heating the pre-dispersion prepared in the step to 60-65 ℃ in a water bath, keeping the temperature constant, adding 1 part of pigment titanium dioxide and 5 parts of filler nano zirconium dioxide powder into the pre-dispersion in batches according to a proportion under the high-speed dispersion state of 3000 plus 5000rpm/min, stirring and dispersing at a high speed for 30-60min to prepare the high-temperature-resistant 3D forming composite material, and then printing and forming on an LCD type 3D printer.
Example four: a high-temperature-resistant 3D molding composite material comprises the following raw materials in parts by weight: 30 parts of polyurethane acrylate, 10 parts of epoxy acrylate, 10 parts of hyperbranched acrylate, 50 parts of functional reactive diluent monomer, 5 parts of photoinitiator, 1 part of ultraviolet absorbent, 1 part of pigment and 10 parts of filler.
Wherein, the urethane acrylate is one or a mixture of aliphatic urethane acrylate and aromatic urethane acrylate, the epoxy acrylate is one or a mixture of bisphenol A epoxy acrylate, novolac epoxy acrylate and modified epoxy acrylate, the functional active diluent monomer is one or a mixture of ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane triacrylate, cyclotrimethylolpropane formal acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, acryloylmorpholine and tris (2-hydroxyethyl) isocyanurate triacrylate, and the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, bis 2,4,6 (trimethylbenzoyl) phenylphosphine oxide, bis (2, 4,6 (trimethylbenzoyl) phenylphosphine oxide, poly (p-phenylene oxide), poly (p-phenylene oxide, p-p, p-p, p-p, p-p, p-p, p-p, p-p, p-p, p, One or more compositions of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-phenyl acetone-1, the ultraviolet absorbent is one of 2, 2' -methylene bis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethyl butyl) phenol) and 2-hydroxy-4-n-octoxy benzophenone, the pigment is one or more compositions of titanium dioxide and iron oxide black, the filler is one or more compositions of nano silica micropowder, nano alumina powder and nano zirconium dioxide powder, and the hyperbranched acrylic ester is thioether hyperbranched polyester acrylate.
Specifically, the ultraviolet absorbent is 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol), the pigment is titanium dioxide, and the filler is nano silica micropowder.
A preparation method of a high temperature-resistant 3D molding composite material comprises the following steps:
s1, weighing 30 parts of aliphatic polyurethane acrylate, 10 parts of novolac epoxy acrylate, 10 parts of thioether hyperbranched acrylate, 20 parts of functional active diluent monomer acryloyl, 30 parts of aliphatic polyurethane acrylate, 5 parts of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, and 1 part of ultraviolet absorbent 2, 2' -methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol according to a proportion, and stirring and pre-dispersing on an independent suspension stirrer at 400 rpm/min;
s2, heating the pre-dispersion prepared in the step to 60-65 ℃ in a water bath, keeping the temperature constant, adding 1 part of pigment titanium dioxide and 5 parts of filler nano-silica powder into the pre-dispersion in batches according to a proportion under the high-speed dispersion state of 3000 plus 5000rpm/min, stirring and dispersing at a high speed for 30-60min to prepare the high-temperature-resistant 3D forming composite material, and then printing and forming on an LCD type 3D printer.
And (4) judging the standard: examples 1-4 heat deflection temperature under load test data vs. the following table:
Figure BDA0003305177120000081
among them, the temperature resistance HDT of example 4 can reach 180 ℃, and the temperature resistance is higher than that of examples 1-3, so that example 4 is the most preferable example.
The invention has the beneficial effects that: the high-temperature-resistant composite material based on the 3D forming technology is prepared by pre-dividing polyurethane acrylate with high crosslinking density, epoxy acrylate and hyperbranched acrylate prepolymer and a high-glass-transition-temperature diluent monomer into liquid and powder according to a certain proportion, and mixing the liquid and the solid-phase nano powder into a multi-phase mixed system in a high-speed dispersion mode, wherein the temperature-resistant HDT of the material can reach 180 ℃, and the 3D forming precision is improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. The high-temperature-resistance 3D molding composite material is characterized by comprising the following raw materials in parts by weight: 30-50 parts of polyurethane acrylate, 10-30 parts of epoxy acrylate, 10-30 parts of hyperbranched acrylate, 30-50 parts of functional reactive diluent monomer, 1-5 parts of photoinitiator, 0-1 part of ultraviolet absorbent, 0-1 part of pigment and 1-10 parts of filler.
2. The high temperature resistant 3D molding composite material as claimed in claim 1, wherein the urethane acrylate is one or more mixture of aliphatic urethane acrylate and aromatic urethane acrylate, the epoxy acrylate is one or more mixture of bisphenol A epoxy acrylate, novolac epoxy acrylate and modified epoxy acrylate, the functional reactive diluent monomer is one or more combination of ethoxylated bisphenol A diacrylate, ethoxylated trimethylolpropane triacrylate, cyclotrimethylolpropane formal acrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, acryloyl morpholine and tris (2-hydroxyethyl) isocyanurate triacrylate, the photoinitiator is one or a plurality of compositions of 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, bis 2,4,6 (trimethylbenzoyl) phenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-phenyl acetone-1, the ultraviolet absorbent is one or a plurality of compositions of 2, 2' -methylene bis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethyl butyl) phenol) and 2-hydroxy-4-n-octoxy benzophenone, the pigment is one or a plurality of compositions of titanium dioxide and iron oxide black, the filler is one or a plurality of compositions of nano silicon micropowder, nano aluminum trioxide powder and nano zirconium dioxide powder, the hyperbranched acrylic ester is thioether hyperbranched polyester acrylic ester.
3. The high temperature resistant 3D molding composite material according to claim 2, wherein the urethane acrylate is aliphatic urethane acrylate, and the epoxy acrylate is novolac epoxy acrylate.
4. The high temperature resistant 3D molding composite material of claim 2, wherein the functional reactive diluent monomer comprises 10-20 parts of acryloyl morpholine and 20-30 parts of tris (2-hydroxyethyl) isocyanurate triacrylate.
5. The high temperature resistant 3D composite molding material of claim 2, wherein the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide.
6. The high temperature resistant 3D molding composite material according to claim 2, characterized in that the ultraviolet absorber is 2, 2' -methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol).
7. The high temperature resistant 3D molding composite material according to claim 2, characterized in that the pigment is titanium dioxide.
8. The high temperature resistant 3D molding composite material according to claim 2, characterized in that the filler is nanometer silica micropowder or nanometer zirconium dioxide powder.
9. The preparation method of the high temperature-resistant 3D molding composite material according to claim 1, characterized by comprising the following steps:
s1, weighing polyurethane acrylate, epoxy acrylate, hyperbranched acrylate, a functional reactive diluent monomer, a photoinitiator and an ultraviolet absorbent in proportion, and stirring and pre-dispersing on an independent suspension stirrer at 400 rpm/min;
s2, heating the pre-dispersion prepared in the step to 60-65 ℃ in a water bath, keeping the temperature constant, adding the pigment and the nano powder filler into the pre-dispersion in batches according to a proportion under the high-speed dispersion state of 3000 plus 5000rpm/min, and stirring and dispersing at a high speed for 30-60min to prepare the high-temperature-resistant 3D forming composite material.
CN202111201816.7A 2021-10-15 2021-10-15 High-temperature-resistance 3D (three-dimensional) molding composite material and preparation method thereof Pending CN113698544A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111201816.7A CN113698544A (en) 2021-10-15 2021-10-15 High-temperature-resistance 3D (three-dimensional) molding composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111201816.7A CN113698544A (en) 2021-10-15 2021-10-15 High-temperature-resistance 3D (three-dimensional) molding composite material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113698544A true CN113698544A (en) 2021-11-26

Family

ID=78646769

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111201816.7A Pending CN113698544A (en) 2021-10-15 2021-10-15 High-temperature-resistance 3D (three-dimensional) molding composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113698544A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552461A (en) * 2020-11-24 2021-03-26 深圳光华伟业股份有限公司 Photocuring-molded high-temperature-resistant photosensitive resin and preparation method and application thereof
CN113321797A (en) * 2021-07-20 2021-08-31 威海飞牛高分子科技有限公司 Dendritic or hyperbranched modified photocuring 3D printing material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552461A (en) * 2020-11-24 2021-03-26 深圳光华伟业股份有限公司 Photocuring-molded high-temperature-resistant photosensitive resin and preparation method and application thereof
CN113321797A (en) * 2021-07-20 2021-08-31 威海飞牛高分子科技有限公司 Dendritic or hyperbranched modified photocuring 3D printing material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张勇等: "巯基丙烯酸酯树脂的合成及自引发光聚合反应", 高等学校化学学报, vol. 33, pages 635 - 639 *

Similar Documents

Publication Publication Date Title
CN1315950C (en) Transparent composite composition
KR100932129B1 (en) Marble chip, Marble chip manufacturing method, and artificial marble using the same
CN101747468B (en) Copolymer and photosensitive resin composition
CN107698718B (en) Photosensitive resin for laser 3D printing and preparation method thereof
CN112859519A (en) Photosensitive resin composition and preparation method and application thereof
CN111454657A (en) Fullerene-based super-wear-resistant photocureable coating and application thereof
EP2907833A1 (en) Curable resin composition, and cured product thereof
CN113817109B (en) 3D printing photocuring composition, 3D printing method and 3D printing product
CN104011130B (en) Photocurable fluorine-containing copolymer composition
KR101025721B1 (en) Non-Solvent Type, UV-Curable White Ink Composition
CN118048016B (en) Transparent composite material prepreg reinforced resin and preparation method and application thereof
EP2119731A1 (en) Silica sol having reactive monomer dispersed therein, method for producing the silica sol, curing composition, and cured article produced from the curing composition
CN114057959A (en) Resin for wind power and corresponding preparation method thereof
CN113698544A (en) High-temperature-resistance 3D (three-dimensional) molding composite material and preparation method thereof
CN111410907B (en) Self-repairing type temperature-resistant wear-resistant polyaspartic acid ester coating and preparation method thereof
TW201927398A (en) Inorganic microparticle dispersion, curable composition, and optical member
CN113372512A (en) Photocuring resin for wind power and corresponding preparation method thereof
CN117402458A (en) Prepreg resin for composite material, and preparation method and application thereof
CN115197375B (en) Photosensitive resin composition suitable for 3D printing transparent elastomer and preparation method thereof
CN105474084B (en) The manufacturing method of liquid crystal sealing agent and liquid crystal display panel
CN114539908A (en) High yellowing-resistant UV (ultraviolet) photocureable coating applied to decorative sheet and preparation method thereof
JP7525295B2 (en) Pigment dispersion composition for black matrix, resist composition for black matrix, and black matrix
CN115466567A (en) LED-UV gloss oil and preparation method thereof
US11912860B2 (en) Highly loaded inorganic filled organic resin systems
CN114213810A (en) High-strength 3D printing photosensitive resin material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20211126