CN113896839A - Hollow porous silica microsphere reinforced photocuring 3D printing composite material - Google Patents
Hollow porous silica microsphere reinforced photocuring 3D printing composite material Download PDFInfo
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- CN113896839A CN113896839A CN202111201955.XA CN202111201955A CN113896839A CN 113896839 A CN113896839 A CN 113896839A CN 202111201955 A CN202111201955 A CN 202111201955A CN 113896839 A CN113896839 A CN 113896839A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000010146 3D printing Methods 0.000 title claims abstract description 79
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 66
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000004005 microsphere Substances 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 230000002745 absorbent Effects 0.000 claims abstract description 27
- 239000002250 absorbent Substances 0.000 claims abstract description 27
- 239000003085 diluting agent Substances 0.000 claims abstract description 25
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000000805 composite resin Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 28
- 238000007639 printing Methods 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 8
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- -1 2-hydroxy-2-methyl-phenyl Chemical group 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- JDMWKQBUVLLVQR-UHFFFAOYSA-N CC1=C(C(=C(C(=O)P(C2=CC=CC=C2)=O)C=C1)C)C Chemical compound CC1=C(C(=C(C(=O)P(C2=CC=CC=C2)=O)C=C1)C)C JDMWKQBUVLLVQR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000004530 micro-emulsion Substances 0.000 claims description 2
- QKQSRIKBWKJGHW-UHFFFAOYSA-N morpholine;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCCN1 QKQSRIKBWKJGHW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 10
- 238000001723 curing Methods 0.000 abstract description 8
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 21
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 10
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 6
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- NSFGOWGWLHAJPC-UHFFFAOYSA-N COCOC.C(C=C)(=O)O Chemical compound COCOC.C(C=C)(=O)O NSFGOWGWLHAJPC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000110 selective laser sintering Methods 0.000 description 2
- 101100356682 Caenorhabditis elegans rho-1 gene Proteins 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
- C08F2/44—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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)
Abstract
The invention relates to the technical field of 3D printing high polymer materials, and discloses a hollow porous silica microsphere reinforced photocuring 3D printing composite material which comprises the following raw materials in parts by weight: 40-55 parts of acrylate resin prepolymer; 45-55 parts of reactive diluent monomer; 1-2 parts of a photoinitiator; 0.05-0.1 part of ultraviolet absorbent and 0.1-10 parts of porous silicon dioxide, wherein the acrylate resin prepolymer is a mixture consisting of 55-65 parts of aliphatic polyurethane acrylate and 35-45 parts of aromatic polyurethane acrylate according to mass fraction. According to the hollow porous silica microsphere reinforced photocuring 3D printing composite material, the physical cross-linking points are formed between the hollow porous silica microsphere reinforced photocuring 3D printing composite material and resin through the unique spatial structure of the hollow porous silica, so that the mechanical property of the prepared hollow porous silica microsphere reinforced photocuring 3D printing resin composite material is improved, and the hollow porous silica microsphere reinforced photocuring 3D printing composite material has the advantages of high strength and low curing shrinkage.
Description
Technical Field
The invention relates to the technical field of 3D printing high polymer materials, in particular to a hollow porous silica microsphere reinforced photocuring 3D printing composite material.
Background
3D printing, also known as additive manufacturing, has rapidly evolved and is widely used in many aspects of our lives, because of its advantages of flexible design, freedom in processing, low energy consumption for full utilization of materials, etc., it is receiving unprecedented attention from both academic and industrial circles, and the development of various 3D printing technologies, including stereolithography equipment (SLA), Fused Deposition Modeling (FDM), inkjet printing, direct writing (DIW), digital light processing (LCD or DLP), Selective Laser Sintering (SLS) and Selective Laser Melting (SLM), has prompted the application of 3D printing technologies and also has attracted people's attention to 3D printing materials, to further meet the different manufacturing methods and specific requirements, a variety of 3D printing materials have been developed, including metallic materials, ceramic materials and polymeric materials, among these materials, high molecular materials stand out from the fact that they can produce various complex structures.
LCD or DLP3D printing technologies have the following features: high build resolution, smooth part surfaces (usually without finishing processes), good Z-axis strength due to interlayer chemical bonds, possibility of fast build and ability to print sharp objects, LCD or DLP are superior to other additive manufacturing technologies only in terms of precision and resolution, with the smallest detail size being 50-200 μm in most manufacturing technologies, many commercially available LCD or DLP devices can build objects of several cubic centimeters with a precision of 20 μm, and in some special fields, high efficiency and precision are required, including biomedicine, automotive industry, microelectronics, leather industry, shoe industry, clothing and ergonomics, etc., LCD or DLP technologies just can meet their needs, thus rapidly developing.
In spite of the above advantages, the application of LCD or DLP3D printing mainly depends on photosensitive resin, and at present, LCD or DLP3D printing resin has many problems such as limited resin types, insufficient mechanical strength, resin odor, long-term stability and cost, and even at room temperature, the phase change through a very rapid reaction is a great challenge for developing new materials, so a hollow porous silica microsphere reinforced photocuring 3D printing composite material is proposed to solve the problems.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a hollow porous silica microsphere reinforced photocuring 3D printing composite material which has the advantages of excellent mechanical property, low shrinkage rate and the like, and solves the problems of limited resin types, insufficient mechanical strength, resin odor, long-term stability, cost and the like of LCD or DLP3D printing resin.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following raw materials in parts by weight: 40-55 parts of acrylate resin prepolymer; 45-55 parts of reactive diluent monomer; 1-2 parts of a photoinitiator; 0.05-0.1 part of ultraviolet absorbent and 0.1-10 parts of porous silicon dioxide.
Preferably, the acrylate resin prepolymer is a mixture consisting of 55-65 parts by mass of aliphatic polyurethane acrylate and 35-45 parts by mass of aromatic polyurethane acrylate.
Preferably, the reactive diluent is selected from one or more of isobornyl acrylate, morpholine acrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate and pentaerythritol triacrylate.
Preferably, the photoinitiator is selected from 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide; bis 2, 4, 6 (trimethylbenzoyl) phenylphosphine oxide; one or more of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-phenyl acetone-1.
Preferably, the ultraviolet absorber comprises one of 2, 2-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol) and 2-hydroxy-4-n-octoxybenzophenone.
Preferably, the particle size of the hollow porous silica microspheres is 10-50 μm.
The invention provides a preparation method of a hollow porous silica microsphere reinforced photocuring 3D printing composite material, which comprises the following steps:
1) preparation of the photocurable resin: weighing 40-55 parts of acrylate resin prepolymer and 45-55 parts of active diluent monomer, heating to 60-80 ℃, stirring at 400rpm for 30min, weighing 1-2 parts of photoinitiator and 0.05-0.1 part of ultraviolet absorbent by an electronic balance, adding, stirring and dissolving for 2h to obtain the 3D printing photosensitive resin.
2) Preparing hollow porous silica microspheres: dissolving 0.6g of acrylic acid homopolymer in 60mL of absolute ethanol, stirring at normal temperature at the stirring speed of 500rpm, adding 4.0mL of ammonia water when polyacrylic acid is completely dissolved, gradually forming white microemulsion, continuously adding 30mL of polyether F127 ethanol solution, wherein the mass fraction of polyether F127 is 1.2%, adding 2mL of tetraethoxysilane into the system for hydrolysis reaction at an interval of 1h for 5 times, centrifuging after 12h of reaction, washing with ethanol for 3 times, separating, drying, transferring a sample into a muffle furnace, calcining at 550 ℃ for 6h, and removing a template to obtain the hollow porous silicon dioxide.
3) Preparing a composite material: and uniformly mixing the obtained photocuring 3D printing resin and the hollow porous silica microspheres according to a certain mass ratio, mechanically stirring for 1-2h, then placing the mixture into a vacuum drying oven 10min to remove bubbles, and finally obtaining the hollow porous silica microsphere reinforced photocuring 3D printing resin composite material.
4) 3D printing of resin: and (3) printing by using a DLP (digital light processing) type 3D printer, wherein the printing parameters are set to 5s of normal exposure time, 15s of bottom exposure time, 6 layers of bottom layers and 50 microns of slicing layer thickness.
(III) advantageous effects
Compared with the prior art, the invention provides a hollow porous silica microsphere reinforced photocuring 3D printing composite material, which has the following beneficial effects:
according to the hollow porous silica microsphere reinforced photocuring 3D printing composite material, the physical cross-linking points are formed between the hollow porous silica microsphere reinforced photocuring 3D printing composite material and resin through the unique spatial structure of the hollow porous silica, so that the mechanical property of the prepared hollow porous silica microsphere reinforced photocuring 3D printing resin composite material is improved, and the hollow porous silica microsphere reinforced photocuring 3D printing composite material has the advantages of high strength and low curing shrinkage.
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 hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following raw materials in parts by weight: 40 parts of acrylate resin prepolymer, 58 parts of reactive diluent monomer, 2 parts of photoinitiator, 0.05 part of ultraviolet absorbent, 2 parts of hollow porous silicon dioxide, the acrylate resin prepolymer comprises 25 parts by weight of aliphatic polyurethane acrylate and 20 parts by weight of aromatic polyurethane acrylate, an active diluent comprises 15 parts by weight of acryloyl morpholine, 10 parts by weight of cyclotrimethylolpropane methylal acrylate and 25 parts by weight of 1, 6-hexanediol diacrylate, and a photoinitiator comprises 2 parts by weight of 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide and 2 parts by weight of 1-hydroxycyclohexyl benzophenone, wherein the ultraviolet absorbent is 2, 2-methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol).
A preparation method of a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following steps:
1) preparing resin: and mixing the acrylate resin prepolymer with an active diluent monomer, heating to 60-80 ℃, stirring at 400rpm for 30min, then weighing a corresponding photoinitiator and an ultraviolet absorbent by an electronic balance, adding the photoinitiator and the ultraviolet absorbent, stirring and dissolving for 2h, and thus obtaining the 3D printing photosensitive resin.
2) Preparing a composite material: and uniformly mixing the obtained photocuring 3D printing resin and the hollow porous silica microspheres according to the mass ratio, mechanically stirring for 1-2h, then putting the mixture into a vacuum drying oven for 10min to remove bubbles, and finally obtaining the hollow porous silica microsphere reinforced photocuring 3D printing resin composite material.
3)3D printing sample preparation: and printing by adopting an LCD or DLP type 3D printer, wherein the printing parameters are set to 5s of normal exposure time, 15s of bottom exposure time, 6 layers of bottom layers and 50 microns of slicing layer thickness.
Example two: a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following raw materials in parts by weight: 41 parts of acrylate resin prepolymer, 55 parts of active diluent monomer, 2 parts of photoinitiator, 0.05 part of ultraviolet absorbent and 4 parts of hollow porous silicon dioxide, wherein, the prepolymer comprises 25 parts of aliphatic urethane acrylate and 25 parts of aromatic urethane acrylate by weight parts, the active diluent comprises 15 parts of acryloyl morpholine, 15 parts of cyclotrimethylolpropane formal acrylate and 20 parts of 1, 6-hexanediol diacrylate by weight parts, and the photoinitiator comprises 3 parts of 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide and 2 parts of 1-hydroxycyclohexyl benzophenone (184) by weight parts, wherein the ultraviolet absorbent is 2, 2-methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol).
A preparation method of a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following steps:
1) preparing resin: and mixing the acrylate resin prepolymer with an active diluent monomer, heating to 60-80 ℃, stirring at 400rpm for 30min, then weighing a corresponding photoinitiator and an ultraviolet absorbent by an electronic balance, adding the photoinitiator and the ultraviolet absorbent, stirring and dissolving for 2h, and thus obtaining the 3D printing photosensitive resin.
2) Preparing a composite material: and uniformly mixing the obtained photocuring 3D printing resin and the hollow porous silica microspheres according to the mass ratio, mechanically stirring for 1-2h, then putting the mixture into a vacuum drying oven for 10min to remove bubbles, and finally obtaining the hollow porous silica microsphere reinforced photocuring 3D printing resin composite material.
3)3D printing sample preparation: and printing by adopting an LCD or DLP type 3D printer, wherein the printing parameters are set to 5s of normal exposure time, 15s of bottom exposure time, 6 layers of bottom layers and 50 microns of slicing layer thickness.
Example three: a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following raw materials in parts by weight: 50 parts of acrylate resin prepolymer, 44 parts of reactive diluent monomer, 2 parts of photoinitiator, 0.05 part of ultraviolet absorbent, 6 parts of hollow porous silicon dioxide, wherein, the prepolymer comprises 25 parts of aliphatic urethane acrylate and 20 parts of aromatic urethane acrylate by weight parts, the active diluent comprises 10 parts of acryloyl morpholine, 15 parts of cyclotrimethylolpropane formal acrylate and 25 parts of 1, 6-hexanediol diacrylate by weight parts, and the photoinitiator comprises 3 parts of 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide and 2 parts of 1-hydroxycyclohexyl benzophenone (184) by weight parts, wherein the ultraviolet absorbent is 2, 2-methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol).
A preparation method of a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following steps:
1) preparing resin: and mixing the acrylate resin prepolymer with an active diluent monomer, heating to 60-80 ℃, stirring at 400rpm for 30min, then weighing a corresponding photoinitiator and an ultraviolet absorbent by an electronic balance, adding the photoinitiator and the ultraviolet absorbent, stirring and dissolving for 2h, and thus obtaining the 3D printing photosensitive resin.
2) Preparing a composite material: and uniformly mixing the obtained photocuring 3D printing resin and the hollow porous silica microspheres according to the mass ratio, mechanically stirring for 1-2h, then placing the mixture into a vacuum drying oven 10min to remove bubbles, and finally obtaining the hollow porous silica microsphere reinforced photocuring 3D printing resin composite material.
3)3D printing sample preparation: and printing by adopting an LCD or DLP type 3D printer, wherein the printing parameters are set to 5s of normal exposure time, 15s of bottom exposure time, 6 layers of bottom layers and 50 microns of slicing layer thickness.
Example four: a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following raw materials in parts by weight: 48 parts of acrylate resin prepolymer, 44 parts of reactive diluent monomer, 2 parts of photoinitiator, 0.05 part of ultraviolet absorbent, 8 parts of hollow porous silicon dioxide, wherein the prepolymer comprises 15 parts by weight of aliphatic urethane acrylate and 25 parts by weight of aromatic urethane acrylate, the active diluent comprises 10 parts by weight of acryloyl morpholine, 10 parts by weight of cyclotrimethylolpropane formal acrylate and 20 parts by weight of 1, 6-hexanediol diacrylate, and the photoinitiator comprises 3 parts by weight of 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide and 2 parts by weight of 1-hydroxycyclohexyl benzophenone (184), wherein the ultraviolet absorbent is 2, 2-methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol).
A preparation method of a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following steps:
1) preparing resin: and mixing the acrylate resin prepolymer with an active diluent monomer, heating to 60-80 ℃, stirring at 400rpm for 30min, then weighing a corresponding photoinitiator and an ultraviolet absorbent by an electronic balance, adding the photoinitiator and the ultraviolet absorbent, stirring and dissolving for 2h, and thus obtaining the 3D printing photosensitive resin.
2) Preparing a composite material: and uniformly mixing the obtained photocuring 3D printing resin and the hollow porous silica microspheres according to the mass ratio, mechanically stirring for 1-2h, then putting the mixture into a vacuum drying oven for 10min to remove bubbles, and finally obtaining the hollow porous silica microsphere reinforced photocuring 3D printing resin composite material.
3)3D printing sample preparation: and printing by adopting an LCD or DLP type 3D printer, wherein the printing parameters are set to 5s of normal exposure time, 15s of bottom exposure time, 6 layers of bottom layers and 50 microns of slicing layer thickness.
Comparative example one: a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following raw materials in parts by weight: 43 parts of acrylate resin prepolymer, 57 parts of active diluent monomer, 2 parts of photoinitiator and 0.05 part of ultraviolet absorber, wherein the prepolymer comprises 25 parts of aliphatic urethane acrylate and 25 parts of aromatic urethane acrylate according to parts by weight, the active diluent comprises 15 parts of acryloyl morpholine, 15 parts of cyclotrimethylolpropane methylal acrylate and 20 parts of 1, 6-hexanediol diacrylate according to parts by weight, and the photoinitiator comprises 3 parts of 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide and 2 parts of 1-hydroxycyclohexyl benzophenone (184) according to parts by weight, and the ultraviolet absorber is 2, 2-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol).
A preparation method of a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following steps:
1) preparing resin: and mixing the acrylate resin prepolymer with an active diluent monomer, heating to 60-80 ℃, stirring at 400rpm for 30min, then weighing a corresponding photoinitiator and an ultraviolet absorbent by an electronic balance, adding the photoinitiator and the ultraviolet absorbent, stirring and dissolving for 2h, and thus obtaining the 3D printing photosensitive resin.
2) Preparing a composite material: and uniformly mixing the obtained photocuring 3D printing resin and the hollow porous silica microspheres according to the mass ratio, mechanically stirring for 1-2h, then putting the mixture into a vacuum drying oven for 10min to remove bubbles, and finally obtaining the hollow porous silica microsphere reinforced photocuring 3D printing resin composite material.
3)3D printing sample preparation: and printing by adopting an LCD or DLP type 3D printer, wherein the printing parameters are set to 5s of normal exposure time, 15s of bottom exposure time, 6 layers of bottom layers and 50 microns of slicing layer thickness.
Comparative example two: a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following raw materials in parts by weight: 41 parts of acrylate resin prepolymer, 55 parts of active diluent monomer, 2 parts of photoinitiator, 0.05 part of ultraviolet absorbent, 4 parts of hollow non-porous silicon dioxide, wherein, the prepolymer comprises 25 parts of aliphatic urethane acrylate and 25 parts of aromatic urethane acrylate by weight parts, the active diluent comprises 15 parts of acryloyl morpholine, 15 parts of cyclotrimethylolpropane formal acrylate and 20 parts of 1, 6-hexanediol diacrylate by weight parts, and the photoinitiator comprises 3 parts of 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide and 2 parts of 1-hydroxycyclohexyl benzophenone (184) by weight parts, wherein the ultraviolet absorbent is 2, 2-methylenebis (6- (2H-benzotriazole-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol).
A preparation method of a hollow porous silica microsphere reinforced photocuring 3D printing composite material comprises the following steps:
1) preparing resin: and mixing the acrylate resin prepolymer with an active diluent monomer, heating to 60-80 ℃, stirring at 400rpm for 30min, then weighing a corresponding photoinitiator and an ultraviolet absorbent by an electronic balance, adding the photoinitiator and the ultraviolet absorbent, stirring and dissolving for 2h, and thus obtaining the 3D printing photosensitive resin.
2) Preparing a composite material: and uniformly mixing the obtained photocuring 3D printing resin and the hollow porous silica microspheres according to the mass ratio, mechanically stirring for 1-2h, then putting the mixture into a vacuum drying oven for 10min to remove bubbles, and finally obtaining the hollow porous silica microsphere reinforced photocuring 3D printing resin composite material.
3)3D printing sample preparation: and printing by adopting an LCD or DLP type 3D printer, wherein the printing parameters are set to 5s of normal exposure time, 15s of bottom exposure time, 6 layers of bottom layers and 50 microns of slicing layer thickness.
The test items and the measurement methods in the following examples of the present invention are as follows, and each test was carried out at 25 ℃ unless otherwise specified. The results are shown in Table 1.
Tensile strength was tested according to GB/T1040.1-2006 standard, bar size (mm): 80X 4X 2, and a drawing speed of 1 mm/min.
Flexural strength was tested according to GB/T9341-: 80X 10X 4, bending rate 1 mm/min.
Notched impact strength was tested according to GB/T1843-2008, specimen size (mm): 80 multiplied by 10 multiplied by 4, the notch type of the notch impact strength is A type, the radius of the bottom of the notch is 0.25 plus or minus 0.05mm, and the residual width of the bottom of the notch is 8.0 plus or minus 0.2 mm.
The volume shrinkage (volume shrinkage rate) of the photosensitive resin is determined by the following method: the density of the resin before curing is measured by using a pycnometer at normal temperature, the density of the resin after curing is measured by using a drainage volume method, the curing shrinkage rate of the liquid resin is calculated by a formula, wherein rho 1 is the density of the liquid resin, rho 2 is the density of the resin after ultraviolet curing of the liquid resin, and the volume shrinkage rate is calculated by the following formula:
TABLE 1 mechanical Properties and shrinkage test data for examples and comparative examples
From the test data of table 1, the following conclusions can be drawn: from example 2 and comparative example 1 comparison it can be concluded that: the addition of the hollow porous silica can obviously improve the tensile strength and the bending strength of the resin material, but can reduce the impact strength of the resin material, and the comparison of the data of the experimental examples 1 to 4 can show that the addition amount of the hollow porous silica has an optimal value for the tensile and bending properties of the composite material, and the comparison of the data of the experimental example 2 and the comparative examples 1 and 2 can show that the improvement of the mechanical properties of the resin composite material by the hollow porous silica is derived from the unique hollow porous spatial structure, and the data of the experimental examples 1 to 4 can show that the curing shrinkage rate of the acrylate resin composite material is obviously reduced along with the addition of the hollow porous silica.
The invention has the beneficial effects that: according to the hollow porous silica microsphere reinforced photocuring 3D printing composite material, the physical cross-linking points are formed between the hollow porous silica microsphere reinforced photocuring 3D printing composite material and resin through the unique spatial structure of the hollow porous silica, so that the mechanical property of the prepared hollow porous silica microsphere reinforced photocuring 3D printing resin composite material is improved, and the hollow porous silica microsphere reinforced photocuring 3D printing composite material has the advantages of high strength and low curing shrinkage.
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 (7)
1. The hollow porous silica microsphere reinforced photocuring 3D printing composite material is characterized by comprising the following raw materials in parts by weight: 40-55 parts of acrylate resin prepolymer; 45-55 parts of reactive diluent monomer; 1-2 parts of a photoinitiator; 0.05-0.1 part of ultraviolet absorbent and 0.1-10 parts of porous silicon dioxide.
2. The hollow porous silica microsphere reinforced photocuring 3D printing composite material as claimed in claim 1, wherein the acrylate resin prepolymer is a mixture of 55-65 parts by mass of aliphatic urethane acrylate and 35-45 parts by mass of aromatic urethane acrylate.
3. The hollow porous silica microsphere reinforced photocuring 3D printing composite as claimed in claim 1, wherein the reactive diluent is selected from one or more of isobornyl acrylate, morpholine acrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate and pentaerythritol triacrylate.
4. The hollow porous silica microsphere reinforced photocuring 3D printing composite as claimed in claim 1 wherein the photoinitiator is selected from 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide; bis 2, 4, 6 (trimethylbenzoyl) phenylphosphine oxide; one or more of 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-phenyl acetone-1.
5. The hollow porous silica microsphere-reinforced photocurable 3D printing composite material according to claim 1, wherein the uv absorber comprises one of 2, 2-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1, 1, 3, 3-tetramethylbutyl) phenol) and 2-hydroxy-4-n-octoxybenzophenone.
6. The hollow porous silica microsphere-reinforced photocuring 3D printing composite material as claimed in claim 1, wherein the particle size of the hollow porous silica microsphere is 10-50 μm.
7. A preparation method of a hollow porous silica microsphere reinforced photocuring 3D printing composite material is characterized by comprising the following steps:
1) preparation of the photocurable resin: weighing 40-55 parts of acrylate resin prepolymer and 45-55 parts of active diluent monomer, heating to 60-80 ℃, stirring at 400rpm for 30min, weighing 1-2 parts of photoinitiator and 0.05-0.1 part of ultraviolet absorbent by an electronic balance, adding, stirring and dissolving for 2h to obtain the 3D printing photosensitive resin.
2) Preparing hollow porous silica microspheres: dissolving 0.6g of acrylic acid homopolymer in 60mL of absolute ethanol, stirring at normal temperature at the stirring speed of 500rpm, adding 4.0mL of ammonia water when polyacrylic acid is completely dissolved, gradually forming white microemulsion, continuously adding 30mL of polyether F127 ethanol solution, wherein the mass fraction of polyether F127 is 1.2%, adding 2mL of tetraethoxysilane into the system for hydrolysis reaction at an interval of 1h for 5 times, centrifuging after 12h of reaction, washing with ethanol for 3 times, separating, drying, transferring a sample into a muffle furnace, calcining at 550 ℃ for 6h, and removing a template to obtain the hollow porous silicon dioxide.
3) Preparing a composite material: and uniformly mixing the obtained photocuring 3D printing resin and the hollow porous silica microspheres according to a certain mass ratio, mechanically stirring for 1-2h, then placing in a vacuum drying oven for 10min to remove bubbles, and finally obtaining the hollow porous silica microsphere reinforced photocuring 3D printing resin composite material.
4) 3D printing of resin: and (3) printing by using a DLP (digital light processing) type 3D printer, wherein the printing parameters are set to 5s of normal exposure time, 15s of bottom exposure time, 6 layers of bottom layers and 50 microns of slicing layer thickness.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073674A (en) * | 2022-06-22 | 2022-09-20 | 深圳锐沣科技有限公司 | 3D printing resin composition for shoe material, 3D printing product and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836946A (en) * | 2019-01-24 | 2019-06-04 | 上海坚弗特种涂料有限公司 | A kind of ultraviolet-curing paint and its preparation method and application efficiently removing formaldehyde |
| CN111253854A (en) * | 2020-04-07 | 2020-06-09 | 广州四面体新材料科技有限公司 | Anti-reflective coating material containing modified porous silica, preparation method and anti-reflective film |
| 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 |
| CN113185645A (en) * | 2021-04-23 | 2021-07-30 | 东莞理工学院 | Photosensitive resin for 3D printing based on DLP type photocuring and preparation method thereof |
-
2021
- 2021-10-15 CN CN202111201955.XA patent/CN113896839A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836946A (en) * | 2019-01-24 | 2019-06-04 | 上海坚弗特种涂料有限公司 | A kind of ultraviolet-curing paint and its preparation method and application efficiently removing formaldehyde |
| CN111253854A (en) * | 2020-04-07 | 2020-06-09 | 广州四面体新材料科技有限公司 | Anti-reflective coating material containing modified porous silica, preparation method and anti-reflective film |
| 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 |
| CN113185645A (en) * | 2021-04-23 | 2021-07-30 | 东莞理工学院 | Photosensitive resin for 3D printing based on DLP type photocuring and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李成阳等: "中空介孔SiO2纳米球的制备、改性及其对Al3＋荧光识别研究", 《人工晶体学报》, vol. 47, no. 2, pages 326 - 332 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073674A (en) * | 2022-06-22 | 2022-09-20 | 深圳锐沣科技有限公司 | 3D printing resin composition for shoe material, 3D printing product and preparation method thereof |
| CN115073674B (en) * | 2022-06-22 | 2023-09-15 | 深圳锐沣科技有限公司 | 3D printing resin composition for shoe material, 3D printing product and preparation method thereof |
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