CN107141418B - A kind of halloysite nanotubes compound resin and its application as photocuring 3D printing material - Google Patents
A kind of halloysite nanotubes compound resin and its application as photocuring 3D printing material Download PDFInfo
- Publication number
- CN107141418B CN107141418B CN201710285468.3A CN201710285468A CN107141418B CN 107141418 B CN107141418 B CN 107141418B CN 201710285468 A CN201710285468 A CN 201710285468A CN 107141418 B CN107141418 B CN 107141418B
- Authority
- CN
- China
- Prior art keywords
- halloysite nanotubes
- compound resin
- resin
- parts
- photocuring
- 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.)
- Active
Links
- 239000002071 nanotube Substances 0.000 title claims abstract description 56
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 238000010146 3D printing Methods 0.000 title claims abstract description 22
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims abstract description 10
- 229920002635 polyurethane Polymers 0.000 claims abstract description 16
- 239000004814 polyurethane Substances 0.000 claims abstract description 16
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 14
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 16
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 15
- 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
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 11
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group 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
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 claims 2
- -1 2- hydroxyl -4- (2- hydroxy ethoxy) -2- methyl phenyl Chemical group 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 229940113165 trimethylolpropane Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- LKFAPHHHWRMPGC-UHFFFAOYSA-N butan-1-ol prop-2-enoic acid Chemical compound CCCCO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C LKFAPHHHWRMPGC-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- 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)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to technical field of composite materials, disclose a kind of halloysite nanotubes compound resin and its application as photocuring 3D printing material.The compound resin is grouped as by the group of following mass parts: 20~60 parts of polyurethane acrylate resin, 40~80 parts of reactive diluent, 0.5~2 part of radical photoinitiator, 1~5 part of halloysite nanotubes.Preparation method are as follows: ultrasonic disperse and mechanical stirring are uniform in reactive diluent by halloysite nanotubes, then it is uniform that polyurethane acrylate resin mechanical stirring is added, it adds radical photoinitiator mechanical stirring to be uniformly dissolved, obtains the halloysite nanotubes compound resin.The present invention is suitable for the compound resin of photocuring 3D printing using polyurethane acrylate resin and halloysite nanotubes preparation, has excellent mechanical property, has further widened the application range of photocuring 3D printing technique.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of halloysite nanotubes compound resin and its as light
Solidify the application of 3D printing material.
Background technique
3D printing (3D printing) is one kind of rapid shaping (Rapidprototyping, RP) technology, is also referred to as increased
Material manufacturing technology.3D printing is unanimously considered 21 century most subversive forming processing technology, working principle both at home and abroad
It is the three-dimensional digital model formed using scanning, according to the principle that " Layered manufacturing is successively superimposed ", quickly prepares 3D solid
A kind of Layered Manufacturing Technology.Stereolithography (SLA and DLP) is one kind of 3D printing technique.SLA master's raw material to be used is
Ultraviolet curable resin is successively to be scanned and exposed on photosensitive resin surface by UV laser beam, is scanned and exposed region
Resin layer photopolymerization reaction and final solidified forming occurs.
But the generally existing mechanical property of photocurable resin material used at present is poor, is easy bending cracking, hardness is inclined
The problems such as low, these problems limit the popularization of photocuring 3D printing rapid shaping technique.
Polyurethane acrylate resin has preferable comprehensive performance.There are ammonia ester bond, energy in urethane acrylate molecule
A variety of hydrogen bonds are formed between macromolecular chain, there is excellent wearability and flexibility, elongation at break is high, while having good after solidification
Resistance to active drug moral character well, high and low temperature resistance, preferable impact resistance.
Halloysite nanotubes (HNTs) are a kind of natural nanotube-shaped clay minerals, with special structure and excellent
Performance.General 40~the 100nm of pipe outside diameter of HNTs, length is about 0.2~2um.HNTs is double deck type aluminosilicate, by internal layer alumina
Octahedra and outer layer oxygen-octahedron lattice mismatch crimps, and there are the crystallizations water for interlayer.The outer surface of HNTs is mainly
It is made of Si-O-Si key, inner wall is then mainly the light base of aluminium.There are sial hydroxyls on the end face of halloysite nanotubes, and in crystalline substance
There is also a small amount of embedding hydroxyls for the inner wall of body.HNTs agglomeration is relatively weak, the hydroxyl and content of siloxane on the surface HNTs
It is relatively fewer, it is combined in the form of the secondary bonds such as hydrogen bond and Van der Waals force between structural unit, is easier to realize structural unit
Dissociation and dispersion, it is not easy to reunite；And between nanotube, aspect ratio tube-like condition appropriate reduces connecing between pipe
Contacting surface product.Therefore, the HNTs with longer draw ratio can be evenly dispersed in polymer, be to prepare high-performance polymer to receive
The novel cheap nanofiller of nano composite material.
Summary of the invention
For in place of shortcoming and defect of the existing technology, received the primary purpose of the present invention is that providing a kind of galapectite
Mitron compound resin.
Another object of the present invention is to provide the preparation methods of above-mentioned halloysite nanotubes compound resin.
A further object of the present invention is to provide above-mentioned halloysite nanotubes compound resins as photocuring 3D printing material
Application.
The object of the invention is achieved through the following technical solutions:
A kind of halloysite nanotubes compound resin, is grouped as by the group of following mass parts: polyurethane acrylate resin 20
~60 parts, 40~80 parts of reactive diluent, 0.5~2 part of radical photoinitiator, 1~5 part of halloysite nanotubes.
Preferably, the degree of functionality of the polyurethane acrylate resin is 2~6, and viscosity is 200~10000mPa.s.
Preferably, the reactive diluent is acryloyl morpholine (ACMO), glycidyl methacrylate (GMA), three
At least one of hydroxymethyl-propane triacrylate (TMPTA) and trimethylol-propane trimethacrylate (TMPTMA)；
The mixing of more preferable trimethylolpropane trimethacrylate (TMPTA) and acryloyl morpholine (ACMO).
Preferably, the radical photoinitiator is 1- hydroxycyclohexyl phenyl ketone (photoinitiator 184), 2- hydroxyl
Base -4- (2- hydroxy ethoxy) -2- methyl phenyl ketone (photoinitiator 2959), phenyl bis- (2,4,6- trimethylbenzoyls) oxidation
At least one of phosphine (photoinitiator 819), (2,4,6- trimethylbenzoyl) diphenyl phosphine oxide (photoinitiator TPO)；
More preferably (2,4,6- trimethylbenzoyl) diphenyl phosphine oxide (photoinitiator TPO).
The preparation method of above-mentioned halloysite nanotubes compound resin, including following preparation step:
By halloysite nanotubes, ultrasonic disperse and mechanical stirring are uniform in reactive diluent, and polyurethane propylene is then added
Acid ester resin mechanical stirring is uniform, adds radical photoinitiator mechanical stirring and is uniformly dissolved, and obtains the galapectite and receives
Mitron compound resin.
Application of the above-mentioned halloysite nanotubes compound resin as photocuring 3D printing material.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
The present invention is suitable for answering for photocuring 3D printing using polyurethane acrylate resin and halloysite nanotubes preparation
Resin has excellent mechanical property, has further widened the application range of photocuring 3D printing technique.
Detailed description of the invention
Fig. 1 is that halloysite nanotubes dispersion is swept in 1 gained halloysite nanotubes compound resin of the embodiment of the present invention
Retouch Electronic Speculum (SEM) figure.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of halloysite nanotubes compound resin for photocuring 3D printing of the present embodiment, by following parts by weight meter
Raw material composition: 6 30 parts of degree of functionality urethane acrylates, 30 parts of 2 degree of functionality urethane acrylate, trimethylolpropane tris
20 parts of acrylate TMPTA, 20 parts of acryloyl morpholine ACMO, 2 parts of photoinitiator TPO, 2.5 parts of halloysite nanotubes.
The preparation method is as follows:
Halloysite nanotubes are added into reactive diluent, while carrying out 700KW ultrasonic vibration and 1000r/min machinery stirs
It mixes, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, 1500r/min is mechanical at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical stirring 2 hours at 25 DEG C obtain angstrom Lip river
Stone nanotube compound resin.
The scanning electron microscope (SEM) of halloysite nanotubes dispersion in halloysite nanotubes compound resin obtained by the present embodiment
Figure is as shown in Figure 1.As seen from Figure 1, halloysite nanotubes are well dispersed in compound resin.
Embodiment 2
A kind of halloysite nanotubes compound resin for photocuring 3D printing of the present embodiment, by following parts by weight meter
Raw material composition: 6 30 parts of degree of functionality urethane acrylates, 30 parts of 2 degree of functionality urethane acrylate, trimethylolpropane tris
20 parts of acrylate TMPTA, 20 parts of acryloyl morpholine ACMO, 2 parts of photoinitiator TPO, 1.5 parts of halloysite nanotubes.
The preparation method is as follows:
Halloysite nanotubes are added into reactive diluent, while carrying out 700KW ultrasonic vibration and 1000r/min machinery stirs
It mixes, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, 1500r/min is mechanical at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical stirring 2 hours at 25 DEG C obtain angstrom Lip river
Stone nanotube compound resin.
Embodiment 3
A kind of halloysite nanotubes compound resin for photocuring 3D printing of the present embodiment, by following parts by weight meter
Raw material composition: 6 30 parts of degree of functionality urethane acrylates, 30 parts of 2 degree of functionality urethane acrylate, trimethylolpropane tris
20 parts of acrylate TMPTA, 20 parts of acryloyl morpholine ACMO, 2 parts of photoinitiator TPO, 3.5 parts of halloysite nanotubes.
The preparation method is as follows:
Halloysite nanotubes are added into reactive diluent, while carrying out 700KW ultrasonic vibration and 1000r/min machinery stirs
It mixes, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, 1500r/min is mechanical at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical stirring 2 hours at 25 DEG C obtain angstrom Lip river
Stone nanotube compound resin.
Embodiment 4
A kind of halloysite nanotubes compound resin for photocuring 3D printing of the present embodiment, by following parts by weight meter
Raw material composition: 6 10 parts of degree of functionality urethane acrylates, 10 parts of 2 degree of functionality urethane acrylate, trimethylolpropane tris
40 parts of acrylate TMPTA, 40 parts of acryloyl morpholine ACMO, 1 part of photoinitiator TPO, 1 part of halloysite nanotubes.
Halloysite nanotubes are added into reactive diluent, while carrying out 700KW ultrasonic vibration and 1000r/min machinery stirs
It mixes, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, 1500r/min is mechanical at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical stirring 2 hours at 25 DEG C obtain angstrom Lip river
Stone nanotube compound resin.
Embodiment 5
A kind of halloysite nanotubes compound resin for photocuring 3D printing of the present embodiment, by following parts by weight meter
Raw material composition: 6 20 parts of degree of functionality urethane acrylates, 20 parts of 2 degree of functionality urethane acrylate, trimethylolpropane tris
30 parts of acrylate TMPTA, 30 parts of acryloyl morpholine ACMO, 1 part of photoinitiator TPO, 1 part of halloysite nanotubes.
Halloysite nanotubes are added into reactive diluent, while carrying out 700KW ultrasonic vibration and 1000r/min machinery stirs
It mixes, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, 1500r/min is mechanical at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical stirring 2 hours at 25 DEG C obtain angstrom Lip river
Stone nanotube compound resin.
Comparative example
Compared with Example 1, the difference is that not adding halloysite nanotubes, other components and preparation method are identical,
Obtain the composite material of this comparative example.
Exist according to GB/T 9341-2008, GB/T 1040.2-2006 to composite material obtained by Examples 1 to 3 and comparative example
Mechanical test batten is printed on DLP printer and carries out mechanical test, and test result is as shown in table 1.
The mechanical property of the halloysite nanotubes compound resin of 1 photocuring 3D printing of table
The polyurethane acrylate resin mechanical property that halloysite nanotubes are added to it can be seen from 1 result of table obtains
It is obviously improved.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. a kind of halloysite nanotubes compound resin, it is characterised in that the compound resin is grouped as by the group of following mass parts:
20~60 parts of polyurethane acrylate resin, 40~80 parts of reactive diluent, 0.5~2 part of radical photoinitiator, galapectite
1~5 part of nanotube；The reactive diluent is the mixing of trimethylolpropane trimethacrylate and acryloyl morpholine.
2. a kind of halloysite nanotubes compound resin according to claim 1, it is characterised in that: the polyurethane acroleic acid
The degree of functionality of ester resin is 2~6, and viscosity is 200~10000mPa.s.
3. a kind of halloysite nanotubes compound resin according to claim 1, it is characterised in that: the free radical type light draws
Hair agent is 1- hydroxycyclohexyl phenyl ketone, 2- hydroxyl -4- (2- hydroxy ethoxy) -2- methyl phenyl ketone, phenyl bis- (2,4,6- tri-
Methyl benzoyl) phosphine oxide, at least one of (2,4,6- trimethylbenzoyl) diphenyl phosphine oxide.
4. a kind of halloysite nanotubes compound resin according to claim 3, it is characterised in that: the free radical type light draws
Hair agent is (2,4,6- trimethylbenzoyl) diphenyl phosphine oxide.
5. a kind of described in any item preparation methods of halloysite nanotubes compound resin of Claims 1 to 4, it is characterised in that packet
Include following preparation step:
By halloysite nanotubes, ultrasonic disperse and mechanical stirring are uniform in reactive diluent, and urethane acrylate is then added
Resin machinery stirs evenly, and adds radical photoinitiator mechanical stirring and is uniformly dissolved, obtains the halloysite nanotubes
Compound resin.
6. a kind of described in any item halloysite nanotubes compound resins of Claims 1 to 4 are as photocuring 3D printing material
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710285468.3A CN107141418B (en) | 2017-04-27 | 2017-04-27 | A kind of halloysite nanotubes compound resin and its application as photocuring 3D printing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710285468.3A CN107141418B (en) | 2017-04-27 | 2017-04-27 | A kind of halloysite nanotubes compound resin and its application as photocuring 3D printing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107141418A CN107141418A (en) | 2017-09-08 |
| CN107141418B true CN107141418B (en) | 2019-01-29 |
Family
ID=59773934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710285468.3A Active CN107141418B (en) | 2017-04-27 | 2017-04-27 | A kind of halloysite nanotubes compound resin and its application as photocuring 3D printing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107141418B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880223B (en) * | 2017-11-16 | 2019-12-24 | 浙江维彬三维科技有限公司 | 3D printing resin with rapid curing and low shrinkage rate |
| CN113861359B (en) * | 2021-10-11 | 2024-01-30 | 中国电建集团中南勘测设计研究院有限公司 | Modified halloysite nanotube, photo-curing lining material, and preparation methods and applications thereof |
| CN114656597A (en) * | 2022-02-28 | 2022-06-24 | 深圳锐沣科技有限公司 | Washable DLP3D printing dental cast resin |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634242A (en) * | 2012-04-18 | 2012-08-15 | 天津大学 | Method for preparing composite material by modifying halloysite nanotube and compounding waterborne polyurethane |
| CN103819656B (en) * | 2014-02-18 | 2017-06-23 | 青岛科技大学 | A kind of graphene oxide/light-cured resin composite and its preparation method and application |
| CN104861145A (en) * | 2015-05-06 | 2015-08-26 | 上海应用技术学院 | Polyurethane elastomer/ halloysite nanotube composite material and preparation method thereof |
| CN105199340A (en) * | 2015-10-19 | 2015-12-30 | 福建师范大学 | PBS (poly butylenes succinate)/halloysite nanotubes composite wire for 3D printing and preparation method of PBS/halloysite nanotubes composite wire |
-
2017
- 2017-04-27 CN CN201710285468.3A patent/CN107141418B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107141418A (en) | 2017-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107141418B (en) | A kind of halloysite nanotubes compound resin and its application as photocuring 3D printing material | |
| Salavagione et al. | Recent advances in the covalent modification of graphene with polymers | |
| CN101343386B (en) | Preparation method for rubber/keramite nano-tube nano-composite material | |
| CN108546393A (en) | A kind of resistance to ultralow temperature 3D printing photosensitive nanocomposite and its preparation | |
| US11385541B2 (en) | Radiation-curable resin composition and production method thereof | |
| CN1288206C (en) | Epoxy resin/montmorillonoid nano-compoiste-material and its preparation method | |
| EP2514728A1 (en) | Concrete reinforced with hybrid nanomaterials | |
| CN102295823B (en) | Epoxy resin lightweight high-strength composite material easy to disperse carbon nano-tubes, and preparation method thereof | |
| CN108046665A (en) | A kind of micro-nano composite hollow structure nano material modification high durability concrete material and preparation method thereof | |
| CN107189385A (en) | A kind of graphene 3D printing material of high intensity | |
| CN108314876B (en) | A kind of grinding and polishing graphene/epoxy resin composite material preparation method | |
| CN107353397A (en) | A kind of graphene water-base epoxy high dispersive system and its synthetic method | |
| CN110396266A (en) | 3D printing photosensitive resin | |
| CN105199640A (en) | Method for improving mechanical properties of epoxy resin adhesive by using activated calcium carbonate whisker | |
| CN108148354A (en) | A kind of hybrid particle modified polymer composites of self assembly and preparation method thereof | |
| CN1850694A (en) | Gypsum base material system for 3-D spraying binding and preparing method therefor | |
| CN1121450C (en) | Nm-class unsaturated polyester/montmorillonite composition and its preparing process | |
| CN112724605B (en) | Photosensitive resin composition for photocuring rapid prototyping and preparation method and application thereof | |
| Xing et al. | Effect of organic polymers on mechanical property and toughening mechanism of slag geopolymer matrix | |
| Bhatrola et al. | An updated review on scientometric analysis and physico-mechanical performance of nanomaterials in cementitious composites | |
| CN101891936A (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN111018403A (en) | Nano titanium dioxide ceramic paste for photocuring and preparation method thereof | |
| CN112480329A (en) | Light-cured resin model material based on DLP (digital light processing) type 3D printing and preparation method thereof | |
| CN1423075A (en) | Rubber sealing washer and method of manufacturing the same | |
| CN113416383B (en) | Flexible linear polymer and inorganic nanoparticle composite modified graphene oxide-epoxy resin composite material and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |