CN107141418A - 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
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- CN107141418A CN107141418A CN201710285468.3A CN201710285468A CN107141418A CN 107141418 A CN107141418 A CN 107141418A CN 201710285468 A CN201710285468 A CN 201710285468A CN 107141418 A CN107141418 A CN 107141418A
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- Prior art keywords
- halloysite nanotubes
- compound resin
- parts
- photocuring
- resin
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Links
- 239000002071 nanotube Substances 0.000 title claims abstract description 58
- 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 51
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 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 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 14
- 238000013019 agitation Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical group C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 238000003756 stirring Methods 0.000 claims description 11
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical group C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- XHIKSLHIZYVEQI-UHFFFAOYSA-N CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C Chemical compound CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C XHIKSLHIZYVEQI-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 10
- 206010001497 Agitation Diseases 0.000 description 8
- 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
- 239000007983 Tris buffer Substances 0.000 description 5
- 238000005516 engineering process Methods 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000010276 construction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 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
- 230000009286 beneficial effect Effects 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
- 230000008859 change Effects 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
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 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
- 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
Abstract
The invention belongs to technical field of composite materials, a kind of halloysite nanotubes compound resin and its application as photocuring 3D printing material are disclosed.The compound resin is made up of the component 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.Its preparation method is：By halloysite nanotubes, ultrasonic disperse and mechanical agitation are uniform in reactive diluent, then add polyurethane acrylate resin mechanical agitation uniformly, add radical photoinitiator mechanical agitation and be uniformly dissolved, obtain the halloysite nanotubes compound resin.The present invention prepares the compound resin suitable for photocuring 3D printing using polyurethane acrylate resin and halloysite nanotubes, with excellent mechanical property, has further widened the application 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 be used as light
Solidify the application of 3D printing material.
Background technology
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, its operation principle both at home and abroad
It is the three-dimensional digital model formed using scanning, according to the principle of " 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.The raw material that SLA is mainly used is
Ultraviolet curable resin, is to carry out successively scanning and exposing on photosensitive resin surface by UV laser beam, is scanned and exposed region
Resin bed occur photopolymerization reaction and final solidified forming.
But, the photocurable resin material generally existing mechanical property used at present is poor, easily bending cracking, and hardness is inclined
Low problem, these problems limit the popularization of photocuring 3D printing rapid shaping technique.
Polyurethane acrylate resin has preferably combination property.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 pliability after solidification, elongation at break is high, while having good
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.HNTs 40~100nm of general pipe external diameter, length is about 0.2~2um.HNTs is double deck type aluminosilicate, by internal layer alumina
The silicon-oxy tetrahedron lattice mismatch curling of octahedra and outer layer is formed, and its interlayer has the crystallization water.HNTs outer surface is mainly
It is made up of Si-O-Si keys, inwall is then mainly the light base of aluminium.There is sial hydroxyl on the end face of halloysite nanotubes, and in crystalline substance
There is also a small amount of embedding hydroxyl for the inwall of body.HNTs agglomerations are relatively weak, the hydroxyl and content of siloxane on HNTs surfaces
It is relatively fewer, combined between construction unit in the form of the secondary bond such as hydrogen bond and Van der Waals force, be easier to realize construction unit
Dissociate and scattered, it is not easy to reunite；And between nanotube, the appropriate tube-like condition of its aspect ratio reduces connecing between pipe
Contacting surface is accumulated.Therefore, the HNTs with longer draw ratio can be evenly dispersed in polymer, is to prepare high-performance polymer to receive
The new cheap Nano filling of nano composite material.
The content of the invention
In place of the shortcoming and defect existed for prior art, primary and foremost purpose of the invention is that providing a kind of galapectite receives
Mitron compound resin.
Another object of the present invention is to provide the preparation method of above-mentioned halloysite nanotubes compound resin.
Photocuring 3D printing material is used as it is still another object of the present invention to provide above-mentioned halloysite nanotubes compound resin
Application.
The object of the invention is achieved through the following technical solutions：
A kind of halloysite nanotubes compound resin, is made up of the component 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), GMA (GMA), three
At least one of hydroxymethyl-propane triacrylate (TMPTA) and trimethylol-propane trimethacrylate (TMPTMA)；
The more preferably mixing of trimethylolpropane trimethacrylate (TMPTA) and acryloyl morpholine (ACMO).
Preferably, the radical photoinitiator is 1- hydroxycyclohexyl phenyl ketones (light trigger 184), 2- hydroxyls
Base -4- (2- hydroxy ethoxies) -2- methyl phenyl ketones (light trigger 2959), phenyl double (2,4,6- trimethylbenzoyls) oxidation
At least one of phosphine (light trigger 819), (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide (light trigger TPO)；
More preferably (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide (light trigger TPO).
The preparation method of above-mentioned halloysite nanotubes compound resin, including following preparation process：
By halloysite nanotubes, ultrasonic disperse and mechanical agitation are uniform in reactive diluent, then add polyurethane propylene
Acid ester resin mechanical agitation is uniform, adds radical photoinitiator mechanical agitation and is uniformly dissolved, obtains the galapectite and receive
Mitron compound resin.
Above-mentioned halloysite nanotubes compound resin as photocuring 3D printing material application.
The preparation method and resulting product of the present invention has the following advantages that and beneficial effect：
The present invention prepares answering suitable for photocuring 3D printing using polyurethane acrylate resin and halloysite nanotubes
Resin, with excellent mechanical property, has further widened the application of photocuring 3D printing technique.
Brief description of the drawings
Fig. 1 is that halloysite nanotubes deployment conditions are swept in the embodiment of the present invention 1 gained halloysite nanotubes compound resin
Retouch Electronic Speculum (SEM) figure.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
A kind of halloysite nanotubes compound resin for photocuring 3D printing of the present embodiment, it is 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 light trigger TPO, 2.5 parts of halloysite nanotubes.
Preparation method is as follows：
Halloysite nanotubes are added into reactive diluent, while progress 700KW ultrasonic vibrations and 1000r/min machineries are stirred
Mix, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, the 1500r/min machineries at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical agitations 2 hours at 25 DEG C obtain angstrom Lip river
Stone nanotube compound resin.
The ESEM (SEM) of halloysite nanotubes deployment conditions 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, it is 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 light trigger TPO, 1.5 parts of halloysite nanotubes.
Preparation method is as follows：
Halloysite nanotubes are added into reactive diluent, while progress 700KW ultrasonic vibrations and 1000r/min machineries are stirred
Mix, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, the 1500r/min machineries at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical agitations 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, it is 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 light trigger TPO, 3.5 parts of halloysite nanotubes.
Preparation method is as follows：
Halloysite nanotubes are added into reactive diluent, while progress 700KW ultrasonic vibrations and 1000r/min machineries are stirred
Mix, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, the 1500r/min machineries at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical agitations 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, it is 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 light trigger TPO, 1 part of halloysite nanotubes.
Halloysite nanotubes are added into reactive diluent, while progress 700KW ultrasonic vibrations and 1000r/min machineries are stirred
Mix, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, the 1500r/min machineries at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical agitations 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, it is 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 light trigger TPO, 1 part of halloysite nanotubes.
Halloysite nanotubes are added into reactive diluent, while progress 700KW ultrasonic vibrations and 1000r/min machineries are stirred
Mix, temperature is 40 DEG C, and stirring continues 2 hours.Then polyurethane acrylate resin is added, the 1500r/min machineries at 40 DEG C
Stirring 2 hours.Radical photoinitiator is added, 1000r/min mechanical agitations 2 hours at 25 DEG C obtain angstrom Lip river
Stone nanotube compound resin.
Comparative example
Compared with Example 1, difference is that, without halloysite nanotubes, other components and preparation method are identical,
Obtain the composite of this comparative example.
Composite obtained by embodiment 1~3 and comparative example is existed according to GB/T 9341-2008, GB/T 1040.2-2006
Mechanical test batten is printed on DLP printers and mechanical test is carried out, test result is as shown in table 1.
The mechanical property of the halloysite nanotubes compound resin of the photocuring 3D printing of table 1
The polyurethane acrylate resin mechanical property that halloysite nanotubes are with the addition of it can be seen from the result of table 1 is obtained
It is obviously improved.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of halloysite nanotubes compound resin, it is characterised in that the compound resin is made up of the component 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.
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 reactive diluent is
Acryloyl morpholine, GMA, trimethylolpropane trimethacrylate and trimethylol propane trimethyl third
At least one of olefin(e) acid ester.
4. a kind of halloysite nanotubes compound resin according to claim 3, it is characterised in that：The reactive diluent is
The mixing of trimethylolpropane trimethacrylate and acryloyl morpholine.
5. 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 ketones, 2- hydroxyls -4- (2- hydroxy ethoxies) -2- methyl phenyl ketones, phenyl double (2,4,6- tri-
Methyl benzoyl) phosphine oxide, at least one of (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide.
6. a kind of halloysite nanotubes compound resin according to claim 5, it is characterised in that：The free radical type light draws
Hair agent is (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide.
7. a kind of preparation method of halloysite nanotubes compound resin described in any one of claim 1~6, it is characterised in that bag
Include following preparation process：
By halloysite nanotubes, ultrasonic disperse and mechanical agitation are uniform in reactive diluent, then add urethane acrylate
Resin machinery stirs, and adds radical photoinitiator mechanical agitation and is uniformly dissolved, obtains the halloysite nanotubes
Compound resin.
8. a kind of halloysite nanotubes compound resin described in any one of claim 1~6 is used 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 |
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| 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 |
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| Publication Number | Publication Date |
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| CN107141418A true CN107141418A (en) | 2017-09-08 |
| CN107141418B CN107141418B (en) | 2019-01-29 |
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| 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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880223A (en) * | 2017-11-16 | 2018-04-06 | 杭州维彬科技有限公司 | A kind of 3D printing resin of novel fast curing, low-shrinkage |
| CN113861359A (en) * | 2021-10-11 | 2021-12-31 | 中国电建集团中南勘测设计研究院有限公司 | Modified halloysite nanotube, photocuring lining material, and preparation methods and applications thereof |
Citations (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 |
| CN103819656A (en) * | 2014-02-18 | 2014-05-28 | 青岛科技大学 | 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
Patent Citations (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 |
| CN103819656A (en) * | 2014-02-18 | 2014-05-28 | 青岛科技大学 | 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880223A (en) * | 2017-11-16 | 2018-04-06 | 杭州维彬科技有限公司 | A kind of 3D printing resin of novel fast curing, low-shrinkage |
| 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 |
| CN113861359A (en) * | 2021-10-11 | 2021-12-31 | 中国电建集团中南勘测设计研究院有限公司 | Modified halloysite nanotube, photocuring lining material, and preparation methods and applications thereof |
| 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 |
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