CN112409779A - 3D printing photosensitive composite material and preparation method and application thereof - Google Patents
3D printing photosensitive composite material and preparation method and application thereof Download PDFInfo
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- CN112409779A CN112409779A CN202011205711.4A CN202011205711A CN112409779A CN 112409779 A CN112409779 A CN 112409779A CN 202011205711 A CN202011205711 A CN 202011205711A CN 112409779 A CN112409779 A CN 112409779A
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- 238000010146 3D printing Methods 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 229920001971 elastomer Polymers 0.000 claims abstract description 46
- 239000005060 rubber Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 13
- 238000010008 shearing Methods 0.000 claims description 13
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- 229920002943 EPDM rubber Polymers 0.000 claims description 7
- 229920002379 silicone rubber Polymers 0.000 claims description 7
- 239000004945 silicone rubber Substances 0.000 claims description 7
- 229920005549 butyl rubber Polymers 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000005077 polysulfide Substances 0.000 claims description 5
- 229920001021 polysulfide Polymers 0.000 claims description 5
- 150000008117 polysulfides Polymers 0.000 claims description 5
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000005062 Polybutadiene Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- RUNBDQGENXJZOO-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]hept-5-ene-3,4-dicarboxylate Chemical compound C1C2OC2=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 RUNBDQGENXJZOO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
Abstract
The invention discloses a 3D printing photosensitive composite material and a preparation method thereof, wherein sulfydryl in sulfydryl modified rubber is used for reacting with double bonds and epoxy groups in photosensitive resin, so that the compatibility and interface effect between the rubber and the resin are improved, the enhancement and toughening effects of the rubber are conveniently and fully exerted, the toughness, tensile strength and impact strength of the cured photosensitive composite material are effectively increased, the method has the advantages of easily obtained raw materials, fewer modification process steps and accordance with the green chemical principle, and the prepared 3D printing photosensitive composite material can be widely applied to the technical field of rapid forming.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a 3D printing photosensitive composite material and a preparation method and application thereof.
Background
The 3D printing technology is also called a rapid prototyping technology or an additive manufacturing technology, and is currently widely used in various fields such as medical treatment, bioengineering, aerospace, and the like. Compared with the traditional material reduction manufacturing, the 3D printing improves the utilization rate of materials, reduces the cost, can manufacture a workpiece with extremely high precision through computer simulation design, and can shorten the production time while ensuring the quality. However, at present, the 3D printing photosensitive resin is often a brittle material with higher strength and weaker toughness after photocuring, which limits the application range. In order to increase the toughness of the 3D printing photosensitive resin, the filler can be doped into the resin, so that the resin cost can be reduced while the reinforcing and toughening effects (tensile strength, impact strength and toughness) are achieved.
For example, chinese patent CN105175651A (published japanese 2015.12.23) discloses a 3D printing photosensitive resin material containing solid rubber and a preparation method thereof, wherein natural rubber is used to modify photosensitive resin, so that the unique toughness of natural rubber can be exerted, but the compatibility between rubber and 3D printing photosensitive resin is a problem, and thus the reinforcing and toughening effects of photosensitive resin are not ideal.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects and defects of poor tensile strength, impact strength and toughness of the conventional 3D printing photosensitive resin, and provides a 3D printing photosensitive composite material, which improves the compatibility and interface action of rubber and photosensitive resin by utilizing the reaction of sulfydryl in sulfydryl modified rubber and double bonds and epoxy groups in the photosensitive resin, and simultaneously improves the tensile strength, impact strength and toughness of the 3D printing composite material.
The invention further aims to provide a preparation method of the 3D printing photosensitive composite material.
Another object of the present invention is to provide an application of the photosensitive composite material for 3D printing.
The above purpose of the invention is realized by the following technical scheme:
the 3D printing photosensitive composite material comprises the following components in parts by mass:
80-100 parts of photosensitive resin;
1-20 parts of sulfydryl modified rubber.
The invention utilizes the reaction of sulfydryl in the sulfydryl modified rubber and double bonds and epoxy groups in the photosensitive resin, thereby increasing the compatibility and interface action of the rubber and the photosensitive resin, and simultaneously, the sulfydryl modified rubber also serves as ductile particles in a system to form a uniform interface, thereby increasing the tensile strength, impact strength and toughness of the composite system.
Preferably, the composition is prepared from the following components in parts by mass:
90-100 parts of photosensitive resin;
2-10 parts of sulfydryl modified rubber.
Preferably, the raw materials for preparing the mercapto-modified rubber comprise 80-100 parts by mass of rubber and 20-60 parts by mass of a multi-mercapto compound.
Preferably, the raw materials for preparing the mercapto-modified rubber further comprise 0.5-5 parts of a catalyst.
Preferably, the rubber is one or more of natural rubber, nitrile rubber, styrene butadiene rubber, butyl rubber, chloroprene rubber, ethylene propylene diene monomer rubber, isoprene rubber and vinyl silicone rubber.
Preferably, the multi-mercapto compound is one or more of a multi-mercapto aliphatic compound, a multi-mercapto aromatic compound, polysulfide rubber and pentaerythritol tetra-3-mercaptopropionate.
Preferably, the catalyst is one or more of 1, 8-diazabicycloundec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, N-dimethyl-1, 3-propanediamine and 4-dimethylaminopyridine.
Specifically, the preparation method of the mercapto-modified rubber comprises the following steps: banburying rubber and a multi-mercapto compound at 40-80 ℃ for 5-10 min, then adding 0.5-5 parts of a catalyst, banburying for 5-20 min, and cooling to obtain the mercapto modified rubber. The invention utilizes unsaturated double bonds in rubber and sulfydryl in a multi-sulfydryl compound to graft sulfydryl on the surface of the rubber through a sulfydryl-alkene Michael addition reaction to prepare the sulfydryl modified rubber.
The invention protects the preparation method of the 3D printing photosensitive composite material, which comprises the following steps:
and uniformly mixing the photosensitive resin and the mercapto modified rubber, and shearing and dispersing for 10-30 min to obtain the 3D printing photosensitive composite material.
The invention also protects the application of the 3D printing photosensitive composite material in the rapid prototyping technology.
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes the reaction of sulfydryl in sulfydryl modified rubber and double bonds and epoxy groups in resin to improve the compatibility and interface action between the rubber and the resin, thereby being convenient for fully playing the reinforcing and toughening effects of the rubber, effectively increasing the toughness, tensile strength and impact strength of the cured photosensitive composite material, having easily obtained raw materials and fewer modification process steps, conforming to the green chemical principle, and being capable of being widely applied to the technical field of rapid forming.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The photosensitive resins described in the respective examples and comparative examples were prepared by the following methods:
50 parts of polyurethane acrylate, 25 parts of 4, 5-epoxy tetrahydrophthalic acid diglycidyl ester, 1.5 parts of 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 3.5 parts of diphenyl iodohexafluorophosphate and 25 parts of isobornyl methacrylate are dispersed for 15min at room temperature by a high-speed dispersion machine to obtain the photocuring 3D printing photosensitive resin.
Example 1
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
2 parts of mercapto-modified nitrile rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of nitrile rubber and 40 parts of pentaerythritol tetra-3-mercaptopropionate into an internal mixer, carrying out internal mixing for 5min at 50 ℃, then adding 2 parts of 1, 8-diazabicycloundec-7-ene, carrying out internal mixing for 5min, and cooling a reaction system to room temperature to obtain mercapto-modified nitrile rubber; taking 100 parts of photosensitive resin and 2 parts of mercapto-modified nitrile rubber, mixing the mercapto-modified nitrile rubber into the photosensitive resin, and carrying out high-speed shearing and dispersion for 15min to obtain the 3D printing photosensitive composite material.
Example 2
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
2 parts of mercapto-modified nitrile rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of nitrile rubber and 80 parts of pentaerythritol tetra-3-mercaptopropionate into an internal mixer, carrying out internal mixing for 5min at 50 ℃, then adding 2 parts of 1, 8-diazabicycloundec-7-ene, carrying out internal mixing for 5min, and cooling a reaction system to room temperature to obtain mercapto-modified nitrile rubber; taking 100 parts of photosensitive resin and 2 parts of mercapto-modified nitrile rubber, mixing the mercapto-modified nitrile rubber into the photosensitive resin, and carrying out high-speed shearing and dispersion for 15min to obtain the 3D printing photosensitive composite material.
Example 3
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
2 parts of mercapto-modified nitrile rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of nitrile rubber and 120 parts of pentaerythritol tetra-3-mercaptopropionate into an internal mixer, carrying out internal mixing for 5min at 50 ℃, then adding 2 parts of 1, 8-diazabicycloundec-7-ene, carrying out internal mixing for 5min, and cooling a reaction system to room temperature to obtain mercapto-modified nitrile rubber; taking 100 parts of photosensitive resin and 2 parts of mercapto-modified nitrile rubber, mixing the mercapto-modified nitrile rubber into the photosensitive resin, and carrying out high-speed shearing and dispersion for 15min to obtain the 3D printing photosensitive composite material.
Example 4
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
5 parts of mercapto-modified nitrile rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of nitrile rubber and 40 parts of pentaerythritol tetra-3-mercaptopropionate into an internal mixer, carrying out internal mixing for 5min at 50 ℃, then adding 2 parts of 1, 8-diazabicycloundec-7-ene, carrying out internal mixing for 5min, and cooling a reaction system to room temperature to obtain mercapto-modified nitrile rubber; taking 100 parts of photosensitive resin and 5 parts of mercapto-modified nitrile rubber, mixing the mercapto-modified nitrile rubber into the photosensitive resin, and carrying out high-speed shearing and dispersion for 15min to obtain the 3D printing photosensitive composite material.
Example 5
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
10 parts of mercapto-modified nitrile rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of nitrile rubber and 40 parts of pentaerythritol tetra-3-mercaptopropionate into an internal mixer, carrying out internal mixing for 5min at 50 ℃, then adding 2 parts of 1, 8-diazabicycloundec-7-ene, carrying out internal mixing for 5min, and cooling a reaction system to room temperature to obtain mercapto-modified nitrile rubber; taking 100 parts of photosensitive resin and 10 parts of mercapto-modified nitrile rubber, mixing the mercapto-modified nitrile rubber into the photosensitive resin, and carrying out high-speed shearing and dispersion for 15min to obtain the 3D printing photosensitive composite material.
Example 6
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
25 parts of mercapto-modified nitrile rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of nitrile rubber and 40 parts of pentaerythritol tetra-3-mercaptopropionate into an internal mixer, carrying out internal mixing for 5min at 50 ℃, then adding 2 parts of 1, 8-diazabicycloundec-7-ene, carrying out internal mixing for 5min, and cooling a reaction system to room temperature to obtain mercapto-modified nitrile rubber; taking 100 parts of photosensitive resin and 25 parts of mercapto-modified nitrile rubber, mixing the mercapto-modified nitrile rubber into the photosensitive resin, and carrying out high-speed shearing and dispersion for 15min to obtain the 3D printing photosensitive composite material.
Example 7
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
10 parts of sulfydryl modified butadiene rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of butadiene rubber and 80 parts of polysulfide rubber (JLY-121) into an internal mixer, carrying out internal mixing for 10min at 45 ℃, then adding 1 part of N, N-dimethyl-1, 3-propane diamine, carrying out internal mixing for 3min, and cooling a reaction system to room temperature to obtain sulfydryl modified butadiene rubber; taking 100 parts of photosensitive resin and 10 parts of sulfydryl modified butadiene rubber, mixing the sulfydryl modified butadiene rubber into the photosensitive resin, and shearing and dispersing at high speed for 10min to obtain the 3D printing photosensitive composite material.
Example 8
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
10 parts of mercapto-modified silicone rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of vinyl silicone rubber and 20 parts of polysulfide rubber (JLY-121) into an internal mixer, carrying out internal mixing for 5min at 60 ℃, then adding 0.5 part of 1, 5-diazabicyclo [4.3.0] non-5-ene, carrying out internal mixing for 5min, and cooling a reaction system to room temperature to obtain mercapto-modified silicone rubber; taking 100 parts of photosensitive resin and 10 parts of mercapto-modified silicone rubber, mixing the mercapto-modified silicone rubber into the photosensitive resin, and shearing and dispersing at high speed for 20min to obtain the 3D printing photosensitive composite material.
Example 9
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
10 parts of mercapto-modified butyl rubber.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of butyl rubber and 25 parts of polysulfide rubber (JLY-121) into an internal mixer, carrying out internal mixing for 10min at 70 ℃, then adding 1.5 parts of 1, 5-diazabicyclo [4.3.0] non-5-ene, carrying out internal mixing for 12min, and cooling a reaction system to room temperature to obtain sulfydryl modified butyl rubber; and mixing 100 parts of photosensitive resin and 8 parts of mercapto-modified butyl rubber into the photosensitive resin, and shearing and dispersing at high speed for 15min to obtain the 3D printing photosensitive composite material.
Example 10
The 3D printing photosensitive composite material comprises the following components in parts by mass:
100 parts of photosensitive resin;
10 parts of mercapto-modified ethylene propylene diene monomer.
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
adding 100 parts of ethylene propylene diene monomer and 30 parts of pentaerythritol tetra-3-mercaptopropionate into an internal mixer, carrying out internal mixing for 13min at 80 ℃, then adding 2.5 parts of 1, 8-diazabicycloundecen-7-ene, carrying out internal mixing for 15min, and cooling a reaction system to room temperature to obtain mercapto-modified ethylene propylene diene monomer; and mixing 100 parts of photosensitive resin and 7.5 parts of mercapto-modified ethylene propylene diene monomer, and mixing the mercapto-modified ethylene propylene diene monomer into the photosensitive resin, and shearing and dispersing at a high speed for 20min to obtain the 3D printing photosensitive composite material.
Example 11
The composition of the 3D printing photosensitive composite material of the present example was the same as that of example 1 except that the photosensitive resin was replaced with 80 parts.
Example 12
The composition of the 3D printing photosensitive composite material of this example was the same as example 1 except that the photosensitive resin was replaced with 90 parts and the mercapto-modified nitrile rubber was replaced with 1 part.
Comparative example 1
This comparative example is a photosensitive resin which had not been subjected to modification treatment.
Comparative example 2
The preparation method of the 3D printing photosensitive composite material comprises the following steps:
banburying 100 parts of nitrile rubber at 50 ℃ for 10min, and cooling a reaction system to room temperature to obtain unmodified nitrile rubber; taking 100 parts of photosensitive resin and 5 parts of unmodified nitrile rubber, mixing the unmodified nitrile rubber into the photosensitive resin, and carrying out high-speed shearing and dispersion for 15min to obtain the 3D printing photosensitive composite material.
Performance testing
The prepared product is printed and cured through 3D, and the 3D printing specifically comprises the following operations:
using a Form 2 desktop level 3D printer from Formlabs, USA, the basic parameters are: the laser wavelength is 405nm, the laser spot size is 140 mu m, and the layer thickness is 100 mu m; after printing is finished, the resin adhered to the surface of the device is cleaned by absolute ethyl alcohol, and then post-curing is carried out for 15min in a 405nm ultraviolet curing box, so that the 3D printing sample can be obtained.
1. Test method
(1) Tensile strength
After the prepared product is solidified through 3D printing, a standard dumbbell-mounted tensile sample is obtained, the sample is subjected to tensile test by adopting a CMT4204 type microcomputer controlled electronic universal testing machine of the American Industrial System (China) Limited company, the tensile rate is 50mm/s, the test is carried out for five times in parallel, and the tensile strength is obtained by taking the average value.
(2) Impact strength
After the prepared product is solidified through 3D printing, the standard punch is obtainedImpacting a sample, and testing the impact strength by using a GC-XBL-5.5D type digital display cantilever beam impact tester of a wide-range instrument, wherein the size of the sample is (80 multiplied by 10 multiplied by 4) mm3The method comprises the steps of testing the impact strength of a sample by using a pendulum impact tester, selecting a cantilever beam mode, wherein the sample is a notch sample, the impact energy is 5.5J, and the execution standard is GB/T1843-.
(3) Elongation at break
After the prepared product is solidified through 3D printing, a standard dumbbell-mounted tensile sample is obtained, the tensile test is carried out on the sample by adopting a CMT4204 type microcomputer controlled electronic universal testing machine of the Meister Industrial System (China) Limited company, the tensile rate is 50mm/s, the sample is tested for five times in parallel, and the breaking elongation is obtained by taking the average value.
2. Test results
TABLE 2 product Performance test results of examples and comparative examples
The results in table 2 show that the products obtained after curing the 3D printing photosensitive resins prepared in examples 1 to 12 of the present invention all have better tensile strength, impact strength and toughness, while comparative example 1 is a photosensitive resin without rubber modification, comparative example 2 is a photosensitive composite material toughened by unmodified rubber, and comparative example 1 is compared with comparative example 2, which proves that the strength and toughness of the photosensitive resin can be improved to a certain extent by adding the non-mercapto-modified rubber, but the results of comparative example 2 and examples 1 to 12 show that the reinforcing and toughening effects of the non-mercapto-modified rubber are far less than those of the mercapto-modified rubber.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The 3D printing photosensitive composite material is characterized by comprising the following components in parts by mass:
80-100 parts of photosensitive resin;
1-20 parts of sulfydryl modified rubber.
2. The 3D printing photosensitive composite material according to claim 1, comprising the following components in parts by mass:
90-100 parts of photosensitive resin;
2-10 parts of sulfydryl modified rubber.
3. The 3D printing photosensitive composite material according to claim 1 or 2, wherein raw materials for preparing the mercapto-modified rubber comprise 80-100 parts by mass of rubber and 20-60 parts by mass of a multi-mercapto compound.
4. The 3D printing photosensitive composite material according to claim 3, wherein the raw material for preparing the mercapto-modified rubber further comprises 0.5-5 parts of a catalyst.
5. The 3D printing photosensitive composite material according to claim 3, wherein the rubber is one or more of natural rubber, nitrile rubber, styrene butadiene rubber, butyl rubber, chloroprene rubber, ethylene propylene diene monomer rubber, isoprene rubber and vinyl silicone rubber.
6. The 3D printing photosensitive composite of claim 3, wherein the multi-thiol compound is one or more of a multi-thiol aliphatic compound, a multi-thiol aromatic compound, a polysulfide rubber, and pentaerythritol tetra-3-mercaptopropionate.
7. The 3D printing photosensitive composite according to claim 4, wherein the catalyst is one or more of 1, 8-diazabicycloundecen-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, N-dimethyl-1, 3-propanediamine, 4-dimethylaminopyridine.
8. The 3D printing photosensitive composite material according to claim 3, wherein the mercapto-modified rubber is prepared by a method comprising: banburying rubber and a multi-mercapto compound at 40-80 ℃ for 5-10 min, then adding 0.5-5 parts of a catalyst, banburying for 5-20 min, and cooling to obtain the mercapto modified rubber.
9. The preparation method of the 3D printing photosensitive composite material as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
and uniformly mixing the photosensitive resin and the mercapto modified rubber, and shearing and dispersing for 10-30 min to obtain the 3D printing photosensitive composite material.
10. Use of the 3D printed photosensitive composite of any of claims 1 to 8 in the field of rapid prototyping.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011205711.4A CN112409779A (en) | 2020-11-02 | 2020-11-02 | 3D printing photosensitive composite material and preparation method and application thereof |
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| CN115232466A (en) * | 2022-08-03 | 2022-10-25 | 南京铖联激光科技有限公司 | Photosensitive resin for 3D printing, preparation method and preparation device thereof |
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