CN115260405B - Light-cured resin and preparation method thereof - Google Patents
Light-cured resin and preparation method thereof Download PDFInfo
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- CN115260405B CN115260405B CN202211195207.XA CN202211195207A CN115260405B CN 115260405 B CN115260405 B CN 115260405B CN 202211195207 A CN202211195207 A CN 202211195207A CN 115260405 B CN115260405 B CN 115260405B
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- 239000011347 resin Substances 0.000 title claims abstract description 91
- 229920005989 resin Polymers 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 44
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000000016 photochemical curing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 4
- -1 4-methylthiophenyl Chemical group 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims description 2
- BBAGPRAUWBSYDH-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O BBAGPRAUWBSYDH-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 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 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 16
- 238000012986 modification Methods 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 11
- 238000002834 transmittance Methods 0.000 abstract description 7
- 238000007639 printing Methods 0.000 abstract description 6
- 239000002356 single layer Substances 0.000 abstract description 4
- 238000010146 3D printing Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Abstract
A light-cured resin and a preparation method thereof belong to the technical field of light-cured resins. The photocuring resin is used as an additive resin for 3D printing, the curing shrinkage rate is large, and the printing precision of a product is directly influenced by the semitransparent resin. The raw materials of the invention comprise 65 to 85 parts of resin matrix, 15 to 35 parts of active diluent, 0.5 to 10 parts of carbon nano tube, 0.4 to 0.6 part of initiator, 0.3 to 0.8 part of polymerization inhibitor, 0.1 to 0.9 part of antioxidant and 0.3 to 3 parts of dispersant by weight; wherein, the active diluent, the carbon nano tube, the polymerization inhibitor, the antioxidant and the dispersant are mixed and ground uniformly. The light transmittance of the light-cured resin is effectively reduced, the single-layer curing thickness is reduced, the curing shrinkage is also reduced, the electric and heat conductivity and the mechanical property of the light-cured resin are greatly improved, the modification capability of the carbon nano tube is more fully exerted, and the modification efficiency of the carbon nano tube is improved.
Description
Technical Field
A light-cured resin and a preparation method thereof belong to the technical field of light-cured resins.
Background
Under the irradiation of ultraviolet light, light and a photoinitiator interact, the photoinitiator absorbs the ultraviolet radiation energy to form excited state molecules, the photoinitiator molecules are chemically rearranged and decomposed into free radicals or other active group intermediates, the groups react with unsaturated groups in the resin to initiate double bonds in the molecules of the photocuring resin and the active diluent to be disconnected, continuous polymerization is carried out, and thus, mutual grafting and crosslinking are carried out, liquid components are converted into solid polymers, and the aim of curing is achieved. Chemical kinetics research shows that the ultraviolet light promotes the mechanism of resin curing to belong to a chain reaction mechanism, namely, the polymerization process of prepolymer initiated by active species (free radicals or cations) is firstly a photoinitiation stage and secondly a chain growth reaction stage, and the system can generate graft crosslinking along with the progress of chain growth in the stage and is changed from a liquid state to a solid state; eventually the chain free radicals will complete chain termination by coupling or disproportionation.
The light-cured resin is widely applied to 3D printing, electric element coating and adhesives nowadays, but the light-cured resin is a resin and has many defects on application due to the characteristics of the resin: as an additive resin for 3D printing, the curing shrinkage rate is large, and a single-layer cured thickness of a translucent resin is large to obtain good opacity, which directly affects the printing accuracy of a product, and the application of the product is also limited by its mechanical strength and thickness.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides the photocuring resin with low curing shrinkage, low light transmittance and high printing precision and the preparation method thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows: a photocurable resin characterized by: the raw materials comprise 65 to 85 parts of resin matrix, 15 to 35 parts of active diluent, 0.5 to 10 parts of carbon nano tube, 0.4 to 0.6 part of initiator, 0.3 to 0.8 part of polymerization inhibitor, 0.1 to 0.9 part of antioxidant and 0.3 to 3 parts of dispersant by weight; wherein, the active diluent, the carbon nano tube, the polymerization inhibitor, the antioxidant and the dispersant are mixed and ground uniformly;
the resin matrix is an acrylate prepolymer, the reactive diluent is multifunctional acrylate, the carbon nanotube is a multi-walled carbon nanotube, and the initiator is one of benzoin dimethyl ether, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide and 2,4, 6-trimethylbenzoyl ethyl phosphonate; the polymerization inhibitor is hydroquinone or tert-butyl catechol; the antioxidant is triphenyl phosphite; the dispersant is polyacrylamide;
the acrylic ester prepolymer is one of epoxy propylene resin oligomer, polyurethane propylene resin and acrylic resin oligomer; the multifunctional acrylate is one or a mixture of more of tripropylene glycol diacrylate, glycerol propoxylate triacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate and tripropylene glycol diacrylate in any proportion.
The carbon nano tube has large length-diameter ratio, high strength and high modulus, and can be made into a composite material with a resin matrix, so that the composite material can show good strength, and the thermal conductivity of the material can be improved; the p electrons of the carbon atoms of the carbon nano tube form a large-range delocalized pi bond, so that the good electrical property can be provided for the photocuring resin; however, due to the above characteristics of the carbon nanotubes themselves, agglomeration is likely to occur during the addition of the resin matrix, and the carbon nanotubes cannot be effectively added into the resin matrix to modify the resin matrix, and even if the addition amount is small, the phenomenon of uneven dispersion occurs, and the carbon nanotubes are dispersed on the surface of the resin, so that the light transmittance cannot be reduced, and other properties cannot be improved.
According to the invention, the carbon nano tubes are added in the raw materials of the light-cured resin, and the carbon nano tubes are mixed and ground by pre-matching with the active diluent, the initiator, the polymerization inhibitor, the antioxidant and the dispersing agent, so that the carbon nano tubes are well matched with the resin matrix, and a large amount of carbon nano tubes can be fully, uniformly and effectively dispersed in the resin matrix, thereby effectively reducing the light transmittance of the light-cured resin, reducing the single-layer curing thickness, enabling the light-cured resin to obtain higher printing precision under lower thickness and diameter, reducing the curing shrinkage rate, greatly improving the electric and thermal conductivity and mechanical properties of the light-cured resin, more fully exerting the modification capability of the carbon nano tubes and improving the modification efficiency of the carbon nano tubes.
The acrylate resin system is a free radical resin system, has high curing speed and low price, and adopts the prepolymer for photocuring, so that the photocuring speed is higher; secondly, the resin matrix and the reactive diluent are both acrylates, the compatibility of the two is better, the two can be compatible in any proportion, the preferred reactive diluent and the carbon nano tube have better uniform dispersion effect under the grinding condition, the resin matrix, the reactive diluent and the carbon nano tube are matched, the dispersion effect of the carbon nano tube in the resin matrix is improved, the modification efficiency of the carbon nano tube on the resin matrix is improved, the light transmittance of the light-cured resin is further reduced, and the mechanical property and the conductivity are improved
The preparation method of the light-cured resin is characterized by comprising the following steps: the method comprises the following steps:
1) Mixing and stirring an active diluent, a carbon nano tube, a dispersant, an antioxidant and a polymerization inhibitor in a dispersion kettle, then feeding the mixture into a sand mill, grinding the mixture by using a grinding medium with the particle size of 1.5-2.5 mm, the medium filling rate of 70-80% and the rotation speed of 1000-1500 rpm, detecting a D50 value by using a laser particle size analyzer every 1h until the change range of the D50 value is 15-40 mu m, grinding the mixture by using a grinding medium with the particle size of less than 0.5mm, the medium filling rate of 80-90% and the rotation speed of 1000-1500 rpm, detecting the D50 value by using the laser particle size analyzer every 1h, and grinding the mixture until the change range of the D50 value is 10-20 mu m;
2) Adding an initiator and a resin matrix into the material obtained in the step 1), and uniformly mixing to obtain the photocuring resin.
The carbon nano tube obtained by the sand mill and the grinding conditions in the preparation method has a good modification effect, and can avoid poor dispersion effect and light transmittance due to insufficient grinding, or avoid agglomeration phenomenon and reduced electric and heat conductivity or inverse dispersion phenomenon due to excessive grinding. The antioxidant and the polymerization inhibitor are added as early as possible, so that the dispersion uniformity of the antioxidant and the polymerization inhibitor can be improved, and on the other hand, the components including the active diluent can be effectively protected under the condition of high temperature generated by grinding, the modification effect is ensured, and multiple purposes are achieved.
Preferably, the mixing and stirring conditions in the dispersion kettle in the step 1) are 500 to 800rpm and stirring for 1 to 3h.
Preferably, the temperature of the sand mill in the step 1) is controlled to be 40-50 ℃ in the grinding process.
The high-temperature self-aggregation of the reactive diluent monomer or the carbon nano tube can be avoided under the preferable temperature control, the high-temperature aggregation and adsorption of the carbon nano tube on the wall of the kettle can also be prevented, and the grinding efficiency is improved.
Preferably, the mixing condition in the step 2) is 500 to 600rpm and stirring for 1 to 3h.
Compared with the prior art, the invention has the beneficial effects that: the carbon nano tubes are added into the raw materials of the light-cured resin, and the carbon nano tubes are mixed and ground by pre-matching with the active diluent, the initiator, the polymerization inhibitor, the antioxidant and the dispersing agent, so that the carbon nano tubes are well matched with the resin matrix, and a large amount of carbon nano tubes can be fully, uniformly and effectively dispersed into the resin matrix, thereby effectively reducing the light transmittance of the light-cured resin, reducing the single-layer curing thickness, enabling the light-cured resin to obtain higher printing precision under lower thickness and diameter, greatly improving the electric and thermal conductivity and mechanical properties of the light-cured resin, more fully playing the modifying capability of the carbon nano tubes, improving the modifying efficiency of the carbon nano tubes and reducing the using amount of the carbon nano tubes.
Detailed Description
The present invention is further illustrated by the following examples, example 1 being the best mode of carrying out the invention.
In the following examples, the acrylic resin oligomer and the reactive diluent were selected from Changxing chemical industry products, the initiator was selected from Tianjin Jiu Co., ltd, and the carbon nanotube was a multiwalled carbon nanotube.
Examples 1 to 5
A photocurable resin, the raw materials used in each example are shown in Table 1 below.
Table 1 examples materials
The preparation method of the light-cured resin in each embodiment comprises the following steps:
1) Putting an active diluent, a carbon nano tube, a dispersant, an antioxidant and a polymerization inhibitor into a dispersion kettle, mixing and stirring the mixture, stirring the dispersion kettle for 1h at the speed of 500rpm, then feeding the mixture into a sand mill, controlling the temperature of the mill to be 40-50 ℃, grinding the mixture at the rotation speed of 1200rpm at the grain size of a grinding medium of 1.5-2.5 mm, the filling rate of the grinding medium of 75%, detecting the D50 value by using a laser particle size analyzer every 1h, and grinding the mixture until the change amplitude of the D50 value is 15-40 mu m; grinding with a grinding medium with the particle size of less than 0.5mm and the medium filling rate of 85% at a rotating speed of 1200rpm, detecting a D50 value by using a laser particle size analyzer every 1h, and grinding until the change range of the D50 value is 10-20 mu m; grinding and pumping into a dispersion kettle for later use;
2) Adding an initiator and a resin matrix into the material obtained in the step 1), and stirring for 3 hours at 500rpm by using a dispersion kettle to obtain the photocuring resin.
Example 6
Based on example 1, in the preparation method, only the first grinding is set in step 1), the second grinding is not set, the stirring speed of the dispersion kettle in step 1) is set to 800rpm, stirring is carried out for 3 hours, uneven dispersion in subsequent steps is prevented, the missing second grinding is compensated, and other conditions are the same as example 1.
Example 7
A light-cured resin is prepared by the method of example 1, wherein only the second grinding condition is set in the step 1) of the preparation method, the first grinding condition is not performed, and other conditions are the same as example 1.
Example 8
A light-cured resin is prepared on the basis of the example 1, in the preparation method, the filling rate of a first grinding medium in the step 1) is set to be 70%, and the rotating speed is set to be 1500rpm; the second grinding media fill was set to 90% and the rotation speed was set to 1000rpm, with the other conditions being the same as in example 1.
Example 9
A light-cured resin is prepared by setting the filling rate of a first grinding medium in the step 1) in the preparation method to be 80% and setting the rotating speed to be 1000rpm on the basis of the example 1; the second grinding media fill was set at 80%, the rotation speed was set at 1500rpm, and the dispersion tank was stirred at 600rpm for 1 hour in step 2), and the other conditions were the same as in example 1.
Comparative example 1
A light-cured resin is prepared according to the formula of example 1, carbon nano tubes are not added, and the preparation method is that a dispersion kettle is only used for stirring at 500rpm for 3 hours to uniformly disperse, so that the light-cured resin is prepared.
Comparative example 2
A light-cured resin is prepared according to the formula of example 1, no dispersing agent is added, and the preparation method is that a dispersing kettle is only used for stirring at 500rpm for 3 hours to uniformly disperse, so that the light-cured resin is prepared.
Comparative example 3
A light-cured resin is prepared according to the formula of example 1 by directly mixing and then stirring in a dispersion kettle at 500rpm for 4h to obtain the light-cured resin.
Comparative example 4
A light-cured resin is prepared by setting the dosage of carbon nano tubes to be 20kg on the basis of the formula of example 5, and the preparation method only adopts the steps of directly mixing, stirring in a dispersion kettle at 800rpm for 5h, and dispersing to obtain the light-cured resin.
Comparative example 5
A photocurable resin was prepared according to the same method as in example 1, except that no dispersant was added to the formulation of example 1.
Performance testing
And (3) scanning and curing the resin by using a laser rapid prototyping machine according to the standard and quantity requirements of a bending sample in GB/T2567-2021, printing a sample strip, and testing according to the test standard.
The resin was coated using a four-sided preparation machine, and the natural light cured sample was normalized to 100mm 0.5mm, and tested for surface resistance.
Density measurement of liquid resin using pycnometer: cleaning a pycnometer, drying and weighing M 1 Adding water, keeping the temperature at 25 ℃ for 1 hour, and weighing out the total weight M 2 And calculating the volume V of the pycnometer according to the density rho water of the water. Pouring off water, oven drying, adding liquid resin, keeping the temperature at 25 deg.C for 8 hr, and weighing M 3 Calculating the density rho of the liquid resin 1 。
Wherein:
scanning and curing the resin by a laser rapid forming machine, wherein the number of cured layers is ten, and measuring the density rho on a density balance after the curing is finished and cleaned 2 。
The data was used to calculate the shrinkage S:
and scanning and curing the resin by using a laser rapid forming machine, wherein the cured shape is circular, the number of cured layers is one, taking out the resin after curing, and cleaning the resin by using alcohol to measure the thickness of the resin by using a vernier caliper.
The thermal conductivity of the cured wafer in step 4 was measured using a thermal conductivity meter.
The results of the tests of the examples and comparative examples are shown in Table 2 below.
Table 2 results of performance testing
The comparison experiment results of the comparative example 2 and the comparative example 1 prove that the performance of each test item of a common epoxy acrylic resin cured product is obviously improved by adding the carbon nano tube and the dispersing agent, and the comparison of the performance test results of the comparative examples 3 to 5 and the example 1 can show that the modification efficiency of the carbon nano tube can be improved only after the carbon nano tube and the dispersing agent are added and matched and ground, and in addition, the comparison of the performance test results of the examples 6 to 9 and the example 1 can prove that the modification efficiency of the carbon nano tube can be further improved by a specific grinding mode.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (4)
1. A photocurable resin characterized by: the raw materials comprise, by weight, 65 to 85 parts of a resin matrix, 15 to 35 parts of an active diluent, 0.5 to 10 parts of a carbon nano tube, 0.4 to 0.6 part of an initiator, 0.3 to 0.8 part of a polymerization inhibitor, 0.1 to 0.9 part of an antioxidant and 0.3 to 3 parts of a dispersant; wherein, the active diluent, the carbon nano tube, the polymerization inhibitor, the antioxidant and the dispersant are mixed and ground uniformly;
the resin matrix is an acrylate prepolymer, the reactive diluent is polyfunctional acrylate, the carbon nanotube is a multi-walled carbon nanotube, and the initiator is one of benzoin dimethyl ether, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone, 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide and 2,4, 6-trimethylbenzoyl ethyl phosphonate; the polymerization inhibitor is hydroquinone or tert-butyl catechol; the antioxidant is triphenyl phosphite; the dispersant is polyacrylamide;
the acrylic ester prepolymer is one of epoxy propylene resin oligomer, polyurethane propylene resin and acrylic resin oligomer; the multifunctional acrylate is one or a mixture of more of tripropylene glycol diacrylate, glycerol propoxylate triacrylate and trimethylolpropane triacrylate in any proportion;
the preparation method of the light-cured resin comprises the following steps:
1) Mixing and stirring an active diluent, a carbon nano tube, a dispersant, an antioxidant and a polymerization inhibitor in a dispersion kettle, then putting the mixture into a sand mill, grinding the mixture by using a grinding medium with the particle size of 1.5-2.5 mm, the medium filling rate of 70-80% and the rotation speed of 1000-1500 rpm, detecting the D50 value by using a laser particle size analyzer every 1h until the D50 value variation range is 15-40 mu m, grinding the mixture by using a grinding medium with the particle size of less than 0.5mm, the medium filling rate of 80-90% and the rotation speed of 1000-1500 rpm, detecting the D50 value by using the laser particle size analyzer every 1h, and grinding the mixture until the D50 value variation range is 10-20 mu m;
2) Adding an initiator and a resin matrix into the material obtained in the step 1), and uniformly mixing to obtain the photocuring resin.
2. The photocurable resin according to claim 1, wherein: and (2) stirring the mixture in the dispersion kettle in the step 1) for 1 to 3 hours at 500 to 800rpm.
3. The photocurable resin according to claim 1, wherein: the temperature of the sand mill in the step 1) is controlled to be 40-50 ℃ in the grinding process.
4. The photocurable resin according to claim 1, wherein: the mixing condition of the step 2) is 500-600rpm and stirring for 1-3h.
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| CN106634089B (en) * | 2016-09-18 | 2019-01-29 | 江南大学 | A kind of ultraviolet-curing paint and preparation method thereof based on carbon nanotube |
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Denomination of invention: A UV curable resin and its preparation method Effective date of registration: 20231026 Granted publication date: 20221227 Pledgee: Industrial and Commercial Bank of China Limited Jingmen Duodao Branch Pledgor: Hubei Wanglin New Material Technology Co.,Ltd. Registration number: Y2023980062557 |
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