CN117551237A - High-thermal-conductivity high-hardness UV polyurethane composition and preparation method thereof, and protective coating - Google Patents
High-thermal-conductivity high-hardness UV polyurethane composition and preparation method thereof, and protective coating Download PDFInfo
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- CN117551237A CN117551237A CN202210924175.6A CN202210924175A CN117551237A CN 117551237 A CN117551237 A CN 117551237A CN 202210924175 A CN202210924175 A CN 202210924175A CN 117551237 A CN117551237 A CN 117551237A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 41
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011253 protective coating Substances 0.000 title claims abstract description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000001723 curing Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000003973 paint Substances 0.000 claims abstract description 9
- 238000010146 3D printing Methods 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 35
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 29
- -1 hydroxy acrylic ester Chemical class 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 25
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 16
- 239000011888 foil Substances 0.000 description 16
- 239000000178 monomer Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000001678 irradiating effect Effects 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000003848 UV Light-Curing Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 210000003934 vacuole Anatomy 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- ZOCMPVMKPVJTEP-UHFFFAOYSA-N diphepanol Chemical compound C=1C=CC=CC=1C(O)(C=1C=CC=CC=1)C(C)N1CCCCC1 ZOCMPVMKPVJTEP-UHFFFAOYSA-N 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C08K3/08—Metals
- C08K2003/0856—Iron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a high-thermal-conductivity high-hardness UV polyurethane composition and a preparation method thereof, and a protective coating. The composition comprises the following components: two photo-curable urethane acrylates, graphite Xiang Tie doped with carbon nitride, photoinitiator, and monofunctional reactive diluents. The composition does not need to use a polyfunctional reactive diluent to increase the crosslinking density and further improve the hardness, but adjusts the hardness through the addition content of the resin and graphite phase iron doped carbon nitride, and simultaneously improves the thermal conductivity of the polyurethane material. The introduction of graphite phase iron doped carbon nitride can improve the photo-curing efficiency of the composition and can continue deep curing under natural light. The yield is greatly reduced by introducing the lamellar graphite phase iron doped carbon nitride, so that the adhesion between the cured film and the substrate is improved. The composition can be used as a protective layer or a decorative layer, such as automobile paint, UV three-proofing paint, a mobile phone protective sleeve, a 3D printing material and the like.
Description
Technical Field
The invention belongs to the technical field of ultraviolet light curing polyurethane materials, and particularly relates to a high-thermal-conductivity high-hardness UV polyurethane composition and a preparation method thereof.
Background
The UV curing coating technology has been rapidly developed in recent years, and has the following advantages: the curing speed is high, the curing can be completed in a few seconds or tens of seconds under the irradiation of an ultraviolet lamp with a power of a plurality of kilowatts, and the traditional solvent-based paint can be dried in a plurality of hours or even days; the environment-friendly photo-curing coating basically contains no volatile solvent, and along with the increasing environmental protection call in recent years, the emission limit of VOC to the atmosphere is more and more strict, and the photo-curing coating meets the requirements of the age; energy is saved; can be coated on various base materials with low cost.
The photo-curing paint has various varieties and various properties, and the main components generally comprise: photoinitiator, reactive diluent, oligomer and various additives. Polyurethane acrylic ester (PUA for short) is an important photo-curing oligomer, which is synthesized by two steps of reaction of polyisocyanate, polyether polyol and acrylic ester, and is widely applied to photo-curing paint, printing ink and adhesive.
The graphite phase carbon nitride is nontoxic, has good biocompatibility, has good photocatalytic performance, can absorb blue-violet light with wavelength less than 475 in solar spectrum, and has been applied to the field of photocatalytic organic synthesis mainly through oxidation-reduction reaction in the photocatalytic process.
The prior preparation method of the high-hardness UV polyurethane composition mainly comprises the following steps: (1) By adjusting the types and proportion of the reactive diluents, the method often needs to use monomers with high functionality, has large shrinkage stress, is easy to crack and has high shrinkage rate, so that the adhesive force of the materials is reduced, the price is high, and the toxicity to human bodies and the environment is high; (2) The method has the problems that the control of the synthesis process is complex or special raw materials are needed, the product structure is complex and the price is high by using the acrylate oligomer with high functionality. In addition, in the UV curing process, there are cases where the residual monomer is not completely cured, and the residual monomer affects the comprehensive properties such as hardness in the system.
A variety of high functionality acrylate monomers and difunctional acrylate monomers and epoxy acrylates are used in patent CN112029384B to adjust hardness. Polyfunctional acrylates tend to have problems of high toxicity, high skin irritation, high price, and the like; and the adhesive force is reduced due to larger shrinkage in the curing process; because of the high crosslinking density, the problem of brittle fracture of the material is easily generated. The introduction of epoxy acrylates also brings about the problem of high brittleness.
The high-hardness high-wear-resistance fingerprint-resistant photo-curing coating disclosed in the patent CN109536001B uses high-functionality acrylate oligomer or epoxy acrylate oligomer, wherein the high-functionality acrylate oligomer is polyurethane acrylate oligomer with functionality of 9 and above, and the control of the production process and the price cost of the high-functionality acrylate oligomer are all challenged.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art and provide a high-thermal-conductivity high-hardness UV polyurethane composition and a preparation method thereof, wherein polyurethane acrylate containing polyether segments and polyurethane acrylate containing hardness and not containing soft segments are matched for use, so that the UV polyurethane composition with flexibility and hardness is obtained; and the introduction of graphite phase iron doped carbon nitride can improve the photo-curing efficiency of the composition, and can continue deep curing under natural light, so that the shrinkage rate is greatly reduced, and the adhesive force between the cured film and the substrate is improved.
The present invention achieves the above object by the following means.
The invention provides a high-thermal conductivity high-hardness UV polyurethane composition, which comprises the following components:
the high thermal conductivity high hardness UV polyurethane composition of the invention does not contain a polyfunctional reactive diluent.
The preparation method of the photo-curable polyurethane acrylic ester A comprises the following steps: reacting diisocyanate A with polyether polyol, and then blocking by hydroxy acrylic ester; the diisocyanate is one or more selected from isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, dicyclohexylmethane diisocyanate HMDI, 2, 4-trimethylhexamethylene diisocyanate TMDI and pentamethylene diisocyanate PDI.
In the preparation method of the photo-curable polyurethane acrylic ester A, the hydroxy acrylic ester is one or more of hydroxyethyl methacrylate HEMA, hydroxyethyl acrylate HEA and hydroxypropyl acrylate HPA; HEMA is preferred.
In the preparation method of the photo-curable polyurethane acrylic ester A, the polyether polyol is one or more of polypropylene glycol PPG, polytetrahydrofuran glycol PTMEG and polyethylene glycol PEG, and the weight average molecular weight is 1000-8000 g/mol, preferably 2000-5000 g/mol; the polyether polyol has a functionality of 2 to 3, preferably a functionality of 2.
The preparation method of the photo-curable polyurethane acrylic ester B comprises the following steps: reacting diisocyanate B with hydroxy acrylic ester; the diisocyanate B is selected from one or more of IPDI, HMDI and PDI.
In the preparation method of the photo-curable polyurethane acrylic ester B, the used hydroxyl acrylic ester is one or more of HEMA, HEA, HPA; HEMA is preferred.
The preparation method of the high-thermal-conductivity high-hardness UV polyurethane composition comprises the following steps: the proportion is as follows: uniformly mixing graphite phase iron doped carbon nitride acrylate dispersion, photo-curable polyurethane acrylate A, photo-curable polyurethane acrylate B, a photoinitiator and a monofunctional reactive diluent, and curing under UV illumination.
As a preferred embodiment, the preparation method of the photo-curable urethane acrylate a according to the present invention comprises the following steps:
(1) The diisocyanate A and polyether polyol are subjected to prepolymerization reaction at 70-80 ℃ in the presence of a catalyst;
(2) And (3) carrying out end capping reaction on the product of the step (1) and hydroxy acrylic ester, and ending the reaction when the NCO mass content of the system is reduced to below 0.2%.
In the preparation method of the photo-curable polyurethane acrylic ester A, the NCO/OH molar ratio of diisocyanate A to polyether polyol is 1.7-2.
In the preparation method of the photo-curable urethane acrylate A, in the step (2), the molar ratio of the hydroxyl acrylate to the NCO molar amount of the product in the step (1) is about 1:1.
in the preparation method of the photo-curable polyurethane acrylic ester A, the end capping reaction temperature in the step (2) is 60-65 ℃.
As a preferred embodiment, the preparation method of the photo-curable urethane acrylate B of the present invention comprises the following steps:
and (3) carrying out end-capping reaction on diisocyanate B and hydroxy acrylic ester in the presence of a catalyst at 60-70 ℃ until the NCO mass content of the system is reduced to below 0.5%, and ending the reaction.
In the preparation method of the photo-curable polyurethane acrylic ester B, the molar ratio of diisocyanate to hydroxyl acrylic ester NCO/OH is about 1:1.
The preparation method of the graphite phase iron doped carbon nitride comprises the following steps: and (3) uniformly mixing melamine and ferric trichloride, and grinding, calcining, secondary grinding, washing by HCl, washing by water and drying to obtain graphite-phase iron-doped carbon nitride.
In the preparation method of graphite-phase iron-doped carbon nitride, the mass ratio of melamine to ferric trichloride is (0.2-88): 1, preferably (0.875-1.75): 1.
In the preparation method of graphite-phase iron-doped carbon nitride, the calcining temperature is 500-800 ℃ and the calcining time is 2-3h.
In the graphite-phase iron-doped carbon nitride, the content of Fe is 0.1-40 wt%; preferably 5wt% to 10wt%.
The photoinitiator is one or more of 1173, 184 and TPO; preferably 1173 with TPO.
The monofunctional reactive diluents are one or more than one of HEMA, HEA, HPA; HEMA is preferred.
The monofunctional means in the present invention that one photocurable double bond is contained, and the polyfunctional means that two or more photocurable double bonds are contained.
The present invention can achieve high hardness materials with only the use of monofunctional reactive diluents while greatly alleviating the above-described problems.
The composition can be used as a protective layer or a decorative layer, such as automobile paint, UV three-proofing paint, a mobile phone protective sleeve, a 3D printing material and the like.
The high-hardness scheme in the prior art needs to add a polyfunctional reactive diluent to increase the crosslinking density, and has the problems of high toxicity, high shrinkage rate of materials, high internal stress, high brittleness, easy cracking and the like caused by the high crosslinking density. In the invention, the cross-linking density is not required to be increased by using a polyfunctional reactive diluent, so that the hardness is improved, the problems are avoided, and the invention has the following advantages and technical effects:
(1) The invention does not use high-functionality acrylic ester for improving the hardness of the material, avoids the problems of large coating shrinkage, poor adhesive force, large brittleness and the like caused by the curing of the high-functionality acrylic ester, and simultaneously, a plurality of high-functionality acrylic esters have large skin irritation and are harmful to human bodies;
(2) The invention does not use high-functionality resin for improving the hardness of the material, and the high-functionality resin has the problems of complex synthesis process, expensive and difficult synthetic raw materials, high cost, high product viscosity and the like, and is not suitable for large-scale production and use;
(3) The resin used in the invention is easy to produce and prepare, has simple process and easily available raw materials, and is suitable for large-scale production and use; the flexibility and hardness of the material are easy to control, and the material can be easily realized by the addition amount of the resin B; the material does not use active monomers with high functionality, so that the cost is saved, and the material does not have the phenomenon of hard and brittle fracture caused by overlarge crosslinking density;
(4) The composite use of graphite phase iron doped carbon nitride and polyurethane can improve the heat conductivity, flame retardance and hardness of polyurethane materials.
(5) The introduction of graphite phase iron doped carbon nitride can improve the photo-curing efficiency of the composition, and can continue deep curing under natural light, so that the shrinkage rate is greatly reduced, and the adhesive force between the cured film and the substrate is improved.
Detailed Description
The invention will be further described with reference to specific examples.
Example 1
7.2g FeCl was taken 3 ·6H 2 Dispersing O and 12.6g melamine in deionized water, stirring for 1h, collecting a precipitate, grinding the product in a 50 ℃ drying oven overnight, putting the dried solid into a tubular furnace, introducing argon for protection, calcining at 800 ℃ for 2h, cooling the product to room temperature, grinding, washing with HCl (6M) and deionized water for multiple times, collecting the precipitate, and drying in the 50 ℃ drying oven again to obtain the 5% Fe-doped graphite-phase carbon nitride.
22.2g IPDI,100g PPG (weight average molecular weight 2000, functionality 2) and 100ppm dibutyltin dilaurate were added into a four-necked flask, and stirring was continued with a reaction temperature of 75 ℃; the NCO change in the system is monitored by an NCO titration instrument, and when the NCO mass content of the system reaches 3.43%, the reaction temperature is reduced to 65 ℃. 13g of HEMA is added into the prepolymer, the reaction is continued for end capping, NCO change in the system is monitored until the NCO content is less than 0.2%, and the reaction is ended, so that the photo-curable polyurethane acrylate A is obtained.
22.2g of IPDI and 26g of HEMA are added into a four-neck flask, the reaction temperature is 65 ℃, stirring is continued, NCO change in the system is monitored until the NCO content is less than 0.2%, and the reaction is ended, so that the photo-curable polyurethane acrylic ester B is obtained.
And 5 parts of graphite-phase iron-doped carbon nitride with the Fe content of 5% is taken and ultrasonically dispersed in 15 parts of HEMA for 1h, so as to obtain graphite-phase iron-doped carbon nitride acrylate dispersion.
50 parts of photo-curable polyurethane acrylate A,30 parts of photo-curable polyurethane acrylate B,20 parts of graphite-phase iron doped carbon nitride acrylate dispersoid, 17 parts of active monomer HEMA and 1.5 parts of photoinitiator 1173,1.5 parts of photoinitiator TPO are taken, after being uniformly mixed, the mixture is poured into an aluminum foil groove (5 cm x 10 cm) with the thickness of 8mm, vacuum pumping and bubble removal are carried out in a vacuum drying oven, and then UV light irradiation curing is carried out. And taking out the cured wafer from the aluminum foil groove, and testing the Shore hardness and the heat conductivity. And (5) continuously irradiating the wafer for 500 hours under natural illumination, and testing the Shore hardness and the shrinkage rate.
Example 2
14.4g FeCl was taken 3 ·6H 2 Dispersing O and 12.6g melamine in deionized water, stirring for 1h, collecting a precipitate, grinding the product in a 50 ℃ drying oven overnight, putting the dried solid into a tubular furnace, introducing argon for protection, calcining at 800 ℃ for 2h, cooling the product to room temperature, grinding, washing with HCl (6M) and deionized water for multiple times, collecting the precipitate, and drying in the 50 ℃ drying oven again to obtain 10% Fe-doped graphite-phase carbon nitride.
And 5 parts of graphite-phase iron-doped carbon nitride with the Fe content of 10% is taken and ultrasonically dispersed in 20 parts of HEMA for 1h, so as to obtain graphite-phase iron-doped carbon nitride acrylate dispersion.
50 parts of the photocurable urethane acrylate A of example 1, 30 parts of the photocurable urethane acrylate B of example 1, 20 parts of the graphite-phase iron-doped carbon nitride acrylate dispersion, 17 parts of active monomer HEMA,1.5 parts of photoinitiator 1173,1.5 parts of photoinitiator TPO are taken, uniformly mixed, the mixture is poured into an aluminum foil tank (5 cm x 10 cm) with a thickness of 8mm, vacuoles are removed in a vacuum drying oven, and then UV light curing is performed. And taking out the cured wafer from the aluminum foil groove, and testing the Shore hardness and the heat conductivity. And (5) continuously irradiating the wafer for 500 hours under natural illumination, and testing the Shore hardness and the shrinkage rate.
Example 3
26.2g HMDI,100g PPG (weight average molecular weight 2000, functionality 2) and 100ppm dibutyltin dilaurate were added into a four-necked flask, and stirring was continued with a reaction temperature of 75 ℃; the NCO change in the system is monitored by an NCO titration instrument, and when the NCO mass content of the system reaches 3.33%, the reaction temperature is reduced to 65 ℃. 13g of HEMA is added into the prepolymer, the reaction is continued for end capping, NCO change in the system is monitored until the NCO content is less than 0.2%, and the reaction is ended, so that the photo-curable polyurethane acrylate A is obtained.
22.2g of HMDI (high-melting-point polyethylene glycol) and 26g of HEMA (high-melting-point polyethylene glycol) are added into a four-neck flask, the reaction temperature is 65 ℃, stirring is continued, NCO change in the system is monitored until the NCO content is less than 0.2%, and the reaction is ended, so that the photo-curable polyurethane acrylate B is obtained.
Taking 5 parts of graphite-phase iron-doped carbon nitride with the Fe content of 5% prepared in example 1, and performing ultrasonic dispersion in 20 parts of HEMA for 1h to obtain graphite-phase iron-doped carbon nitride acrylate dispersion.
50 parts of photo-curable polyurethane acrylate A,30 parts of photo-curable polyurethane acrylate B,20 parts of graphite-phase iron doped carbon nitride acrylate dispersoid, 17 parts of active monomer HEMA and 1.5 parts of photoinitiator 1173,1.5 parts of photoinitiator TPO are taken, after being uniformly mixed, the mixture is poured into an aluminum foil groove (5 cm x 10 cm) with the thickness of 8mm, vacuum pumping and bubble removal are carried out in a vacuum drying oven, and then UV light irradiation curing is carried out. And taking out the cured wafer from the aluminum foil groove, and testing the Shore hardness and the heat conductivity. And (5) continuously irradiating the wafer for 500 hours under natural illumination, and testing the Shore hardness and the shrinkage rate.
Example 4
11.52g FeCl was taken 3 ·6H 2 Dispersing O and 12.6g melamine in deionized water, stirring for 1h, collecting a precipitate, grinding the product in a 50 ℃ drying oven overnight, putting the dried solid into a tubular furnace, introducing argon for protection, calcining at 800 ℃ for 2h, cooling the product to room temperature, grinding, washing with HCl (6M) and deionized water for multiple times, collecting the precipitate, and drying in the 50 ℃ drying oven again to obtain 8% Fe-doped graphite-phase carbon nitride.
And 5 parts of graphite-phase iron-doped carbon nitride with the Fe content of 8% is taken and ultrasonically dispersed in 20 parts of HEMA for 1h, so as to obtain graphite-phase iron-doped carbon nitride acrylate dispersion.
50 parts of the photocurable urethane acrylate A of example 1, 30 parts of the photocurable urethane acrylate B of example 1, 20 parts of the graphite-phase iron-doped carbon nitride acrylate dispersion, 17 parts of active monomer HEMA,1.5 parts of photoinitiator 1173,1.5 parts of photoinitiator TPO are taken, uniformly mixed, the mixture is poured into an aluminum foil tank (5 cm x 10 cm) with a thickness of 8mm, vacuoles are removed in a vacuum drying oven, and then UV light curing is performed. And taking out the cured wafer from the aluminum foil groove, and testing the Shore hardness and the heat conductivity. And (5) continuously irradiating the wafer for 500 hours under natural illumination, and testing the Shore hardness and the shrinkage rate.
Example 5
2 parts of graphite-phase iron-doped carbon nitride with the Fe content of 8% prepared in example 4 is taken and ultrasonically dispersed in 20 parts of HEMA for 1h, so as to obtain graphite-phase iron-doped carbon nitride acrylate dispersion.
50 parts of the photocurable urethane acrylate A of example 1, 30 parts of the photocurable urethane acrylate B of example 1, 20 parts of the graphite-phase iron-doped carbon nitride acrylate dispersion, 17 parts of active monomer HEMA,1.5 parts of photoinitiator 1173,1.5 parts of photoinitiator TPO are taken, uniformly mixed, the mixture is poured into an aluminum foil tank (5 cm x 10 cm) with a thickness of 8mm, vacuoles are removed in a vacuum drying oven, and then UV light curing is performed. And taking out the cured wafer from the aluminum foil groove, and testing the Shore hardness and the heat conductivity. And (5) continuously irradiating the wafer for 500 hours under natural illumination, and testing the Shore hardness and the shrinkage rate.
Comparative example 1
50 parts of photo-curable urethane acrylate A,30 parts of photo-curable urethane acrylate B,32 parts of active monomer HEMA,1.5 parts of photoinitiator 1173,1.5 parts of photoinitiator TPO are taken, uniformly mixed, the mixture is poured into an aluminum foil groove (5 cm x 10 cm) with the thickness of 8mm, vacuum is pumped in a vacuum drying box for removing bubbles, and then UV light irradiation curing is carried out. And taking out the cured wafer from the aluminum foil groove, and testing the Shore hardness and the heat conductivity. And (5) continuously irradiating the wafer for 500 hours under natural illumination, and testing the Shore hardness and the shrinkage rate.
Comparative example 2
Placing 12.6g of melamine into a tubular furnace, introducing argon for protection, calcining for 2 hours at 800 ℃, cooling the product to room temperature, grinding, washing with deionized water for many times, collecting precipitate, and drying in a drying oven at 50 ℃ again to obtain graphite phase carbon nitride.
And 5 parts of graphite-phase carbon nitride is taken and ultrasonically dispersed in 20 parts of HEMA for 1h, so as to obtain graphite-phase carbon nitride dispersion liquid.
50 parts of photo-curable urethane acrylate A,30 parts of photo-curable urethane acrylate B,20 parts of graphite-phase carbon nitride acrylate dispersion, 17 parts of active monomer HEMA and 1.5 parts of photoinitiator 1173,1.5 parts of photoinitiator TPO are taken, uniformly mixed, the mixture is poured into an aluminum foil groove (5 cm x 10 cm) with the thickness of 8mm, vacuumized and bubble removed in a vacuum drying oven, and then UV light irradiation curing is carried out. And taking out the cured wafer from the aluminum foil groove, and testing the Shore hardness and the heat conductivity. And (5) continuously irradiating the wafer for 500 hours under natural illumination, and testing the Shore hardness and the shrinkage rate.
Comparative example 3
Taking 5 parts of graphite-phase iron-doped carbon nitride with the Fe content of 5% prepared in example 1, and performing ultrasonic dispersion in 20 parts of HEMA for 1h to obtain graphite-phase iron-doped carbon nitride acrylate dispersion.
50 parts of photo-curable polyurethane acrylic ester A,20 parts of graphite phase iron doped carbon nitride acrylic ester dispersoid, 17 parts of active monomer HEMA,1.5 parts of photoinitiator 1173,1.5 parts of photoinitiator TPO are taken, after being uniformly mixed, the mixture is poured into an aluminum foil groove (5 cm x 10 cm), the thickness of the mixture is poured into 8mm, vacuum is pumped in a vacuum drying box for removing bubbles, and then UV light irradiation curing is carried out. And taking out the cured wafer from the aluminum foil groove, and testing the Shore hardness and the heat conductivity. And (5) continuously irradiating the wafer for 500 hours under natural illumination, and testing the Shore hardness and the shrinkage rate.
The analytical test data for the examples and comparative examples are shown in Table 1.
Table 1 analysis of test data for examples and comparative examples
Claims (10)
1. A high thermal conductivity high hardness UV polyurethane composition comprising the following composition:
2. the composition of claim 1, wherein the composition is free of polyfunctional reactive diluents.
3. The composition according to claim 1 or 2, wherein the process for the preparation of photo-curable urethane acrylate a comprises the steps of: reacting diisocyanate A with polyether polyol, and then blocking by hydroxy acrylic ester; the diisocyanate is one or more selected from isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2, 4-trimethylhexamethylene diisocyanate and pentamethylene diisocyanate.
4. The composition according to claim 3, wherein the hydroxy acrylate used in the preparation method of the photo-curable urethane acrylate A is one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate; the polyether polyol is one or more of polypropylene glycol, polytetrahydrofuran glycol and polyethylene glycol, and the weight average molecular weight is 1000-8000 g/mol, preferably 2000-5000 g/mol; the polyether polyol has a functionality of 2 to 3, preferably a functionality of 2.
5. The composition of any one of claims 1-4, wherein the process for preparing the photo-curable urethane acrylate B comprises the steps of: reacting diisocyanate B with hydroxy acrylic ester; the diisocyanate B is one or more selected from isophorone diisocyanate, dicyclohexylmethane diisocyanate and pentamethylene diisocyanate.
6. The composition of claim 5, wherein the hydroxy acrylate used in the preparation method of the photo-curable polyurethane acrylate B is one or more of hydroxy ethyl methacrylate, hydroxy ethyl acrylate and hydroxy propyl acrylate.
7. The composition of any one of claims 1-6, wherein the method of preparing graphite-phase iron-doped carbon nitride comprises the steps of: mixing melamine and ferric trichloride uniformly, grinding, calcining, washing by HCl, washing by water, and drying to obtain graphite-phase iron-doped carbon nitride; in the graphite-phase iron-doped carbon nitride, the content of Fe is 0.1-40 wt%; preferably 5wt% to 10wt%.
8. The composition of any one of claims 1-7, wherein the monofunctional reactive diluent is one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate.
9. A process for preparing the composition of any one of claims 1-8, comprising the steps of: uniformly mixing graphite phase iron doped carbon nitride acrylate dispersion, photo-curable polyurethane acrylate A, photo-curable polyurethane acrylate B, a photoinitiator and a monofunctional reactive diluent according to a proportion, and curing under UV illumination.
10. A protective coating comprising the composition of any one of claims 1-8 for automotive paints, UV tri-proof paints, cell phone protective covers, 3D printing materials.
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