CN116904103A - Low-carbon environment-friendly functionalized graphene oxide polyurethane coating and preparation method thereof - Google Patents
Low-carbon environment-friendly functionalized graphene oxide polyurethane coating and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 116
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007822 coupling agent Substances 0.000 claims abstract description 34
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims description 42
- 150000003077 polyols Chemical class 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- IVSXMRBSXVGOJJ-UHFFFAOYSA-N 5-trimethoxysilylpentan-1-ol Chemical compound CO[Si](OC)(OC)CCCCCO IVSXMRBSXVGOJJ-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JPMBLOQPQSYOMC-UHFFFAOYSA-N trimethoxy(3-methoxypropyl)silane Chemical compound COCCC[Si](OC)(OC)OC JPMBLOQPQSYOMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 10
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000013522 chelant Substances 0.000 description 6
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 4
- -1 acid rain Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000221089 Jatropha Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 240000000432 Pistacia chinensis Species 0.000 description 1
- 235000014123 Pistacia chinensis Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OIZVGOMQHJYOIP-UHFFFAOYSA-N dioctyl (4-oxo-1,2,3,4lambda5-trioxaphosphetan-4-yl) phosphate Chemical compound O(P(OCCCCCCCC)(=O)OP1(=O)OOO1)CCCCCCCC OIZVGOMQHJYOIP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The application discloses a low-carbon environment-friendly functionalized graphene oxide polyurethane coating and a preparation method thereof, and belongs to the technical field of coatings. Aiming at the problem of poor compatibility of graphene oxide, epoxy resin and other coating matrix resins in the prior art, the application carries out composite modification on the graphene oxide through the silane coupling agent and the titanate coupling agent, improves the compatibility of the graphene oxide with other substances, so that the dispersion performance of the graphene oxide can be effectively improved, the graphene oxide is continuously functionalized through the titanate coupling agent on the basis, long-chain winding can be carried out on the titanate coupling agent and the silane coupling agent, the impact strength, the elongation and the shearing strength of the long-chain wound graphene oxide can be effectively improved, and meanwhile, the silane coupling agent can enable the titanate coupling agent to be uniformly combined on all parts of the surface of the graphene oxide, so that the titanate coupling agent can be uniformly dispersed in the coating, and the heat resistance of the coating can be better improved.
Description
Technical Field
The application belongs to the technical field of coatings, and particularly relates to a low-carbon environment-friendly functionalized graphene oxide polyurethane coating and a preparation method thereof.
Background
The main components of the polyurethane coating comprise polyol and isocyanate, and the polyol and the isocyanate are crosslinked and cured to obtain the polyurethane coating. While polyols in conventional polyurethane coatings generally originate from petrochemical industry, along with the increasing decrease of petrochemical resources, the price of polyols in conventional polyurethane coatings continues to rise, and thus, development of polyurethane coatings using bio-based polyols as raw materials has become a current research hotspot. However, bio-based polyurethane has the defects of poor high temperature resistance, poor flame retardance, poor mechanical property and the like. When the bio-based polyurethane coating is used as a paint film protective layer of outdoor equipment, the bio-based polyurethane coating is corroded by solvents such as acid rain, oil stains and the like for a long time, is easy to damage and the like, and loses the protective effect. Therefore, in order for the bio-based polyurethane coating to protect outdoor equipment for a long period of time, the performance of the bio-based polyurethane coating has yet to be improved.
Graphene is an effective reinforcing filler for preparing composite coatings due to its large specific surface area, specific layered structure, high mechanical strength and good thermal stability, but strong van der waals interactions between graphene sheets make it easy to re-accumulate and agglomerate in the polymer matrix, which directly affects the performance of the composite coating. Whereas graphene oxide has a planar structure similar to graphene and contains a large number of active groups (such as carboxyl groups, hydroxyl groups, etc.) on the surface. Graphene oxide has better dispersibility and reactivity than graphene, but has a problem of poor compatibility with coating matrix resin such as epoxy resin because hydroxyl groups, carboxyl groups and the like on the surface of GO are hydrophilic groups.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a low-carbon and environment-friendly functionalized graphene oxide polyurethane coating and a preparation method thereof.
The technical scheme adopted by the application is as follows:
the low-carbon environment-friendly functionalized graphene oxide polyurethane coating comprises a component A and a component B, wherein the component A comprises the following raw materials: the composite functional graphene oxide, the bio-based polyol, the petroleum-based polyol and the auxiliary agent, wherein the mass ratio of the composite functional graphene oxide to the bio-based polyol to the petroleum-based polyol is (0.1-1): 100-300:100-300, wherein the composite functionalized graphene oxide is obtained by functionalizing graphene oxide by a silane coupling agent and a titanate coupling agent, and the component B comprises isocyanate and a component B auxiliary agent.
The preparation method of the low-carbon environment-friendly functionalized graphene oxide polyurethane coating comprises the following steps:
step A: preparing composite functionalized graphene oxide;
and (B) step (B): preparing a bio-based polyol;
step C: uniformly mixing petroleum-based polyol, the composite functionalized graphene oxide prepared in the step A, the bio-based polyol prepared in the step B and an auxiliary agent in proportion to obtain a component A;
step D: and (3) uniformly mixing the component B with the component A obtained in the step (C) in proportion to obtain the polyurethane coating.
Further, the specific steps for preparing the composite functionalized graphene oxide in the step A are as follows:
step A1: preparing amino-functionalized graphene oxide by using a silane coupling agent and graphene oxide;
step A2: the composite functionalized graphene oxide is prepared by a titanate coupling agent and amino-functionalized graphene oxide.
Further, the silane coupling agent is one or more of 3-methoxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3- (2-hydroxyethyl) propyl trimethoxysilane or gamma-aminopropyl triethoxysilane.
Further, the titanate coupling agent is one or more of chelating coupling agents, and the chelating coupling agents comprise bis (dioctyl pyrophosphate) glycolate titanate and bis (dioctyl oxy pyrophosphate) ethylene titanate.
Further, the specific steps of the step A1 are as follows:
step A101: adding 1-3g of graphene oxide into 200ml of dimethylformamide for ultrasonic dispersion;
step A102: after ultrasonic dispersion is finished, 1-10g of silane coupling agent is dripped into the system, and the mixture is stirred for 1-5h at the temperature of 50-100 ℃ to obtain the mixed solution containing the amino-functionalized graphene oxide.
Further, the specific steps of the step A2 are as follows:
step a201: dropwise adding 1-10g of titanate coupling agent into the mixed solution containing the amino-functionalized graphene oxide obtained in the step A102, and stirring for 1-3h at the temperature of 50-120 ℃ to obtain a mixed solution containing the composite functionalized graphene oxide;
step A202: filtering the mixed solution containing the composite functionalized graphene oxide, and washing filter residues;
step A203: and drying the washed filter residues to obtain the composite functionalized graphene oxide.
Further, the component A auxiliary agent comprises a chain extender, and the proportion of the composite functionalized graphene oxide, the bio-based polyol, the petroleum-based polyol and the chain extender is 0.1-1:100-300:100-300:1-20.
Further, the specific steps of the step B are as follows:
step B1: pre-mixing ethylene glycol, diethanolamine and potassium acetate according to a proportion to prepare a mixed solution;
step B2: and (2) adding the recycled vegetable oil and the mixed solution obtained in the step (B1) into a reaction kettle in proportion, connecting and stirring for 30-180 minutes at the temperature of 100-400 ℃ to obtain the bio-based polyol, wherein nitrogen flows in the reaction kettle in the process, and the vacuum pressure is 400-800Mpa.
Further, the recovered vegetable oil is soybean oil, peanut oil, palm oil, rapeseed oil, jatropha oil or pistacia chinensis bunge oil or a combination of two or more of the above.
Further, the isocyanate is toluene diisocyanate, xylene diisocyanate, polymeric diphenylmethane diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
Further, the petroleum-based polyol may be a polyether polyol or a polyester polyol, with alkynyl-containing polyols being preferred. Because the petroleum-based polyol has better heat resistance and mechanical property than the polyurethane coating prepared from the bio-based polyol, and the alkynyl-containing polyol has higher heat stability, the polyurethane coating can be used for overcoming the defect brought by the bio-based polyol to the coating.
In summary, due to the adoption of the technical scheme, the beneficial effects of the application are as follows:
1. according to the application, the silane coupling agent and the titanate coupling agent are used for functionalizing the graphene to obtain the composite functionalized graphene oxide, and the plant oil-based polyurethane coating is modified through the composite functionalized graphene oxide, so that the plant oil-based polyurethane coating is more environment-friendly and has better physicochemical properties.
2. According to the application, the graphene oxide is subjected to composite modification by the silane coupling agent and the titanate coupling agent, more groups which can be combined with other substances are arranged on the surface of the graphene oxide after the silane coupling agent is modified, so that the compatibility of the graphene oxide with other substances is improved, the dispersion performance of the graphene oxide can be effectively improved, the graphene oxide is continuously functionalized by the titanate coupling agent on the basis, long-chain winding can be carried out on the titanate coupling agent and the silane coupling agent, the impact strength, the elongation and the shearing strength of the graphene oxide wound by the long chain can be effectively improved, the composite modified graphene oxide has better dispersibility, the silane coupling agent can uniformly combine the titanate coupling agent on all parts of the surface of the graphene oxide, and when the graphene oxide is dispersed in the coating, the titanate coupling agent can be uniformly dispersed in the coating, so that the heat resistance of the coating is better improved. The silane coupling agent and the titanate coupling agent are used for carrying out composite modification on the graphene oxide and functionalization on the graphene oxide, so that the dispersibility of the graphene oxide in the polyurethane coating can be improved, and meanwhile, the comprehensive performance of the polyurethane coating can be improved.
Drawings
FIG. 1 is a flow chart of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments.
Example 1
As shown in fig. 1, the low-carbon environment-friendly functionalized graphene oxide polyurethane coating comprises a component A and a component B, wherein the component A comprises the following raw materials: the multifunctional graphene oxide comprises 0.6g, 250g and 250g of composite functional graphene oxide, 250g of bio-based polyol and 250g of petroleum-based polyol, wherein the auxiliary comprises 0.3g of chain extender dimethylol butyric acid (DMBA), 0.3g of dispersant distributor 9250, 0.3g of dispersant Efka 4015, 0.1g of anti-sagging agent Byk 410 and 0.5g of defoamer Efka 2723, the composite functional graphene oxide is obtained by functionalizing the graphene oxide by amino propyl trimethoxy silane and chelate titanate coupling agent TC-WT in sequence, and the component B comprises toluene diisocyanate and a film forming agent, wherein the mass ratio of the component A to the component B is 2:1.
The preparation method of the low-carbon environment-friendly functionalized graphene oxide polyurethane coating comprises the following steps:
step A: preparing composite functionalized graphene oxide;
step A1: preparing amino-functionalized graphene oxide by using a silane coupling agent and graphene oxide;
step A101: adding 2g of graphene oxide into 200ml of dimethylformamide for ultrasonic dispersion;
step A102: after ultrasonic dispersion is finished, dropwise adding 5g of aminopropyl trimethoxy silane into the system, and stirring for 3 hours at the temperature of 80 ℃ to obtain a mixed solution containing amino-functionalized graphene oxide;
step A2: preparing composite functionalized graphene oxide through a titanate coupling agent and amino-functionalized graphene oxide;
step a201: dropwise adding 6g of chelate titanate coupling agent TC-WT into the mixed solution containing the amino-functionalized graphene oxide obtained in the step A102, and stirring for 3 hours at the temperature of 100 ℃ to obtain a mixed solution containing the composite functionalized graphene oxide;
step A202: filtering the mixed solution containing the composite functionalized graphene oxide, and washing filter residues;
step A203: drying the washed filter residues to obtain composite functionalized graphene oxide;
and (B) step (B): preparing a bio-based polyol;
step B1: pre-mixing ethylene glycol, diethanolamine and potassium acetate according to a ratio of 30:3:1 to prepare a mixed solution;
step B2: adding the recycled vegetable oil and the mixed solution obtained in the step B1 into a reaction kettle according to the ratio of 20:80, and connecting and stirring for 150 minutes at the temperature of 300 ℃ to obtain the bio-based polyol, wherein nitrogen flows in the reaction kettle in the process, and the vacuum pressure is 600Mpa;
step C: adding 25g of propylene oxide ether polyol, 600mg of composite functionalized graphene oxide prepared in the step A, 25g of bio-based polyol prepared in the step B, 0.3g of chain extender dimethylol butyric acid (DMBA), 0.3g of dispersant dispener 9250, 0.3g of dispersant Efka 4015, 0.1g of anti-sagging agent Byk 410 and 0.5g of defoamer Efka 2723 into a container, starting a dispersing machine to stir (1 000-1 200 r/min) for dispersing for 30min, transferring the uniformly mixed solution into a reaction kettle with a vacuumizing function, heating to 100 ℃, starting a vacuumizing device for dewatering for 1h, stopping the vacuumizing device, cooling to room temperature, discharging and canning, and marking as a component A;
step D: and C, uniformly mixing the component B with the component A obtained in the step C in a ratio of 2:1 to obtain polyurethane coating, and coating the polyurethane coating on the surface of the substrate to form a film.
Example 2
This example is substantially the same as example 1 except that the titanate coupling agent is added in an amount of 1g in step A201 of example 2.
Example 3
This example is substantially the same as example 1, except that the titanate coupling agent is added in an amount of 10g in step A201 of example 3.
Example 4
This example is substantially the same as example 1, except that the amount of the composite functionalized graphene oxide added in step C of example 4 is 100mg.
Example 5
This example is substantially the same as example 1, except that the amount of the composite functionalized graphene oxide added in step C of example 5 is 1g.
Comparative example 1
This comparative example is substantially the same as example 1 except that the complex functionalized graphene oxide is not added in comparative example 1.
Comparative example 2
The comparative example is basically the same as example 1, except that the graphene oxide added in comparative example 2 is a single modified graphene oxide, and the specific preparation method thereof is as follows:
adding 2g of graphene oxide into 200ml of dimethylformamide for ultrasonic dispersion;
after ultrasonic dispersion is finished, dropwise adding 5g of aminopropyl trimethoxy silane into the system, and stirring for 3 hours at the temperature of 80 ℃ to obtain a mixed solution containing amino-functionalized graphene oxide;
filtering the mixed solution containing the amino-functionalized graphene oxide, and washing filter residues;
and drying the washed filter residues to obtain the single modified graphene oxide.
Comparative example 3
The comparative example is basically the same as example 1, except that the graphene oxide added in comparative example 3 is a single modified graphene oxide, and the specific preparation method thereof is as follows:
adding 2g of graphene oxide into 200ml of dimethylformamide for ultrasonic dispersion;
after ultrasonic dispersion is finished, dropwise adding 6g of chelate titanate coupling agent TC-WT into the system, and stirring for 3 hours at the temperature of 100 ℃ to obtain a mixed solution containing single modified graphene oxide;
filtering the mixed solution containing the single modified graphene oxide, and washing filter residues;
and drying the washed filter residues to obtain the single modified graphene oxide.
Comparative example 4
The comparative example is basically the same as example 1, except that the chelate titanate coupling agent TC-WT is used for modifying graphene oxide in the comparative example, specifically:
step A101: adding 2g of graphene oxide into 200ml of dimethylformamide for ultrasonic dispersion;
step A102: after ultrasonic dispersion is finished, 6g of chelate titanate coupling agent TC-WT is dripped into the system, and stirred for 3 hours at the temperature of 100 ℃;
step a201: dropwise adding 5g of aminopropyl trimethoxysilane into the mixed solution obtained in the step A102, and stirring for 3 hours at the temperature of 80 ℃ to obtain a mixed solution containing composite functionalized graphene oxide;
step A202: filtering the mixed solution containing the composite functionalized graphene oxide, and washing filter residues;
step A203: drying the washed filter residues to obtain composite functionalized graphene oxide;
comparative example 5
This comparative example is substantially the same as example 1, except that the graphene oxide is modified by adding aminopropyl trimethoxysilane and a chelating titanate coupling agent TC-WT at the same time, specifically:
step A101: adding 2g of graphene oxide into 200ml of dimethylformamide for ultrasonic dispersion;
step A102: after ultrasonic dispersion is finished, dropwise adding 6g of chelate titanate coupling agent TC-WT and 5g of aminopropyl trimethoxy silane into the system, and stirring for 6 hours at the temperature of 100 ℃;
step A202: filtering the mixed solution containing the composite functionalized graphene oxide, and washing filter residues;
step A203: drying the washed filter residues to obtain composite functionalized graphene oxide;
comparative example 6
This comparative example was substantially the same as example 1 except that 25g of petroleum-based propylene oxide ether polyol was not contained in this comparative example, and the amount of the bio-based polyol prepared in the step B was 50g.
Comparative example 7
This comparative example is substantially the same as example 1 except that the bio-based polyol prepared in step B is not contained in this comparative example, but 50g of petroleum-based propylene oxide ether polyol is added.
Mechanical property tests and paint conventional property tests were performed on examples 1 to 5 and comparative examples 1 to 7, wherein the mechanical property test results are shown in table 1, and the paint conventional property test results are shown in table 2:
TABLE 1
TABLE 2
TABLE 3 Table 3
The above examples merely illustrate specific embodiments of the application, which are described in more detail and are not to be construed as limiting the scope of the application. It should be noted that it is possible for a person skilled in the art to make several variants and modifications without departing from the technical idea of the application, which fall within the scope of protection of the application.
Claims (10)
1. The low-carbon environment-friendly functionalized graphene oxide polyurethane coating is characterized by comprising a component A and a component B, wherein the component A comprises the following raw materials: the composite functional graphene oxide, the bio-based polyol, the petroleum-based polyol and the auxiliary agent, wherein the mass ratio of the composite functional graphene oxide to the bio-based polyol to the petroleum-based polyol is (0.1-1): 100-300:100-300, wherein the composite functionalized graphene oxide is obtained by functionalizing graphene oxide by a silane coupling agent and a titanate coupling agent, and the component B comprises isocyanate.
2. A preparation method of a low-carbon environment-friendly functionalized graphene oxide polyurethane coating is characterized by comprising the following steps of: the method comprises the following steps:
step A: preparing composite functionalized graphene oxide;
and (B) step (B): preparing a bio-based polyol;
step C: uniformly mixing petroleum-based polyol, the composite functionalized graphene oxide prepared in the step A, the bio-based polyol prepared in the step B and an auxiliary agent in proportion to obtain a component A;
step D: and (3) uniformly mixing the component B with the component A obtained in the step (C) in proportion to obtain the polyurethane coating.
3. The method for preparing the low-carbon environment-friendly functionalized graphene oxide polyurethane coating, which is disclosed in claim 2, is characterized in that: the specific steps for preparing the composite functionalized graphene oxide in the step A are as follows:
step A1: preparing amino-functionalized graphene oxide by using a silane coupling agent and graphene oxide;
step A2: the composite functionalized graphene oxide is prepared by a titanate coupling agent and amino-functionalized graphene oxide.
4. The method for preparing the low-carbon environment-friendly functionalized graphene oxide polyurethane coating according to claim 3, which is characterized by comprising the following steps: the silane coupling agent is one or more of 3-methoxypropyl trimethoxy silane, 3-aminopropyl trimethoxy silane, 3- (2-hydroxyethyl) propyl trimethoxy silane or gamma-aminopropyl triethoxy silane.
5. The method for preparing the low-carbon environment-friendly functionalized graphene oxide polyurethane coating according to claim 3 or 4, which is characterized by comprising the following steps: the titanate coupling agent is one or more of chelating coupling agents, and the chelating coupling agents comprise bis (dioctyl pyrophosphate) glycolate titanate and bis (dioctyl pyrophosphate) ethylene titanate.
6. The method for preparing the low-carbon environment-friendly functionalized graphene oxide polyurethane coating, which is disclosed in claim 2, is characterized in that: the specific steps of the step A1 are as follows:
step A101: adding 1-3g of graphene oxide into 200ml of dimethylformamide for ultrasonic dispersion;
step A102: after ultrasonic dispersion is finished, 1-10g of silane coupling agent is dripped into the system, and stirred for 1-5h at the temperature of 50-100 ℃ to obtain a mixed solution containing amino-functionalized graphene oxide;
the specific steps of the step A2 are as follows:
step a201: dropwise adding 1-10g of titanate coupling agent into the mixed solution containing the amino-functionalized graphene oxide obtained in the step A102, and stirring for 1-3h at the temperature of 50-120 ℃ to obtain a mixed solution containing the composite functionalized graphene oxide;
step A202: filtering the mixed solution containing the composite functionalized graphene oxide, and washing filter residues;
step A203: and drying the washed filter residues to obtain the composite functionalized graphene oxide.
7. The method for preparing the low-carbon environment-friendly functionalized graphene oxide polyurethane coating, which is disclosed in claim 2, is characterized in that: the component A auxiliary agent comprises a chain extender, wherein the proportion of the composite functional graphene oxide, the bio-based polyol, the petroleum-based polyol and the chain extender is 0.1-1:100-300:100-300:1-20.
8. The method for preparing the low-carbon environment-friendly functionalized graphene oxide polyurethane coating, which is disclosed in claim 7, is characterized in that: the chain extender is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol and glycerol.
9. The method for preparing the low-carbon environment-friendly functionalized graphene oxide polyurethane coating, which is disclosed in claim 2, is characterized in that: the specific steps of the step B are as follows:
step B1: pre-mixing ethylene glycol, diethanolamine and potassium acetate according to the proportion of 20-50:1-5:1-5 to prepare a mixed solution;
step B2: and C, adding the recycled vegetable oil and the mixed solution obtained in the step B1 into a reaction kettle according to the proportion of 20-50:80-50, connecting and stirring for 30-180 minutes at the temperature of 100-400 ℃ to obtain the bio-based polyol, wherein nitrogen flows in the reaction kettle in the process, and the vacuum pressure is 400-800Mpa.
10. The method for preparing the low-carbon environment-friendly functionalized graphene oxide polyurethane coating, which is disclosed in claim 2, is characterized in that: the isocyanate is toluene diisocyanate, xylene diisocyanate, polymeric diphenylmethane diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
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| CN110205023A (en) * | 2019-06-21 | 2019-09-06 | 重庆市科学技术研究院 | With hydrophobic, antiseptic property composite Nano coating material and its preparation method and application |
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| CN101474842A (en) * | 2009-01-24 | 2009-07-08 | 南京红宝丽股份有限公司 | Method for improving filling property of rigid polyurethane foam plastics |
| CN108276551A (en) * | 2017-12-26 | 2018-07-13 | 合肥科天水性科技有限责任公司 | A kind of multiple cross-linked modified aqueous polyurethane resin of biology base and its preparation method and application |
| CN109593454A (en) * | 2018-12-21 | 2019-04-09 | 广东好邦石墨烯新材料科技有限公司 | A kind of polyurethane coating and its preparation method and application |
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