CN115304992A - Water-assisted room temperature self-repairing polyurethane insulating coating and preparation method thereof - Google Patents
Water-assisted room temperature self-repairing polyurethane insulating coating and preparation method thereof Download PDFInfo
- Publication number
- CN115304992A CN115304992A CN202210988429.0A CN202210988429A CN115304992A CN 115304992 A CN115304992 A CN 115304992A CN 202210988429 A CN202210988429 A CN 202210988429A CN 115304992 A CN115304992 A CN 115304992A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- insulating coating
- preparation
- repairing
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000004814 polyurethane Substances 0.000 title claims abstract description 57
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 57
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- PZRPBPMLSSNFOM-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]boronic acid Chemical compound OCC1=CC=C(B(O)O)C=C1 PZRPBPMLSSNFOM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 14
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims abstract description 12
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical group [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 claims description 15
- 150000002009 diols Chemical class 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- OKRNLSUTBJUVKA-UHFFFAOYSA-N n,n,n',n'-Tetrakis(2-hydroxyethyl)adipamide Chemical compound OCCN(CCO)C(=O)CCCCC(=O)N(CCO)CCO OKRNLSUTBJUVKA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 125000003158 alcohol group Chemical group 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000011527 polyurethane coating Substances 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 bis-vinyl-methyl-ethyl-methacrylate Chemical compound 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920006273 intrinsic self-healing polymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009864 tensile test Methods 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
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Insulating Materials (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane insulating coating capable of self-repairing at room temperature under the assistance of water and a preparation method thereof, belonging to the technical field of coatings. The preparation method of the coating comprises the steps of copolymerizing boron-nitrogen coordination dihydric alcohol serving as a chain extender with a polyurethane prepolymer and a cross-linking agent to obtain a polyurethane solution, adding a two-dimensional transition metal carbide, and curing to form a film to obtain the polyurethane insulating coating; the boron-nitrogen coordination dihydric alcohol is obtained by adding 4-hydroxymethyl phenylboronic acid and N, N, N ', N' -tetra (2-hydroxyethyl) adipamide. When the coating has fine cracks or scratches in the using process, the insulating coating can restore to the original state along with the change of humidity and air temperature when water exists or the air humidity is high, and the insulating coating can be recycled and reused.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a polyurethane insulating coating capable of self-repairing at room temperature through water assistance and a preparation method thereof.
Background
The coating is used as a composite material which can well protect the surface of a substrate material, and is widely applied to various aspects of industrial production and daily life. However, due to the influence of self-performance and environmental factors, small cracks which cannot be seen by naked eyes inevitably appear on the surface of the coating, and the micro cracks are exposed in the air and continuously spread, so that the coating is peeled off from the substrate, and the protective life and the effect of the coating are greatly reduced. Therefore, how to realize self-repair of the coating becomes a research hotspot of numerous material researchers.
The self-repairing materials are classified into external self-repairing materials and intrinsic self-repairing materials according to whether a repairing agent needs to be added in the repairing process of a system. The external aid type is characterized in that a repairing agent is added into a matrix, when damage or microcracks occur, the repairing agent seeps to a damaged part, and the damaged part is quickly repaired through chemical reaction. Intrinsic self-healing includes both types of dynamic noncovalent bonds and covalent bonds. The dynamic non-covalent bond includes hydrogen bond, ionic bond, pi-pi bond, van der waals force and the like, and the chemical crosslinking structure of the dynamic covalent bond includes Diels-Alder reaction, disulfide bond, acyl-gland bond, imine bond and the like. The two self-repairing systems have respective advantages and disadvantages, the non-covalent system can enable the material to have good self-repairing performance, but the mechanical property of the material is poor, the strength of the covalent self-repairing system is high, and meanwhile, the cross-linking network limits the movement of chains to reduce the self-repairing capacity.
The polyurethane coating is an important coating, has the characteristics of environmental protection, easy processing, high solid content, easy film forming, chemical corrosion resistance and the like, and is widely applied to the fields of leather finishing, building materials and the like. However, the existing outdoor insulating polyurethane coating material is difficult to have self-repairing capability and short service life under the premise of higher strength.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a polyurethane insulating coating capable of self-repairing at room temperature through water assistance, and the present invention also aims to provide a preparation method of the coating.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a polyurethane insulating coating capable of self-repairing at room temperature through water assistance comprises the steps of firstly preparing a polyurethane prepolymer by using a diol oligomer and isocyanate, then copolymerizing the chain extender, the polyurethane prepolymer and a cross-linking agent by using boron-nitrogen coordination diol as a chain extender to obtain a polyurethane solution, adding a two-dimensional transition metal carbide, and curing to form a film to obtain the polyurethane insulating coating;
the boron-nitrogen coordination dihydric alcohol is obtained by adding 4-hydroxymethyl phenylboronic acid and N, N, N ', N' -tetra (2-hydroxyethyl) adipamide.
The structural formula of the 4-hydroxymethyl phenylboronic acid is as follows:
the structural formula of the N, N, N ', N' -tetra (2-hydroxyethyl) adipamide is as follows:
the structural formula of the boron-nitrogen coordination dihydric alcohol is as follows:
the cross-linking agent is a boron-oxygen six-membered ring.
The two-dimensional transition metal carbonThe compound being Ti 3 C 2 。
The weight parts of the raw materials are as follows: 5 to 8 parts of diol oligomer, 2.7 to 4.5 parts of isocyanate, 0.7 to 2.6 parts of chain extender, 0.5 to 1.8 parts of cross-linking agent and 0.4 to 1 part of two-dimensional transition metal carbide.
The preparation method of the boron-nitrogen coordination dihydric alcohol comprises the following steps: putting 4-hydroxymethylphenylboronic acid into a reactor, adding N, N, N ', N' -tetra (2-hydroxyethyl) adipamide dissolved in N, N-dimethylformamide into a reaction system in the nitrogen atmosphere, then adding N, N-dimethylformamide as a reaction solvent, stirring and refluxing for 4 to 8h at 40 to 60 ℃, finishing the reaction, carrying out rotary evaporation to obtain a crude product, and then washing, crystallizing and drying to obtain the boron-nitrogen coordination dihydric alcohol; wherein the molar ratio of the using amount of the 4-hydroxymethylphenylboronic acid to the using amount of the N, N, N ', N' -tetra (2-hydroxyethyl) adipamide is (2 to 2.5): 1.
The molar ratio of the used 4-hydroxymethylphenylboronic acid to the used N, N, N ', N' -tetrakis (2-hydroxyethyl) adipamide is 2.1.
The preparation method of the cross-linking agent comprises the following steps: putting 4-hydroxymethylphenylboronic acid into a reactor, adding N, N-dimethylformamide as a solvent, stirring at 70-90 ℃ for 10-14h for dehydration condensation, after the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then crystallizing and drying to obtain the boric-oxygen six-membered ring, wherein the structural formula of the boric-oxygen six-membered ring is as follows:
the preparation method of the polyurethane solution comprises the following steps: adding a dihydric alcohol oligomer into a reactor, heating to remove water, adding isocyanate, adding a catalyst, and stirring for reaction to obtain a polyurethane prepolymer; dissolving a polyurethane prepolymer with N, N-dimethylformamide, adding boron-nitrogen coordination dihydric alcohol and a cross-linking agent, and stirring at 70-90 ℃ for reaction for 4-8 hours to obtain the polyurethane solution, wherein the structural formula of the polyurethane is shown in the specification
The preparation method of the polyurethane insulating coating comprises the following steps: adding a two-dimensional transition metal carbide into the polyurethane solution, stirring for 1 to 3 hours at 70 to 90 ℃, then carrying out ultrasonic dispersion, and curing to form a film so as to obtain the polyurethane insulating coating.
The polyurethane insulating coating prepared by the method.
Compared with the prior art, the invention has the beneficial effects that: the invention introduces phenylboronic acid to synthesize a micromolecule chain extension cross-linking agent, copolymerizes the micromolecule chain extension cross-linking agent with a polyurethane prepolymer to obtain a borate type polyurethane coating, and then adds a two-dimensional transition metal carbide MXene to blend to obtain the polyurethane insulating coating with high strength and high volume resistivity. When the coating has fine cracks or scratches in the using process, the insulating coating can be self-repaired to the original state with the aid of water when water exists or the air humidity is high, and the insulating coating can be recycled.
Detailed Description
The invention is further described with reference to specific examples.
Polytetrahydrofuran diol (PTMEG): mn 1000, purchased from Shanghai Michelin Biotech, inc.
Dicyclohexylmethane diisocyanate (HMDI): purchased from warrior chemical.
Isophorone diisocyanate (IPDI): CAS number 4098-71-9, available from Shanghai Merlin Biotech, inc.
4-hydroxymethylphenylboronic acid: CAS number 59016-93-2, available from Shanghai Maxin Biotechnology, inc.
N, N' -tetrakis (2-hydroxyethyl) adipamide: CAS number 6334-25-4, available from Shanghai Merlin Biotech, inc.
Two-dimensional transition metal carbide MXene (Ti) 3 C 2 ): purchased from Jilin, science and technology Limited, and having a specification of 400 mesh.
Hydroxyalkyl-terminated polysiloxane-polyether copolymer: the molecular weight Mn is 2200, and the molecular weight Mn is purchased from Shanghai Tager Polymer technology Co., ltd, and the mark is industrial Tech-2187.
The rest raw materials are conventional commercial products.
Example 1
(1) Synthesis of boron-nitrogen coordination dihydric alcohol chain extender
18.23g of 4-hydroxymethylphenylboronic acid was placed in a reactor, 14.18g of N, N' -tetrakis (2-hydroxyethyl) adipamide dissolved in N, N-Dimethylformamide (DMF) after water removal was added to the reaction system in a nitrogen atmosphere, DMF was then added as a reaction solvent, and stirring was carried out at 50 ℃ under reflux for 6 hours. After the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then washing, recrystallizing and freeze-drying to obtain a target product.
(2) Synthesis of boron-oxygen six-membered ring cross-linking agent
22.79g of 4-hydroxymethylphenylboronic acid is placed in a reactor, and the dehydrated DMF is added as a solvent, stirred at 80 ℃ for 12 hours, dehydrated and condensed. After the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then recrystallizing and freeze-drying to obtain a target product.
(3) Synthesis of polyurethane solution
1. Adding PTMEG into a reactor, heating under vacuum to remove water, adding HMDI, then adding dibutyltin dilaurate (DBTDL), and stirring for reacting for 2h to obtain a polyurethane prepolymer;
2. and dissolving the prepolymer by using the dewatered DMF, sequentially adding a metered boron-nitrogen coordination diol chain extender and a boron-oxygen six-membered ring cross-linking agent, stirring and reacting at 80 ℃ for 6 hours, and performing chain extension and partial cross-linking to obtain a polyurethane solution.
Wherein the dosage of each raw material is respectively as follows: PTMEG 60g, HMDI 39.4g, boron-nitrogen coordination dihydric alcohol chain extender 19.9g, boron-oxygen six-membered ring cross-linking agent 14.5g and DBTDL 0.27g.
(4) Preparation of polyurethane insulating coating
To the resulting polyurethane solution was added 1.4g of MXene (Ti), a two-dimensional transition metal carbide 3 C 2 ) And stirring for 2 hours at 80 ℃, ultrasonically treating the mixed solution while the mixed solution is hot to uniformly disperse the mixed solution, and curing to form a film to obtain the water-assisted room temperature self-repairing polyurethane insulating coating.
Example 2
(1) Synthesis of boron-nitrogen coordination dihydric alcohol chain extender
18.23g of 4-hydroxymethylphenylboronic acid was placed in a reactor, 14.18g of N, N' -tetrakis (2-hydroxyethyl) adipamide dissolved in water-removed DMF was added to the reaction system in a nitrogen atmosphere, and DMF was then added as a reaction solvent, and the mixture was stirred and refluxed at 50 ℃ for 6 hours. After the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then washing, recrystallizing and freeze-drying to obtain a target product.
(2) Synthesis of boron-oxygen six-membered ring cross-linking agent
22.79g of 4-hydroxymethylphenylboronic acid is placed in a reactor, and is added with dehydrated DMF as a solvent, stirred at 80 ℃ for 12 hours for dehydration and condensation. After the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then recrystallizing and freeze-drying to obtain a target product.
(3) Synthesis of polyurethane solution
1. Adding PTMEG into a reactor, heating under vacuum to remove water, adding isophorone diisocyanate (IPDI), adding a catalyst DBTDL, and stirring for reacting for 2 hours to obtain a polyurethane prepolymer;
2. and dissolving the prepolymer by using the dewatered DMF, sequentially adding a metered boron-nitrogen coordination diol chain extender and a boron-oxygen six-membered ring cross-linking agent, stirring and reacting at 80 ℃ for 6 hours, and performing chain extension and partial cross-linking to obtain a polyurethane solution.
Wherein the dosage of each raw material is respectively as follows: PTMEG 60g, IPDI 40g, boron-nitrogen coordination chain extender 9.9g, boron-oxygen six-membered ring cross-linking agent 19.3g and DBTDL 0.26g.
(4) Preparation of polyurethane insulating coating
To the resulting polyurethane solution was added 1.2g of the two-dimensional transition metal carbide MXene (Ti) 3 C 2 ) And stirring for 2 hours at 80 ℃, ultrasonically treating the mixed solution while the mixed solution is hot to uniformly disperse the mixed solution, and curing to form a film to obtain the water-assisted room temperature self-repairing polyurethane insulating coating.
Example 3
(1) Synthesis of boron-nitrogen coordination dihydric alcohol chain extender
18.23g of 4-hydroxymethylphenylboronic acid was placed in a reactor, 14.18g of N, N' -tetrakis (2-hydroxyethyl) adipamide dissolved in water-removed DMF was added to the reaction system in a nitrogen atmosphere, and DMF was added as a reaction solvent, and the mixture was stirred and refluxed at 50 ℃ for 6 hours. After the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then washing, recrystallizing and freeze-drying to obtain a target product.
(2) Synthesis of boron-oxygen six-membered ring cross-linking agent
22.79g of 4-hydroxymethylphenylboronic acid is placed in a reactor, and is added with dehydrated DMF as a solvent, stirred at 80 ℃ for 12 hours for dehydration and condensation. After the reaction is finished, carrying out rotary evaporation to obtain a target crude product, and then recrystallizing and freeze-drying to obtain the target product.
(3) Synthesis of polyurethane solutions
1. Adding PTMEG and a terminal hydroxyalkyl polysiloxane-polyether copolymer into a reactor, heating in vacuum to remove water, adding HMDI, then adding a DBTDL catalyst, and stirring for reacting for 2 hours to obtain a polyurethane prepolymer;
2. and dissolving the prepolymer by using the dewatered DMF, sequentially adding a boron-nitrogen coordination diol chain extender and a boron-oxygen six-membered ring cross-linking agent in a metered amount, stirring and reacting for 6 hours at 80 ℃, and carrying out chain extension and partial cross-linking to obtain a polyurethane solution.
Wherein the dosage of each raw material is respectively as follows: 50g of PTMEG, 13.8g of terminal hydroxyalkyl polysiloxane-polyether copolymer, 36.7g of HMDI, 20.7g of boron-nitrogen coordination chain extender, 12.6g of boron-oxygen six-membered ring cross-linking agent and 0.27g of DBTDL.
(4) Preparation of polyurethane insulating coating
To the resulting polyurethane solution was added 1.3g of MXene (Ti), a two-dimensional transition metal carbide 3 C 2 ) And stirring for 2 hours at 80 ℃, ultrasonically treating the mixed solution while the mixed solution is hot to ensure that the mixed solution is uniformly dispersed, and curing to form a film to obtain the water-assisted room temperature self-repairing polyurethane insulating coating.
Example 4
(1) Synthesis of boron-nitrogen coordination dihydric alcohol chain extender
18.23g of 4-hydroxymethylphenylboronic acid was placed in a reactor, 14.18g of N, N, N ', N' -tetrakis (2-hydroxyethyl) adipamide dissolved with removal of water and DMF was added to the reaction system in a nitrogen atmosphere, DMF was then added as a reaction solvent, and stirred and refluxed at 50 ℃ for 6 hours. After the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then washing, recrystallizing and freeze-drying to obtain a target product.
(2) Synthesis of boron-oxygen six-membered ring cross-linking agent
22.79g of 4-hydroxymethylphenylboronic acid is placed in a reactor, and is added with dehydrated DMF as a solvent, stirred at 80 ℃ for 12 hours for dehydration and condensation. After the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then carrying out recrystallization and freeze drying to obtain a target product.
(3) Synthesis of polyurethane solutions
1. Adding PTMEG and a terminal hydroxyalkyl polysiloxane-polyether copolymer into a reactor, heating in vacuum to remove water, adding IPDI (isophorone diisocyanate), adding a DBTDL (bis-vinyl-methyl-ethyl-methacrylate) catalyst, and stirring for reacting for 2 hours to obtain a polyurethane prepolymer;
2. and dissolving the prepolymer by using the dewatered DMF, sequentially adding a boron-nitrogen coordination diol chain extender and a boron-oxygen six-membered ring cross-linking agent in a metered amount, stirring and reacting for 6 hours at 80 ℃, and carrying out chain extension and partial cross-linking to obtain a polyurethane solution.
The dosage of each raw material is respectively as follows: PTMEG 50g, hydroxyalkyl terminated polysiloxane-polyether copolymer 12.3g, IPDI 37g, boron-nitrogen coordination chain extender 15.3g, boron-oxygen six-membered ring cross-linking agent 22.4g, DBTDL 0.27g
(4) Preparation of polyurethane insulating coating
To the resulting polyurethane solution was added 1.2g of the two-dimensional transition metal carbide MXene (Ti) 3 C 2 ) And stirring for 2 hours at 80 ℃, ultrasonically treating the mixed solution while the mixed solution is hot to ensure that the mixed solution is uniformly dispersed, and curing to form a film to obtain the water-assisted room temperature self-repairing polyurethane insulating coating.
The coatings obtained in the above examples were subjected to performance tests,
the test method comprises the following steps:
1. tensile testing is carried out on the polyurethane composite coating sample strips (the sample strips are 40mmm multiplied by 8mm multiplied by 0.84 mm) prepared in each example by adopting a universal mechanical testing machine; and after manual cutting, soaking the section in water for 1 to 2 minutes, taking out, tightly butting the sections, standing at room temperature for 24 hours, testing the tensile property of the coating sample strip again, and evaluating the room temperature self-repairing effect.
2. And detecting the volume resistivity of the coating by using a volume surface resistance tester, and evaluating the electrical insulation performance of the coating.
3. After chopping the coatings of examples 1 to 4, they were dissolved thoroughly in Tetrahydrofuran (THF) and stirred at 50 ℃ for 6h, the solution was again cured to give a film in a forced air drying cabinet and the resulting polyurethane coatings were again tested for strength according to test method 1.
The test results are as follows:
1. mechanical properties: the tensile strengths of the coatings of examples 1-4 as received were 11.56 MPa, 8.72 MPa, 10.24 MPa and 7.96 MPa, respectively. After the coatings of examples 1-4 are self-repaired for 24 hours at room temperature under the assistance of water, the tensile strengths of the coatings are respectively 11.13 MPa, 8.67 MPa, 9.95 MPa and 7.92 MPa, and the self-repairing efficiencies are respectively 96.28%, 99.43%, 97.17% and 99.45%. The results show that the polyurethane coating has a remarkable room-temperature self-repairing effect under the assistance of water, and maintains excellent mechanical properties.
2. Insulating property: the volume resistivities of the coatings of examples 1 to 4 were 7X 10, respectively 14 Ω·cm、9×10 13 Ω·cm、2×10 15 Omega. Cm and 6X 10 13 Omega cm, has higher volume resistivity and shows excellent electrical insulation property.
3. The repeatable processability is as follows: the tensile strengths of the coatings of examples 1-4 after the recycling process were 11.43 MPa, 8.59 MPa, 10.22 MPa, and 7.87 MPa, respectively. The strength of the coating was similar to that of the original, indicating that the polyurethane insulation coating has good repeated processing characteristics.
Claims (10)
1. A preparation method of a polyurethane insulating coating capable of self-repairing at room temperature through water assistance is characterized in that firstly, a polyurethane prepolymer is prepared by utilizing a diol oligomer and isocyanate, then boron-nitrogen coordination diol is used as a chain extender, the polyurethane prepolymer and a cross-linking agent are copolymerized to obtain a polyurethane solution, then a two-dimensional transition metal carbide is added, and the polyurethane insulating coating is obtained after curing and film forming;
the boron-nitrogen coordination dihydric alcohol is obtained by adding 4-hydroxymethyl phenylboronic acid and N, N, N ', N' -tetra (2-hydroxyethyl) adipamide.
2. The preparation method of the polyurethane insulating coating capable of self-repairing at room temperature through water assistance as claimed in claim 1, wherein the cross-linking agent is a boron-oxygen six-membered ring.
3. The method for preparing the polyurethane insulating coating capable of self-repairing at room temperature through water assistance of claim 1, wherein the two-dimensional transition metal carbide is Ti 3 C 2 。
4. The preparation method of the polyurethane insulating coating capable of self-repairing at room temperature through water assistance according to claim 1, characterized in that the raw materials in parts by weight are: 5 to 8 parts of diol oligomer, 2.7 to 4.5 parts of isocyanate, 0.7 to 2.6 parts of chain extender, 0.5 to 1.8 parts of cross-linking agent and 0.4 to 1 part of two-dimensional transition metal carbide.
5. The preparation method of the polyurethane insulating coating capable of self-repairing at room temperature through water assistance according to claim 1, characterized in that the preparation method of the boron-nitrogen coordination diol comprises the following steps: putting 4-hydroxymethylphenylboronic acid into a reactor, adding N, N, N ', N' -tetra (2-hydroxyethyl) adipamide dissolved in N, N-dimethylformamide into a reaction system in a nitrogen atmosphere, then adding N, N-dimethylformamide as a reaction solvent, stirring and refluxing for 4 to 8 hours at 40 to 60 ℃, ending the reaction, carrying out rotary evaporation to obtain a crude product, and washing, crystallizing and drying to obtain the boron-nitrogen coordination dihydric alcohol, wherein the molar ratio of the usage amount of the 4-hydroxymethylphenylboronic acid to the usage amount of the N, N, N ', N' -tetra (2-hydroxyethyl) adipamide is (2 to 2.5): 1.
6. The preparation method of the polyurethane insulating coating capable of self-repairing at room temperature through water assistance is characterized in that the molar ratio of the 4-hydroxymethylphenylboronic acid to the N, N, N ', N' -tetrakis (2-hydroxyethyl) adipamide is 2.1.
7. The preparation method of the polyurethane insulating coating capable of self-repairing at room temperature through water assistance as claimed in claim 1 or 2, wherein the preparation method of the cross-linking agent is as follows: putting 4-hydroxymethylphenylboronic acid into a reactor, adding N, N-dimethylformamide as a solvent, stirring at 70-90 ℃ for 10-14h for dehydration condensation, after the reaction is finished, carrying out rotary evaporation to obtain a crude product, and then crystallizing and drying to obtain the boron-oxygen six-membered ring.
8. The preparation method of the polyurethane insulating coating capable of self-repairing at room temperature through water assistance as claimed in claim 1, wherein the preparation method of the polyurethane solution is as follows: adding a diol oligomer into a reactor, heating to remove water, adding isocyanate, adding a catalyst, and stirring to react to obtain a polyurethane prepolymer; dissolving a polyurethane prepolymer with N, N-dimethylformamide, adding boron-nitrogen coordination dihydric alcohol and a cross-linking agent, and stirring and reacting at 70-90 ℃ for 4-8 hours to obtain the polyurethane solution.
9. The preparation method of the polyurethane insulating coating capable of self-repairing at room temperature through water assistance as claimed in claim 1, wherein the preparation method of the polyurethane insulating coating is as follows: adding a two-dimensional transition metal carbide into the polyurethane solution, stirring for 1 to 3 hours at 70 to 90 ℃, then carrying out ultrasonic dispersion, and curing to form a film so as to obtain the polyurethane insulating coating.
10. A polyurethane insulating coating prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210988429.0A CN115304992B (en) | 2022-08-17 | 2022-08-17 | Polyurethane insulating coating capable of being self-repaired at room temperature through water assistance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210988429.0A CN115304992B (en) | 2022-08-17 | 2022-08-17 | Polyurethane insulating coating capable of being self-repaired at room temperature through water assistance and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115304992A true CN115304992A (en) | 2022-11-08 |
| CN115304992B CN115304992B (en) | 2024-04-05 |
Family
ID=83863573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210988429.0A Active CN115304992B (en) | 2022-08-17 | 2022-08-17 | Polyurethane insulating coating capable of being self-repaired at room temperature through water assistance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115304992B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897148A (en) * | 2019-02-26 | 2019-06-18 | 西安交通大学 | Renewable polyureas-urethane of dynamic covalent cross-linking based on stable boric acid ester bond and its preparation and application |
| CN111732701A (en) * | 2020-07-20 | 2020-10-02 | 合肥工业大学 | Self-repairing polyurethane based on boron-nitrogen coordination and preparation method thereof |
| CN113004776A (en) * | 2021-02-03 | 2021-06-22 | 中山大学 | Water-based self-repairing coating and application thereof |
| CN113563559A (en) * | 2021-07-20 | 2021-10-29 | 陕西科技大学 | Self-repairing polyurethane based on boron-oxygen hexacyclic ring and preparation method thereof |
| CN114045082A (en) * | 2021-12-14 | 2022-02-15 | 陕西科技大学 | Composite coating with self-repairing, air-permeable and wear-resistant properties, and preparation method and application thereof |
| CN114478992A (en) * | 2022-02-09 | 2022-05-13 | 李玲 | Borate-based self-repairing polyurethane based on internal coordination and preparation method thereof |
| US20220243014A1 (en) * | 2019-06-06 | 2022-08-04 | Technion Research And Development Foundation Limited | Hydrolytically stable self-healing elastomer |
| CN114907755A (en) * | 2022-04-02 | 2022-08-16 | 山东力合新材料科技有限公司 | Preparation method of visible light induced self-repairing coating based on two-dimensional titanium carbide |
-
2022
- 2022-08-17 CN CN202210988429.0A patent/CN115304992B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897148A (en) * | 2019-02-26 | 2019-06-18 | 西安交通大学 | Renewable polyureas-urethane of dynamic covalent cross-linking based on stable boric acid ester bond and its preparation and application |
| US20220243014A1 (en) * | 2019-06-06 | 2022-08-04 | Technion Research And Development Foundation Limited | Hydrolytically stable self-healing elastomer |
| CN111732701A (en) * | 2020-07-20 | 2020-10-02 | 合肥工业大学 | Self-repairing polyurethane based on boron-nitrogen coordination and preparation method thereof |
| CN113004776A (en) * | 2021-02-03 | 2021-06-22 | 中山大学 | Water-based self-repairing coating and application thereof |
| CN113563559A (en) * | 2021-07-20 | 2021-10-29 | 陕西科技大学 | Self-repairing polyurethane based on boron-oxygen hexacyclic ring and preparation method thereof |
| CN114045082A (en) * | 2021-12-14 | 2022-02-15 | 陕西科技大学 | Composite coating with self-repairing, air-permeable and wear-resistant properties, and preparation method and application thereof |
| CN114478992A (en) * | 2022-02-09 | 2022-05-13 | 李玲 | Borate-based self-repairing polyurethane based on internal coordination and preparation method thereof |
| CN114907755A (en) * | 2022-04-02 | 2022-08-16 | 山东力合新材料科技有限公司 | Preparation method of visible light induced self-repairing coating based on two-dimensional titanium carbide |
Non-Patent Citations (1)
| Title |
|---|
| BAO CHUNYANG ET AL: "Room-Temperature Self-Healing and Recyclable Tough Polymer Composites Using Nitrogen-Coordinated Boroxines", pages 2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115304992B (en) | 2024-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111217985B (en) | Metal coordination self-healing polyurethane elastomer and preparation method thereof | |
| Kulkarni et al. | Spectroscopic, transport, and morphological studies of polyaniline doped with inorganic acids | |
| CN112864369B (en) | Modified high-nickel ternary cathode material and preparation method thereof | |
| CN111925642B (en) | Preparation method of self-repairing carbon nano tube-cationic waterborne polyurethane electromagnetic shielding composite material | |
| CN115181232B (en) | Polyurethane material and preparation method and application thereof | |
| CN111187428B (en) | Lignin-based polyol, modified lignin-based polyurethane material, modified lignin-based polyurethane film, and preparation method and application thereof | |
| CN112701419B (en) | SEI film material, preparation method and negative plate | |
| Kwon et al. | Preparation and properties of waterborne-polyurethane coating materials containing conductive polyaniline | |
| CN115232465A (en) | Preparation method of tough self-repairing material capable of realizing self-repairing in seawater | |
| CN103755920A (en) | Solvent-free isocyanate prepolymer, preparartion method of solvent-free isocyanate prepolymer and isocyanate composition | |
| CN113801030A (en) | Active cross-linking agent, cross-linked polyurethane material, preparation method and recovery method thereof | |
| CN101633828A (en) | High-temperature resistant waterborne polyurethane adhesive and preparation method thereof | |
| CN113136017B (en) | Polyurethane with pH response and self-healing performance and preparation method thereof | |
| Lee et al. | Polymer gel electrolytes prepared by thermal curing of poly (vinylidene fluoride)–hexafluoropropene/poly (ethylene glycol)/propylene carbonate/lithium perchlorate blends | |
| CN115304992A (en) | Water-assisted room temperature self-repairing polyurethane insulating coating and preparation method thereof | |
| CN115806514B (en) | Solvent-free self-repairing polyurethane based on dynamic disulfide bonds and preparation method thereof | |
| CN116536000A (en) | PET protective film and preparation method and application thereof | |
| CN115595019A (en) | Locust bean gum conductive coating and preparation method thereof | |
| CN115433482A (en) | Preparation method of water-resistant coating of water-based polyurethane | |
| CN115612054A (en) | Dynamic cross-linked polyurethane material and synthesis method thereof | |
| Paşahan et al. | Synthesis, Characterization anc Dopamine Selectivity of 1, 4-bis (3-aminopropyl) piperazine—Containing Polyimide | |
| CN111592655A (en) | Self-healing flexible composite material and preparation method thereof | |
| CN113956435B (en) | Preparation method of polyurea cross-linked network elastomer | |
| CN116813855A (en) | Cross-linked polymer containing high-density imidazole, preparation method thereof and application thereof in fuel cell | |
| CN118064051B (en) | Graphene oxide-polyurethane paint protective coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240428 Address after: No. 88, Can District South Road, Jiangbei New District, Nanjing City, Jiangsu Province, 210000 Patentee after: NANJING HUIKE POLYMER MATERIAL Co.,Ltd. Country or region after: China Address before: Longpan road Xuanwu District of Nanjing city of Jiangsu Province, No. 159 210037 Patentee before: NANJING FORESTRY University Country or region before: China |
|
| TR01 | Transfer of patent right |