CN115838479A - Preparation method of waterborne room temperature self-repairing polyurethane based on metal coordination bond - Google Patents
Preparation method of waterborne room temperature self-repairing polyurethane based on metal coordination bond Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 94
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 94
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000006175 metal-ion buffer Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 150000002148 esters Chemical class 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
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 40
- 229910021645 metal ion Inorganic materials 0.000 abstract description 30
- -1 carboxyl ions Chemical class 0.000 abstract description 13
- 230000002441 reversible effect Effects 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000003993 interaction Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- SYOXXLBWSQUWBI-UHFFFAOYSA-N 2-[2-hydroxyethyl(pyridin-2-ylmethyl)amino]ethanol Chemical compound OCCN(CCO)CC1=CC=CC=N1 SYOXXLBWSQUWBI-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical class NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 239000013003 healing agent Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000013005 self healing agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of waterborne room temperature self-repairing polyurethane based on metal coordination bonds. The aqueous room temperature self-repairing polyurethane is prepared by blending a metal ion buffer solution and an aqueous polyurethane emulsion, wherein the metal ion buffer solution is prepared by dissolving metal salt in deionized water and then adding a proper amount of ammonia water. According to the invention, the metal ion buffer solution is prepared firstly and then the aqueous polyurethane emulsion is added, so that emulsion breaking caused by metal ions can be avoided, in the film forming process, along with water volatilization, the metal ions and carboxyl ions on a polyurethane molecular chain form dynamic reversible coordinate bonds, and the dynamic reversible coordinate bonds can endow the material with good room temperature self-repairing performance, and meanwhile, the metal ions are used as cross-linking points, so that the mechanical strength, the solvent resistance and the water resistance of the material are improved. The method provided by the invention is environment-friendly and low in cost, and the prepared material has excellent self-repairing efficiency and mechanical strength, excellent solvent resistance and water resistance, and can be applied to the fields of intelligent coatings, flexible electronics and the like.
Description
Technical Field
The invention relates to a preparation method of waterborne room temperature self-repairing polyurethane, in particular to the preparation of waterborne room temperature self-repairing polyurethane based on metal coordination bonds, belonging to the fields of intelligent coatings, flexible electronics and the like.
Background
With the idea of green development, waterborne Polyurethane (WPU) uses water as a dispersion medium, does not cause the release of a large amount of Volatile Organic Compounds (VOCs), shows low temperature resistance, flexibility, resilience and abrasion resistance equivalent to solvent-borne polyurethane, is a promising direction for polyurethane development, and is widely used in the fields of intelligent coatings, flexible electronics and the like (Journal of Materials Science, 2020, 55: 73-87). However, in the using process of the waterborne polyurethane, physical damages such as scratches, microcracks and the like are inevitably generated, the service life of the waterborne polyurethane is shortened due to the damages, the maintenance cost is increased, and certain potential safety hazards are caused. Inspired by biomaterials, the self-repair function imparted to waterborne polyurethane organisms is an effective way to improve their durability, reliability, safety, and reduce their maintenance costs (Journal of materials science, 2017, 52: 197-207).
According to the self-repairing principle, the self-repairing types are generally divided into two types: exopathic self-repair and endogenous self-repair. The former mainly uses self-healing agents embedded in a polymer matrix to activate the self-healing response, but is limited by healing agent depletion, with limited number of repairs (Soft Matter, 2020, 16: 570-590). In contrast, the latter rely primarily on reversible covalent bonds (e.g., diels-Alder reactions, disulfide bonds, diselenide bonds, and the like) or noncovalent interactions (e.g., host-guest interactions, hydrogen bonds, ionic bonds, coordination bonds, or pi-pi stacking, and the like) to effect healing of lesions without the need for repair agents, with the advantage of repeated repair, and thus are of particular interest (Nature Reviews Materials, 2020, 5: 562-583). With the development of endogenous self-repairing materials, the preparation of materials with room temperature rapid repair and high mechanical strength can better meet the requirements of practical application, and becomes a hotspot of current research (Angewandte Chemie International Edition, 2021, 60: 7947-7955). In general, the bond energy of the dynamic covalent bond is higher, and the dissociation and recombination are slower, so that the room temperature self-repairing material based on the dynamic covalent bond has better mechanical strength but slower self-repairing rate (Polymer International, 2019, 68: 1084-1090). Compared with dynamic covalent bonds, the bond energy of non-covalent interactions is low, and dissociation and recombination are fast at room temperature, and therefore, room temperature self-healing materials based on dynamic non-covalent interactions are rapidly developed (Chemical Engineering Journal, 2020, 398.
Metal coordination bonds are typically dynamic non-covalent interactions that have moderate bond energies between van der waals and covalent bond energies, and the presence of a large number of readily available ligands and metal ions makes them highly attractive in the field of self-healing Materials (Advanced Materials, 2020, 32: 1903762). The moderate bonding of the metal coordination bond enables it to have two advantages: on one hand, the material is weaker than a strong dynamic covalent bond, and is more likely to show rapid dissociation and recombination so as to endow the material with a better self-repairing function; on the other hand, it has a higher strength than the usual non-covalent forces to give the material better mechanical properties (Journal of Materials Science, 2020, 55: 14045-14057). Thus, the introduction of coordination bonds into materials is considered to be an ideal method that can impart excellent mechanical and self-healing properties to the materials. For example, chinese patent (CN 109337087A) discloses a method for preparing polyurethane with toughness, fatigue resistance, notch insensitivity and excellent self-repairing performance by metal coordination, which comprises the steps of firstly reacting isocyanate, polyether polyol and N- (2-picolyl) iminodiethanol (PY) as a chain extender to obtain polyurethane, then dissolving the polyurethane and ferric salt in an organic solvent, reacting and removing the solvent to obtain the metal coordination type self-repairing polyurethane. The material has a higher tensile strength of 4.6MPa and a high Young's modulus of 3.2MPa under a strain condition of about 498 percent and utilizes Fe 2+ And the breakage and recombination of the pyridyl coordination bond, and the repair is carried out for 36 hours at room temperature, and the tensile strength of the repaired sample can reach 96 percent of the original tensile strength. Xu et al reacted diphenylmethane diisocyanate with polytetrahydrofuran ether glycol to form a prepolymer, which was then capped with a dopamine derivative to form a dopamine-terminated polyurethane, which was then reacted with CaCl 2 Dissolving the components in N, N-dimethylformamide to react, and removing the solvent to obtain the metal coordination self-repairing polyurethane. The material has higher tensile strength of 4.59MPa and high Young's modulus of 10.93MPa under the condition of 350% strain and is arranged in seaUnder the induction of water, ca is utilized 2+ And the fracture and recombination of catechol are carried out, the repair is carried out for 24 hours at room temperature, and the toughness of the repaired sample can reach 84 percent of the original sample (Polymer International, 2019, 68: 1084-1090). The polyurethane material realizes better mechanical property and room temperature self-repairing property by introducing coordination bonds. However, in the preparation process of these polyurethane materials, a large amount of organic solvents are used, which is not friendly to the environment, and therefore, the preparation of aqueous room temperature self-repairing polyurethane containing metal coordination bonds is an important development trend.
The aqueous polyurethane emulsion generally maintains the stability of the emulsion through carboxyl ions on polymer chains, and when the aqueous polyurethane emulsion is directly blended with metal ions by adopting the preparation method of the materials, emulsion breaking can be caused by aggregation of emulsion particles due to strong interaction of the carboxyl ions and the metal ions. Therefore, how to reasonably introduce metal ions and ensure the stability of the emulsion is the key to preparing the waterborne room temperature self-repairing polyurethane based on metal coordination bonds.
The metal ion can form ammonia coordination complex ion in a proper amount of ammonia water, and when the metal ion exists in the ammonia coordination complex ion, the ligand NH 3 The metal ions can be protected to slow down the complexation of the metal ions and the carboxyl ions on the polyurethane chain, so that the aqueous polyurethane emulsion is in a stable state. In the film forming process, along with the volatilization of ammonia, metal ions are gradually dissociated from the complex and carry out complex crosslinking reaction with carboxyl ions on a polyurethane molecular chain to form a dynamic and reversible coordination bond. The dynamic reversible coordination bond can endow the material with good room temperature self-repairing performance, is used as a cross-linking point, is mainly positioned between interfaces where emulsion particles are mutually fused, is a weak part of the material during extrusion film forming, and can effectively improve the mechanical strength of the material. In addition, the introduction of coordination bonds can enable polyurethane molecular chains to be crosslinked to form a three-dimensional network structure, and the defects of water resistance and solvent resistance of the material are improved. The characteristics enable the waterborne room temperature self-repairing polyurethane to have good application prospects in the fields of intelligent coatings, flexible electronics and the like, however, the metal ion buffer solution and the waterborne polyurethane emulsion are adopted together at presentThe mixed method for preparing the waterborne room temperature self-repairing polyurethane based on the metal coordination bond is not reported.
The metal salt is dissolved in deionized water, then a proper amount of ammonia water is added to prepare a metal ion buffer solution, and then the metal ion buffer solution is mixed with the aqueous polyurethane emulsion to obtain the aqueous room temperature self-repairing polyurethane based on the metal coordination bond. According to the invention, the metal ion buffer solution is added into the aqueous polyurethane emulsion, so that emulsion breaking caused by metal ions can be effectively avoided, and in the film forming process, along with volatilization of ammonia, the metal ions are gradually dissociated from the complex to form a dynamic and reversible coordination bond with carboxyl ions on a polyurethane molecular chain. The dynamic reversible coordination bonds can endow the material with good room temperature self-repairing performance, are used as cross-linking points, are mainly positioned between interfaces fused with emulsion particles and are weak parts of the material during extrusion film forming, so that the mechanical strength of the material can be effectively improved by the dynamic reversible coordination bonds. In addition, the introduction of coordination bonds can enable polyurethane molecular chains to be crosslinked to form a three-dimensional network structure, and the defects of water resistance and solvent resistance of the material are improved. The material prepared by the invention is an aqueous system, does not contain an organic solvent, is environment-friendly and low in cost, overcomes the defect of emulsion instability caused by mixing of metal ions and emulsion, has good mechanical property and room temperature self-repairing efficiency, has good solvent resistance and water resistance, and can be used in the fields of intelligent coatings, flexible electronics and the like.
Disclosure of Invention
The invention relates to a preparation method of waterborne room temperature self-repairing polyurethane based on metal coordination bonds, which comprises the following steps of firstly dissolving metal salt in deionized water, and then adding a proper amount of ammonia water to prepare a metal ion buffer solution; then, reacting high-molecular dihydric alcohol, diisocyanate and dimethylolpropionic acid to prepare a prepolymer, chain extending by 1,4-butanediol, and then neutralizing and emulsifying to obtain an aqueous polyurethane emulsion; and finally, slowly dripping the metal ion buffer solution into the aqueous polyurethane emulsion under the action of magnetic stirring, and uniformly dispersing to obtain the aqueous room-temperature self-repairing polyurethane emulsion.
The invention provides waterborne room temperature self-repairing polyurethane based on metal coordination bonds, which is characterized in that:
(1) The metal coordination bond-based waterborne room temperature self-repairing polyurethane provided by the invention is prepared by mixing a metal ion buffer solution and a waterborne polyurethane emulsion;
(2) The aqueous room temperature self-repairing polyurethane based on metal coordination bonds provided by the invention is characterized in that ammonia water is added into a metal ion solution to enable metal ions to form ammonia-coordinated complex ions, namely ligand NH 3 The metal ions can be protected to slow down the complexing action of the metal ions and the carboxyl ions on the polyurethane chain, so that the water-based polyurethane emulsion is ensured to be in a stable state;
(3) According to the waterborne room temperature self-repairing polyurethane based on the metal coordination bond, in the film forming process, along with volatilization of ammonia, metal ions are gradually dissociated from the complex to form a dynamic reversible coordination bond with carboxyl ions on a polyurethane molecular chain, and the dynamic reversible coordination bond can endow the material with good room temperature self-repairing performance;
(4) According to the waterborne room temperature self-repairing polyurethane based on the metal coordination bond, the metal ions and the carboxyl ions on the polyurethane molecular chain form coordination bonds, the coordination bonds are mainly located between interfaces where emulsion particles are mutually fused and are weak parts of the material when the emulsion particles are extruded to form a film, and the mechanical strength of the material is effectively improved. In addition, the introduction of coordination bonds can enable polyurethane molecular chains to be crosslinked to form a three-dimensional network structure, and the defects of water resistance and solvent resistance of the material are improved.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the self-repairing waterborne polyurethane based on the metal coordination bond comprises the steps of dissolving metal salt in deionized water, and adding a proper amount of ammonia water to prepare a metal ion buffer solution; then, reacting high-molecular dihydric alcohol, diisocyanate and dimethylolpropionic acid to prepare a prepolymer, chain extending by 1,4-butanediol, and then neutralizing and emulsifying to obtain an aqueous polyurethane emulsion; finally, slowly dripping the metal ion buffer solution into the aqueous polyurethane emulsion under the action of magnetic stirring, and uniformly dispersing to obtain the polyurethane emulsion, wherein the mass ratio of each raw material component is as follows:
18 to 30 portions of diisocyanate
1,4 butanediol 1-3
30-100 parts of high-molecular dihydric alcohol
Dimethylolpropionic acid 3-8
2 to 5 portions of triethylamine
0.01-0.02% of dibutyltin dilaurate
1 to 3 of metal salt
3 to 9 portions of ammonia water (25 to 28 percent)
4 to 10 portions of organic solvent
120 to 290 portions of deionized water
The waterborne room temperature self-repairing polyurethane based on the metal coordination bond is prepared by the following specific method:
(1) Firstly, adding metal salt into deionized water to be completely dissolved, and then adding a proper amount of ammonia water to prepare a metal ion buffer solution; (2) Placing high-molecular dihydric alcohol and dimethylolpropionic acid in a rotary evaporator, and distilling for 3-5 h under reduced pressure at 100-130 ℃ and the vacuum degree of 0.09MPa to remove water; sequentially adding the two dried components, diisocyanate and dibutyltin dilaurate into a three-neck flask with a stirring device, reacting at 70-90 ℃ under the protection of nitrogen to obtain an isocyanate-terminated prepolymer, wherein the isocyanate-terminated prepolymer is obtained by 3-5 h; cooling to 50-60 ℃, adding 1, 4-butanediol for chain extension, and reacting for 2-4 h under the protection of nitrogen; cooling to 40 ℃, adding an organic solvent to adjust the system viscosity, adding triethylamine to perform neutralization reaction for 10-15 min, then adding deionized water to perform high-speed emulsification for 15-20 min under the condition of 1500-1800 r/min, adjusting the rotating speed to 500-800 r/min, and continuously stirring for 1.5-2 h; finally, in a rotary evaporator, carrying out reduced pressure distillation on the mixture at the temperature of between 40 and 50 ℃ and under the vacuum degree of between 0.080 and 0.088 MPa for 2 to 3h, and removing an organic solvent to obtain aqueous polyurethane emulsion; (3) Slowly dripping the metal ion buffer solution into the waterborne polyurethane emulsion under the action of magnetic stirring, and stirring and dispersing for 20-30 min to obtain the waterborne room temperature self-repairing polyurethane emulsion.
Wherein the high molecular dihydric alcohol is polypropylene glycol or polyethylene glycolPolytetramethylene ether glycol, poly adipic acid-1,4-butanediol ester glycol, polycaprolactone glycol and polycarbonate glycol, and the number average molecular weight of the poly tetramethylene ether glycol is one of 1000 g/mol, 2000 g/mol and 3000 g/mol; the diisocyanate is one of isophorone diisocyanate, 4,4' -dicyclohexylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate; the metal salt being Zn 2+ 、Cu 2+ 、Co 2+ And Ni 2+ One of acetate, sulfate, nitrate and hydrochloride of (a); the organic solvent is one of tetrahydrofuran, acetone, butanone and chloroform.
The invention has the advantages that: according to the waterborne room temperature self-repairing polyurethane based on the metal coordination bond, the metal salt is dissolved in deionized water, a proper amount of ammonia water is added to prepare a metal ion buffer solution, and then the waterborne polyurethane emulsion is added, so that emulsion breaking caused by metal ions can be avoided, and the waterborne polyurethane emulsion is ensured to be in a stable state; in the film forming process, metal ions and carboxyl ions on a polyurethane molecular chain form a dynamic reversible coordination bond, and the dynamic reversible coordination bond can endow the material with good room-temperature self-repairing performance; the metal ions and the carboxyl on the polymer chain form coordination bonds, and the coordination bonds are mainly positioned between interfaces fused with emulsion particles and are weak parts of the material during extrusion film forming, so that the mechanical strength of the material can be effectively improved; in addition, the introduction of coordination bonds can enable polyurethane molecular chains to be crosslinked to form a three-dimensional network structure, and the water resistance and the solvent resistance of the material are improved.
Detailed Description
The first embodiment is as follows: adding 0.458g of zinc acetate into 10g of deionized water for complete dissolution, and then adding 3g of ammonia water to prepare a metal ion buffer solution; (2) Putting PTMG-2000 and dimethylolpropionic acid in a rotary evaporator, distilling 4h under reduced pressure at 120 ℃ and under the vacuum degree of 0.09MPa, and removing water; sequentially adding 20g of dehydrated and dried PTMG-2000, 1.34g of dimethylolpropionic acid, 6.67g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate into a three-neck flask with a stirring device, and reacting at 80 ℃ for 4 hours under the protection of nitrogen to obtain a prepolymer; then cooling to 60 ℃, adding 0.45g of 1, 4-butanediol for chain extension, and reacting 4h under the protection of nitrogen; cooling to 40 ℃, adding 5g of acetone to adjust the system viscosity, adding 0.87g of triethylamine to perform neutralization reaction for 15min, then adding 68.43g of deionized water to perform high-speed emulsification and dispersion for 20min under the condition of 1500/min, adjusting the rotating speed to 500r/min, and continuously stirring for 2h; finally, 3h is distilled under reduced pressure in a rotary evaporator at 50 ℃ and under the vacuum degree of 0.088 MPa, and the organic solvent is removed to obtain the aqueous polyurethane emulsion; (3) And slowly dripping the metal ion solution into the aqueous polyurethane emulsion under the action of magnetic stirring, and stirring and dispersing for 30 min to obtain the aqueous room-temperature self-repairing polyurethane emulsion.
Example two: adding 0.458g of zinc acetate into 10g of deionized water for complete dissolution, and then adding 3g of ammonia water to prepare a metal ion buffer solution; (2) Placing PPG-2000 and dimethylolpropionic acid in a rotary evaporator, distilling at 100 deg.C under vacuum degree of 0.09MPa for 5h under reduced pressure, and removing water; sequentially adding 20g of dehydrated and dried PPG-2000, 1.34g of dimethylolpropionic acid, 6.67g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate into a three-neck flask with a stirring device, and reacting at 80 ℃ for 4 hours under the protection of nitrogen to obtain a prepolymer; then cooling to 60 ℃, adding 0.45g of 1, 4-butanediol for chain extension, and reacting 4h under the protection of nitrogen; cooling to 40 ℃, adding 5g of butanone to adjust the viscosity of the system, adding 0.87g of triethylamine to neutralize and react for 15min, then adding 68.43g of deionized water to emulsify and disperse for 20min at a high speed under the condition of 1500r/min, adjusting the rotating speed to 800r/min, and continuously stirring for 1.5h; finally, 3h is distilled under reduced pressure in a rotary evaporator at 50 ℃ and under the vacuum degree of 0.088 MPa, and the organic solvent is removed to obtain the aqueous polyurethane emulsion; (3) Slowly dripping the metal ion solution into the aqueous polyurethane emulsion under the action of magnetic stirring, and mechanically stirring and dispersing for 30 min to obtain the aqueous room-temperature self-repairing polyurethane emulsion.
Example three: adding 0.458g of zinc acetate into 10g of deionized water for complete dissolution, and then adding 3g of ammonia water to prepare a metal ion buffer solution; (2) Placing PPG-2000 and dimethylolpropionic acid in a rotary evaporator, and distilling at 120 deg.C and vacuum degree of 0.09MPa under reduced pressure for 4 hr to remove water; sequentially adding 20g of dehydrated and dried PPG-2000, 1.34g of dimethylolpropionic acid, 5.22g of toluene diisocyanate and 0.01g of dibutyltin dilaurate into a three-neck flask with a stirring device, and reacting at 80 ℃ for 4h under the protection of nitrogen to obtain a prepolymer; then cooling to 60 ℃, adding 0.45g of 1, 4-butanediol for chain extension, and reacting 4h under the protection of nitrogen; cooling to 40 ℃, adding 5g of chloroform to adjust the viscosity of the system, adding 0.87g of triethylamine to neutralize and react for 15min, then adding 68.43g of deionized water to emulsify and disperse for 15min at a high speed under the condition of 1800r/min, adjusting the rotating speed to 500r/min, and continuously stirring for 2h; finally, 3h is distilled under reduced pressure in a rotary evaporator at 50 ℃ and under the vacuum degree of 0.088 MPa, and the organic solvent is removed to obtain the aqueous polyurethane emulsion; (3) Slowly dripping the metal ion solution into the aqueous polyurethane emulsion under the action of magnetic stirring, and mechanically stirring and dispersing for 30 min to obtain the aqueous room-temperature self-repairing polyurethane emulsion.
Example four: adding 0.916g of zinc acetate into 10g of deionized water for complete dissolution, and then adding 3g of ammonia water to prepare a metal ion buffer solution; (2) Putting PTMG-1000 and dimethylolpropionic acid in a rotary evaporator, and distilling at 120 deg.C and vacuum degree of 0.09MPa under reduced pressure for 4 hr to remove water; sequentially adding 20g of dehydrated and dried PTMG-1000, 2.68g of dimethylolpropionic acid, 13.34g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate into a three-neck flask with a stirring device, reacting at 80 ℃ for 4h under the protection of nitrogen to obtain a prepolymer; then cooling to 60 ℃, adding 0.9g of 1, 4-butanediol for chain extension, and reacting 4h under the protection of nitrogen; cooling to 40 ℃, adding 5g of acetone to adjust the viscosity of the system, adding 1.74g of triethylamine to perform neutralization reaction for 15min, then adding 90.20g of deionized water to perform high-speed emulsification and dispersion for 20min under the condition of 1500r/min, adjusting the rotating speed to 500r/min, and continuously stirring for 2h; finally, decompressing and distilling 3h in a rotary evaporator at 50 ℃ and under the vacuum degree of 0.088 MPa, and removing an organic solvent to obtain an aqueous polyurethane emulsion; (3) And slowly dripping the metal ion solution into the aqueous polyurethane emulsion under the action of magnetic stirring, and mechanically stirring and dispersing for 20min to obtain the aqueous room-temperature self-repairing polyurethane emulsion.
Example five: 0.472g of zinc nitrate is firstly added into 10g of deionized water to be completely dissolved, and then 3g of ammonia water is added to prepare a metal ion buffer solution; (2) Putting PTMG-2000 and dimethylolpropionic acid in a rotary evaporator, distilling 5h under reduced pressure at 100 deg.C and vacuum degree of 0.09MPa, and removing water; sequentially adding 20g of dehydrated and dried PTMG-2000, 1.34g of dimethylolpropionic acid, 6.67g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate into a three-neck flask with a stirring device, and reacting at 80 ℃ for 4 hours under the protection of nitrogen to obtain a prepolymer; then cooling to 60 ℃, adding 0.45g of 1, 4-butanediol for chain extension, and reacting 4h under the protection of nitrogen; cooling to 40 ℃, adding 5g of acetone to adjust the viscosity of the system, adding 0.87g of triethylamine to perform neutralization reaction for 10-15 min, then adding 68.43g of deionized water to perform high-speed emulsification and dispersion for 15min under the condition of 1800r/min, adjusting the rotating speed to 500r/min, and continuously stirring for 2h; finally, decompressing and distilling 2-3 h in a rotary evaporator at 50 ℃ and under the vacuum degree of 0.088 MPa, and removing the organic solvent to obtain the aqueous polyurethane emulsion; (3) Slowly dripping the metal ion solution into the aqueous polyurethane emulsion under the action of magnetic stirring, and mechanically stirring and dispersing for 30 min to obtain the aqueous room-temperature self-repairing polyurethane emulsion.
Example six: 0.453g of copper acetate is firstly added into 10g of deionized water to be completely dissolved, and then 3g of ammonia water is added to prepare a metal ion buffer solution; (2) Putting PTMG-2000 and dimethylolpropionic acid in a rotary evaporator, distilling 5h under reduced pressure at 100 deg.C and vacuum degree of 0.09MPa, and removing water; sequentially adding 20g of dehydrated and dried PTMG-2000, 1.34g of dimethylolpropionic acid, 6.67g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate into a three-neck flask with a stirring device, and reacting at 90 ℃ for 3h under the protection of nitrogen to obtain a prepolymer; then cooling to 60 ℃, adding 0.45g of 1, 4-butanediol for chain extension, and reacting 4h under the protection of nitrogen; cooling to 40 ℃, adding 5g of acetone to adjust the viscosity of the system, adding 0.87g of triethylamine to neutralize and react for 15min, then adding 68.43g of deionized water to emulsify and disperse for 15min at a high speed under the condition of 1800r/min, adjusting the rotating speed to 500r/min, and continuously stirring for 2h; finally, 3h is distilled under reduced pressure in a rotary evaporator at 50 ℃ and under the vacuum degree of 0.088 MPa, and the organic solvent is removed to obtain the aqueous polyurethane emulsion; (3) Slowly dripping the metal ion solution into the waterborne polyurethane emulsion under the action of magnetic stirring, and mechanically stirring and dispersing for 30 min to obtain the waterborne room-temperature self-repairing polyurethane emulsion.
Claims (2)
1. The invention relates to a preparation method of waterborne room temperature self-repairing polyurethane based on metal coordination bonds, which is characterized in that the waterborne room temperature self-repairing polyurethane is obtained by mixing a metal ion buffer solution and a waterborne polyurethane emulsion, and the mass ratio of the raw material components is as follows:
18 to 30 portions of diisocyanate
1,4 butanediol 1-3
30 to 100 portions of high molecular dihydric alcohol
Dimethylolpropionic acid 3-8
2 to 5 portions of triethylamine
0.01-0.02% of dibutyltin dilaurate
Metal salts 1 to 3
3 to 9 portions of ammonia water (25 to 28 percent)
4 to 10 portions of organic solvent
120 to 290 portions of deionized water
The waterborne room temperature self-repairing polyurethane based on the metal coordination bond is prepared by the following specific method: (1) Firstly, adding metal salt into deionized water to be completely dissolved, and then adding a proper amount of ammonia water to prepare a metal ion buffer solution; (2) Placing the high molecular dihydric alcohol and the dimethylolpropionic acid in a rotary evaporator, and distilling for 3-5 h under reduced pressure at 100-130 ℃ and the vacuum degree of 0.09MPa to remove water; sequentially adding the two dried components, diisocyanate and dibutyltin dilaurate into a three-neck flask with a stirring device, reacting at 70-90 ℃ under the protection of nitrogen to obtain an isocyanate-terminated prepolymer, wherein the isocyanate-terminated prepolymer is prepared by 3-5 h; cooling to 50-60 ℃, adding 1, 4-butanediol for chain extension, and reacting for 2-4 h under the protection of nitrogen; cooling to 40 ℃, adding an organic solvent to adjust the viscosity of the system, adding triethylamine to perform neutralization reaction for 10-15 min, then adding deionized water to perform high-speed emulsification for 15-20 min under the condition of 1500-1800 r/min, adjusting the rotating speed to 500-800 r/min, and continuously stirring for 1.5-2 h; finally, in a rotary evaporator, carrying out reduced pressure distillation on 2-3 h in a vacuum degree of 0.080-0.088 MPa at the temperature of 40-50 ℃, and removing an organic solvent to obtain a waterborne polyurethane emulsion; (3) Slowly dripping the metal ion buffer solution into the aqueous polyurethane emulsion under the action of magnetic stirring, and stirring and dispersing for 20-30 min to obtain the aqueous room-temperature self-repairing polyurethane emulsion.
2. The preparation method of the metal coordination bond-based waterborne room temperature self-repairing polyurethane as claimed in claim 1, wherein the metal coordination bond-based waterborne room temperature self-repairing polyurethane is prepared by the following steps: the high molecular dihydric alcohol is one of polypropylene glycol, polyethylene glycol, polytetramethylene ether glycol, poly adipic acid-1,4-butanediol ester glycol, polycaprolactone glycol and polycarbonate glycol, and the number average molecular weight of the high molecular dihydric alcohol is one of 1000 g/mol, 2000 g/mol and 3000 g/mol; the diisocyanate is one of isophorone diisocyanate, 4,4' -dicyclohexylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate; the metal salt being Zn 2 + 、Cu 2+ 、Co 2+ And Ni 2+ One of acetate, sulfate, nitrate and hydrochloride of (a); the organic solvent is one of tetrahydrofuran, acetone, butanone and chloroform.
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