CN115819703A - Water-based room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds - Google Patents
Water-based room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds Download PDFInfo
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- CN115819703A CN115819703A CN202111101241.1A CN202111101241A CN115819703A CN 115819703 A CN115819703 A CN 115819703A CN 202111101241 A CN202111101241 A CN 202111101241A CN 115819703 A CN115819703 A CN 115819703A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 70
- 239000004814 polyurethane Substances 0.000 title claims abstract description 70
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 52
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 35
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 19
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- -1 ditelluride diol Chemical class 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 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 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 238000004945 emulsification Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 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
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002148 esters Chemical class 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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran 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
- 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 2
- 239000000463 material Substances 0.000 abstract description 52
- 230000008439 repair process Effects 0.000 abstract description 15
- 230000000638 stimulation Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000011527 polyurethane coating Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- JPIIVHIVGGOMMV-UHFFFAOYSA-N ditellurium Chemical compound [Te]=[Te] JPIIVHIVGGOMMV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000008263 repair mechanism Effects 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- ISWPADPOGZPZMU-UHFFFAOYSA-N 2-(2,2-dihydroxyethyldiselanyl)ethane-1,1-diol Chemical compound OC(C[Se][Se]CC(O)O)O ISWPADPOGZPZMU-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- JZXPEQZMRNCVJW-UHFFFAOYSA-N carboxy hydrogen carbonate 2-(2-hydroxyethoxy)ethanol Chemical compound C(=O)(O)OC(=O)O.C(COCCO)O JZXPEQZMRNCVJW-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 230000001939 inductive effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical group OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 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 double tellurium bonds and distorted multiple hydrogen bonds. The method comprises the following steps: diisocyanate, high-molecular dihydric alcohol, dimethylolpropionic acid and ditelluride diol are prepared into an isocyanate-terminated prepolymer, neutralized and emulsified, and then capped by carbohydrazide to obtain the waterborne room temperature self-repairing polyurethane. Double tellurium bonds are introduced into the main chain, so that the large damage repair of the material under the stimulation of visible light can be realized; carbohydrazide is introduced at the chain end to form a twisted multiple hydrogen bond, so that the crystallization is not easy, the repair speed is high, and the microcrack repair is facilitated; in addition, the stronger double tellurium bonds are beneficial to supporting the material structure, the weaker twisted multiple hydrogen bonds are preferentially broken as sacrificial bonds under the action of external force, the toughness of the material is greatly improved, and the self-repairing performance of the material is effectively improved under the synergistic effect of the double dynamic bonds. The method provided by the invention is environment-friendly, and the prepared material has good mechanical property and self-repairing rate, and can be used in the fields of functional polyurethane coating materials 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 double tellurium bonds and distorted multiple hydrogen bonds, belonging to the field of functional polyurethane coating materials and the like.
Background
With the increasing environmental concerns and the close attention paid to the health of people, waterborne Polyurethanes (WPUs) are gradually replacing solvent-borne polyurethanes (ACS Sustainable Chemistry & Engineering, 2020, 8: 17447-17457). Compared with solvent-based polyurethane, the waterborne polyurethane has the advantages of low Volatile Organic Compound (VOC) emission, no toxicity, no flammability and the like, and also has good wear resistance, low temperature resistance and flexibility (Advanced Materials, 2018, 30: 1706237). These advantages have led to the widespread use of waterborne polyurethanes in Coatings, adhesives, finishes, inks and biomaterials (Progress in Organic Coatings, 2021, 150: 105972). However, the waterborne polyurethane inevitably generates physical damages such as scratches, microcracks and even fractures in the using process, the damages seriously affect the service life of the waterborne polyurethane, increase the maintenance cost and cause certain potential safety hazards. It is a very effective strategy to impart self-healing function to waterborne polyurethane, which can significantly improve its safety, stability and prolong its service life (Polymer Chemistry, 2021, 12: 831-842).
According to the repair mechanism, the self-repair modes of the material can be divided into exorbitant self-repair mode and endogenous self-repair mode. Compared with external-aid self-repair, the internal-source self-repair does not need pre-buried repair agents, mainly depends on the breakage and recombination of dynamic chemical bonds to realize the damage repair of Materials, has the advantages of simple preparation process and multiple repair times, and arouses special attention (Nature Reviews Materials, 2020, 5 (8): 562-583). With the rapid development of endogenous self-repairing Materials, the prepared self-repairing Materials with high room temperature repairing rate and strong mechanical properties can better meet the requirements of practical application (Advanced Materials, 2018, 30.
In recent years, researchers have prepared a variety of waterborne room temperature self-repairing polyurethane materials based on dynamic chemical bonds. For example, chinese patent (CN 106497385A) discloses a preparation method of a visible light self-repairing aqueous polyurethane coating material with a main chain containing a double selenium bond, which is obtained by polymerizing diisocyanate, high molecular diol, dihydroxyethyl diselenide and dimethylolpropionic acid. The material realizes a self-repairing function based on visible light-induced reversible exchange reaction of double selenium bonds, and obtains a relatively ideal repairing effect after 24 hours under the condition of visible light irradiation. Huang et al prepared an aqueous room temperature self-healing polyurethane material with a tensile strength of 11 MPa from bis (ortho-amino) phenyl disulfide, polyether polyol and dimethylolpropionic acid, which material had a tensile strength of 83% as-is after 48 h of healing at room temperature based on the reversible exchange properties of aromatic disulfide bonds (Progress in Organic Coatings,2020,146 105717. The material has good mechanical property, but the repair mechanism is single, and only dynamic covalent bonds are relied on, and the self-repair rate of the dynamic covalent bonds (aromatic disulfide bonds) at room temperature is slow, so that the repair time is too long.
In order to improve the repair rate of the material at room temperature, bossion et al firstly carry out ring-opening polymerization on diethylene glycol dicarbonate, eight-membered cyclic carbonate and aminopropyl terminated polysiloxane, and then add citric acid for neutralization and water emulsification to prepare the cationic aqueous room-temperature fast self-repairing polyurethane material. Based on the breaking and recombination of ionic bonds between amino and carboxyl, the scratch can be completely healed after being repaired for 1 hour at room temperature (Polymer, 2019, 166. However, the interaction between the molecular chains of the material only depends on dynamic ionic bonds, and the ionic bond energy is low, so that the mechanical property of the material is poor, and the result shows that the storage modulus of the material is only 0.5MPa at room temperature.
From the examples listed above, weak dynamic chemical bonds allow faster repair rates of aqueous polyurethanes, but their mechanical properties tend to be poor; the strong dynamic chemical bond can endow the waterborne polyurethane with better mechanical property, but the waterborne polyurethane needs longer time to complete self-repairing. Therefore, it is difficult to make the material have high self-repairing rate and high mechanical property only by means of single dynamic chemical bond.
To address this challenge, the combination of multiple classes of dynamic keys is an effective way (Materials Horizons, 2020, 7: 2882-2902). Chinese patent (CN 111171265A) discloses a water-based polyurethane resin containing a pyrimidone structure and a preparation method thereof, wherein the water-based polyurethane resin is obtained by reacting high-molecular diol, diisocyanate, a hydrophilic chain extender, 2-amino-4-hydroxy-6-methylpyrimidinone diol and a cross-linking agent methylated beta-cyclodextrin. According to the material, cyclodextrin is introduced into a main chain to improve mechanical properties, and simultaneously, the UPy reversible quadruple hydrogen bond interaction and dynamic host-guest interaction (the cyclodextrin of the main chain and the UPy of a side chain) are cooperated to endow the material with good self-repairing performance. However, because UPy forms quadruple hydrogen bonds with a regular structure, is easy to crystallize at normal temperature and needs high-temperature activation, the optimal repair temperature of the material is 100 ℃, and room-temperature self-repair is difficult to realize. Chinese patent (CN 108250398A) discloses a preparation method of a water-based polyurethane self-repairing coating material based on a diselenide dynamic covalent bond and multiple hydrogen bonds, which is obtained by reacting diisocyanate, high-molecular diol, dimethylolpropionic acid, a UPy-based chain extender and diselenide glycol. The material improves the mechanical property by forming quadruple hydrogen bond action among molecular chains, and simultaneously achieves better repairing effect at room temperature based on visible light-induced reversible exchange reaction of double selenium bonds and double dynamic action of UPy reversible quadruple hydrogen bond. However, UPy can form regular quadruple hydrogen bonds, is easy to crystallize at normal temperature, and blocks chain segment movement, so that the improvement of the self-repairing rate of the material is very limited. Currently, research on waterborne room temperature self-repairing polyurethane based on multiple types of dynamic effects is still few, and therefore, how to introduce multiple types of dynamic bonds into waterborne polyurethane so as to exert the synergistic effect to further improve the mechanical strength and the room temperature self-repairing rate of the waterborne polyurethane is an important challenge.
Double tellurium bonds can undergo cleavage recombination under visible light induction, and have a bond energy of 126 KJ/mol, which is lower than that of homologous disulfide bonds (240 KJ/mol) and double selenium bonds (172 KJ/mol), meaning that double tellurium bonds are more dynamic under visible light induction (Chemical Communications, 2019, 2813-2816. Therefore, the introduction of double tellurium bonds into the waterborne polyurethane material is expected to realize a faster visible light induced self-repair function. In addition, in order to make up for the deficiency of self-healing systems relying on a single dynamic bond, we further introduce multiple hydrogen bonds into the aqueous polyurethane material. Carbohydrazide can react with isocyanate to form a triureido group with a twisted structure, the twisted triureido group forms irregular multiple hydrogen bonds among polyurethane molecular chains, the twisted multiple hydrogen bonds provide rich crosslinking sites for the polyurethane material, and simultaneously avoid inducing the polyurethane material to form unnecessary crystals at normal temperature, and reduce the barrier effect on chain section movement, thereby achieving the dual purposes of improving mechanical strength and room temperature self-repairing rate (Chemistry-A European Journal,2013, 19. In addition, the twisted triurea structure is introduced into the chain end of a molecular chain through special molecular design, so that the movement capability of the chain is enhanced, and the room temperature self-repairing efficiency and speed of the material are further improved. The double tellurium bonds and the twisted multiple hydrogen bonds can realize self-repairing of the material under mild conditions, the double tellurium dynamic covalent bonds have strong energy but slow self-repairing speed, the twisted multiple hydrogen bonds have weak energy but fast self-repairing speed, in addition, the double tellurium bonds with strong bond energy can maintain the mechanical strength of the material, and the twisted hydrogen bonds with weak bond energy can be used as sacrificial bonds to improve the toughness of the material. The double dynamic bonds are introduced into the same system, so that the fast and slow combination of the self-repairing speed and the strong and weak combination of the mechanical strength are realized, and the bottleneck that the waterborne polyurethane is difficult to have both fast room-temperature self-repairing and high mechanical property is expected to be broken. At present, no report is found on the waterborne room temperature self-repairing polyurethane based on double-tellurium bond and twisted multiple hydrogen bond double-dynamic action.
Diisocyanate, high-molecular dihydric alcohol, dimethylolpropionic acid and ditelluritol are reacted to prepare a prepolymer of which the main chain contains ditellurium bond-terminated isocyanate groups, and after neutralization and emulsification, the prepolymer is terminated by carbohydrazide to obtain the aqueous room-temperature self-repairing polyurethane containing ditellurium bonds and twisted multiple hydrogen bonds. The prepared water-based room temperature self-repairing polyurethane realizes the repair of large damage of materials by introducing double tellurium bonds which can be broken and recombined under the stimulation of visible light on the main chain; the carbohydrazide monomer is added for end capping, so that irregular multiple hydrogen bonds are formed among molecular chains, crystallization is not easy, self-repairing at room temperature is facilitated, the introduced position is at an end group, the flexibility is higher, the repairing efficiency is further improved, and the multiple hydrogen bonds are beneficial to repairing microcracks; the bond energy of two dynamic bonds introduced into the waterborne room temperature self-repairing polyurethane is different, wherein the bond energy of the double tellurium bonds is larger than that of the hydrogen bonds, the stronger double tellurium bonds can play a role in supporting a material structure and contribute to forming a strong molecular network, in the stress process, the weaker multiple hydrogen bonds are broken as sacrificial bonds, the toughness of the material can be greatly improved, and meanwhile, the rapid breaking and recombination of the double tellurium bonds under the stimulation of visible light and the rapid reconstruction of the multiple hydrogen bonds in damaged areas are utilized to realize the rapid self-repairing of the waterborne polyurethane. The material prepared by the invention is a water-based system, does not contain organic solvent, is environment-friendly, has the advantages of high room-temperature self-repairing rate and high mechanical strength, and can be applied to the fields of functional polyurethane coating materials and the like.
Disclosure of Invention
The invention relates to a preparation method of water-based room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
The waterborne room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds is characterized in that:
1. the double-tellurium-bond and twisted multiple hydrogen-bond-based waterborne room temperature self-repairing polyurethane provided by the invention has the advantages that the double-tellurium bonds which can be broken and recombined under the stimulation of visible light are introduced into the main chain, so that the repair of the large damage of the material is realized;
2. according to the double-tellurium-bond and twisted multiple-hydrogen-bond-based waterborne room temperature self-repairing polyurethane provided by the invention, carbohydrazide is introduced into the chain end, so that irregular multiple hydrogen bonds are formed among molecular chains, crystallization is not easy, the room temperature self-repairing is facilitated, and the introduced position is at the end group, so that the flexibility is higher, the repairing efficiency is further improved, and in addition, the multiple hydrogen bonds are beneficial to repairing microcracks;
3. according to the waterborne room temperature self-repairing polyurethane based on the double tellurium bonds and the distorted multiple hydrogen bonds, the bond energies of the two dynamic bonds in the system are different, wherein the double tellurium bonds are higher than the hydrogen bonds, the stronger dynamic bonds can play a role in supporting the structure of the material and are beneficial to forming a strong molecular network, the weaker multiple hydrogen bonds are preferentially broken as sacrificial bonds in the stress process, the toughness of the material can be greatly improved, and meanwhile, the rapid breaking and recombination of the double tellurium bonds under the stimulation of visible light and the rapid reconstruction of the multiple hydrogen bonds in damaged areas are utilized to realize the rapid room temperature self-repairing of the waterborne polyurethane.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a preparation method of water-based room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
The weight ratio of each raw material component is as follows:
10 to 40 portions of diisocyanate
3 to 10 portions of ditellurium diol
Carbohydrazide 1 to 7
30-100 parts of high-molecular dihydric alcohol
Dimethylolpropionic acid 3-10
2 to 8 portions of triethylamine
0.01-0.02% of dibutyltin dilaurate
14 to 20 portions of organic solvent
200-430 parts of deionized water
The waterborne room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds is prepared by the following specific method:
(1) 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;
(2) Sequentially adding the two dried components, diisocyanate and dibutyltin dilaurate into a three-neck flask with a stirring device, and reacting for 3-5 h at 70-90 ℃ under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer;
(3) Cooling to 50-60 ℃, adding ditelluride diol to carry out chain extension, and reacting for 2-4 h under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer with a main chain containing ditelluride bonds;
(4) Cooling to 20-40 ℃, adding an organic solvent to adjust the viscosity of the system, and adding triethylamine to perform neutralization reaction for 15-20 min;
(5) Regulating the rotation speed to 1500-1800 r/min, adding 80% deionized water for emulsification for 1.5-2.0 h, carrying out high-speed emulsification for 15-20 min, then adding carbohydrazide diluted by the rest 20% deionized water for end capping, continuing to stir at high speed for 15-20 min for uniform dispersion, then regulating the rotation speed to 500-800 r/min, and continuously reacting for 2-3 h to obtain the carbohydrazide end capped polyurethane emulsion containing double tellurium bonds;
(6) And carrying out reduced pressure distillation on the obtained polyurethane emulsion containing a small amount of organic solvent for 2-3 h at 40-50 ℃ and 0.080-0.088 MPa of vacuum degree in a rotary evaporator, and removing the organic solvent to obtain the water-based room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
Wherein the high molecular dihydric alcohol is one of polypropylene glycol, polyethylene glycol, polytetramethylene ether glycol, poly adipic acid-1, 4-butanediol ester glycol, polycaprolactone diol and polycarbonate diol, and the number average molecular weight is one of 1000 g/mol, 2000 g/mol and 3000 g/mol; the diisocyanate is one of isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate; the organic solvent is one of tetrahydrofuran, acetone, butanone and chloroform.
The invention has the advantages that: the double-tellurium bond and distorted multiple hydrogen bond-based waterborne room temperature self-repairing polyurethane synthesized by the invention realizes the repair of the large damage of the material by introducing the double-tellurium bond which can be broken and recombined under the stimulation of visible light into the main chain. Carbohydrazide is introduced into the chain end, so that distorted multiple hydrogen bonds are formed among molecular chains, the carbohydrazide is not easy to crystallize and is beneficial to room-temperature self-repair, the introduced position is at the end group, the flexibility is higher, the repair efficiency is further improved, and in addition, the distorted multiple hydrogen bonds are beneficial to the repair of microcracks. The bond energy of two dynamic bonds in the system is different, wherein the double tellurium bond energy is higher than the hydrogen bond, the stronger double tellurium bond can play a role in supporting a material structure, a strong molecular network is facilitated to be formed, in the stress process, the weaker distorted multiple hydrogen bond is preferentially broken as a sacrificial bond, the toughness of the material can be greatly improved, and meanwhile, the rapid room temperature self-repairing of the waterborne polyurethane is realized by means of the rapid breaking and recombination of the double tellurium bond under the stimulation of visible light and the rapid reconstruction of the multiple hydrogen bond in a damaged area.
Detailed Description
The first embodiment is as follows: 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 30g of PPG-2000, 2.01g of dimethylolpropionic acid, 8.9 g of isophorone diisocyanate and 0.01 g of dibutyltin dilaurate into a three-necked flask with a stirring device, and reacting for 5 hours at 70 ℃ under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer; cooling to 50 ℃, adding 2.4 g of ditelluride for chain extension, and reacting for 4 hours under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer with a main chain containing ditelluride bonds; cooling to 40 ℃, adding 10 g of acetone to adjust the viscosity of the system, and adding 1.51 g of triethylamine to perform neutralization reaction for 15 min; adjusting the rotation speed to 1500r/min, adding 84.67 g of deionized water to emulsify for 20min at a high speed, then adding a mixture of 21.17 g of deionized water and 0.54 g of carbohydrazide to carry out end capping, continuing stirring at a high speed for 20min to disperse uniformly, then adjusting the rotation speed to 500r/min, and continuously reacting for 3h to obtain the carbohydrazide-capped polyurethane emulsion containing double tellurium bonds; and carrying out reduced pressure distillation on the obtained polyurethane emulsion containing a small amount of organic solvent for 3h at 40 ℃ and under the vacuum degree of 0.080MPa in a rotary evaporator, and removing the organic solvent to obtain the aqueous room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
Example two: putting PTMG-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 30g of PTMG-2000, 2.01g of dimethylolpropionic acid, 8.9 g of isophorone diisocyanate and 0.01 g of dibutyltin dilaurate into a three-necked flask with a stirring device, and reacting at 70 ℃ for 5 hours under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer; cooling to 50 ℃, adding 2.4 g of ditelluride glycol for chain extension, and reacting for 4 hours under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer with a main chain containing ditelluride bonds; cooling to 40 ℃, adding 10 g of acetone to adjust the viscosity of the system, and adding 1.51 g of triethylamine to perform neutralization reaction for 15 min; adjusting the rotation speed to 1500r/min, adding 84.67 g of deionized water to emulsify for 20min at a high speed, then adding a mixture of 21.17 g of deionized water and 0.54 g of carbohydrazide to carry out end capping, continuing stirring at a high speed for 20min to disperse uniformly, then adjusting the rotation speed to 500r/min, and continuously reacting for 3h to obtain the carbohydrazide-capped polyurethane emulsion containing double tellurium bonds; and carrying out reduced pressure distillation on the obtained polyurethane emulsion containing a small amount of organic solvent for 3h at 40 ℃ and under the vacuum degree of 0.080MPa in a rotary evaporator, and removing the organic solvent to obtain the aqueous room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
Example three: putting PTMG-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 30g of PTMG-2000, 2.01g of dimethylolpropionic acid, 6.73 g of hexamethylene diisocyanate and 0.01 g of dibutyltin dilaurate into a three-neck flask with a stirring device, and reacting for 5 hours at 70 ℃ under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer; cooling to 50 ℃, adding 2.4 g of ditelluride glycol for chain extension, and reacting for 4 hours under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer with a main chain containing ditelluride bonds; cooling to 40 ℃, adding 10 g of acetone to adjust the viscosity of the system, and adding 1.51 g of triethylamine to perform neutralization reaction for 15 min; adjusting the rotation speed to 1500r/min, adding 84.67 g of deionized water to emulsify for 20min at a high speed, then adding a mixture of 21.17 g of deionized water and 0.54 g of carbohydrazide to carry out end capping, continuing stirring at a high speed for 20min to disperse uniformly, then adjusting the rotation speed to 500r/min, and continuously reacting for 3h to obtain the carbohydrazide-capped polyurethane emulsion containing double tellurium bonds; and carrying out reduced pressure distillation on the obtained polyurethane emulsion containing a small amount of organic solvent for 3h at 40 ℃ and under the vacuum degree of 0.080MPa in a rotary evaporator, and removing the organic solvent to obtain the aqueous room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
Example four: 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; adding 15g of PTMG-1000, 2.01g of dimethylolpropionic acid, 8.9 g of isophorone diisocyanate and 0.005 g of dibutyltin dilaurate into a three-necked flask with a stirring device in sequence, and reacting for 5 hours at 70 ℃ under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer; cooling to 50 ℃, adding 2.4 g of ditelluride glycol for chain extension, and reacting for 4 hours under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer with a main chain containing ditelluride bonds; cooling to 40 ℃, adding 7 g of acetone to adjust the viscosity of the system, and adding 1.51 g of triethylamine to perform neutralization reaction for 15 min; adjusting the rotation speed to 1500r/min, adding 80.97 g of deionized water to emulsify for 20min at a high speed, then adding a mixture of 20.24g of deionized water and 0.54 g of carbohydrazide to carry out end capping, continuing stirring at a high speed for 20min to disperse uniformly, then adjusting the rotation speed to 500r/min, and continuously reacting for 3h to obtain the carbohydrazide-capped polyurethane emulsion containing double tellurium bonds; and carrying out reduced pressure distillation on the obtained polyurethane emulsion containing a small amount of organic solvent for 3h at 40 ℃ and under the vacuum degree of 0.080MPa in a rotary evaporator, and removing the organic solvent to obtain the aqueous room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
Example five: putting PTMG-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 30g of PTMG-2000, 2.01g of dimethylolpropionic acid, 8.9 g of isophorone diisocyanate and 0.01 g of dibutyltin dilaurate into a three-necked flask with a stirring device, and reacting for 5 hours at 70 ℃ under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer; cooling to 50 ℃, adding 1.72 g of ditelluride diol for chain extension, and reacting for 4h under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer with a main chain containing ditelluride bonds; cooling to 40 ℃, adding 10 g of butanone to adjust the viscosity of the system, and adding 1.51 g of triethylamine to neutralize and react for 15 min; adjusting the rotation speed to 1500r/min, adding 84.05 g of deionized water to emulsify for 20min at a high speed, then adding a mixture of 21.01g of deionized water and 0.9g of carbohydrazide to carry out end capping, continuing stirring at a high speed for 20min to disperse uniformly, then adjusting the rotation speed to 500r/min, and continuously reacting for 3h to obtain the carbohydrazide-capped polyurethane emulsion containing double tellurium bonds; and carrying out reduced pressure distillation on the obtained polyurethane emulsion containing a small amount of organic solvent for 3h in a rotary evaporator at 40 ℃ under the vacuum degree of 0.080MPa, and removing the organic solvent to obtain the aqueous room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
Claims (2)
1. The invention relates to a preparation method of waterborne room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds, which is characterized in that the waterborne room temperature self-repairing polyurethane comprises double-dynamic actions of the double tellurium bonds and the distorted multiple hydrogen bonds, and the mass ratio of the raw material components is as follows:
10 to 40 portions of diisocyanate
3 to 10 portions of ditellurium diol
Carbohydrazide 1 to 7
30-100 parts of high-molecular dihydric alcohol
Dimethylolpropionic acid 3-10
2 to 8 portions of triethylamine
0.01-0.02% of dibutyltin dilaurate
14 to 20 portions of organic solvent
200-430 parts of deionized water
The waterborne room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds is prepared by the following specific method:
(1) 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;
(2) Sequentially adding the two dried components, diisocyanate and dibutyltin dilaurate into a three-neck flask with a stirring device, and reacting for 3-5 h at 70-90 ℃ under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer;
(3) Cooling to 50-60 ℃, adding ditelluride diol to carry out chain extension, and reacting for 2-4 h under the protection of nitrogen to obtain an isocyanate-terminated polyurethane prepolymer with a main chain containing ditelluride bonds;
(4) Cooling to 20-40 ℃, adding an organic solvent to adjust the viscosity of the system, and adding triethylamine to perform neutralization reaction for 15-20 min;
(5) Adjusting the rotation speed to 1500-1800 r/min, adding 80% deionized water for high-speed emulsification for 15-20 min, then adding carbohydrazide diluted by the rest 20% deionized water for end capping, continuing to stir at high speed for 15-20 min for uniform dispersion, then adjusting the rotation speed to 500-800 r/min, and continuously reacting for 2-3 h to obtain the carbohydrazide-capped polyurethane emulsion containing double tellurium bonds;
(6) And carrying out reduced pressure distillation on the obtained polyurethane emulsion containing a small amount of organic solvent for 2-3 h at 40-50 ℃ and 0.080-0.088 MPa of vacuum degree in a rotary evaporator, and removing the organic solvent to obtain the water-based room temperature self-repairing polyurethane based on double tellurium bonds and distorted multiple hydrogen bonds.
2. The preparation method of the waterborne room temperature self-repairing polyurethane based on double tellurium bonds and twisted multiple hydrogen bonds as claimed in claim 1, characterized in that: the high molecular dihydric alcohol is one of polypropylene glycol, polyethylene glycol, polytetramethylene ether glycol, poly adipic acid-1, 4-butanediol ester glycol, polycaprolactone diol and polycarbonate diol, 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' -dicyclohexylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate; the organic solvent is one of tetrahydrofuran, acetone, butanone and chloroform.
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