CN115947922A - Preparation method of self-repairable waterborne polyurethane elastomer - Google Patents
Preparation method of self-repairable waterborne polyurethane elastomer Download PDFInfo
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- CN115947922A CN115947922A CN202310062354.8A CN202310062354A CN115947922A CN 115947922 A CN115947922 A CN 115947922A CN 202310062354 A CN202310062354 A CN 202310062354A CN 115947922 A CN115947922 A CN 115947922A
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Abstract
The invention discloses a preparation method of a self-repairable waterborne polyurethane elastomer, belongs to the technical field of self-repairing materials, and particularly relates to a preparation method of a polyurethane elastomer. The invention aims to solve the problems of long reaction time, high energy consumption and complex preparation process of a polyurethane self-repairing material prepared by the existing method due to the use of a large amount of toxic organic solvents. The method comprises the following steps: 1. reacting diisocyanate with deoxythymidine; 2. adding polyether polyol, 2,2-dimethylolpropionic acid and a solvent; 3. adding triethylamine; 4. dispersing in distilled water containing chain extender; 5. and curing to obtain the self-repairable waterborne polyurethane elastomer. The waterborne polyurethane elastomer prepared by the invention can be repaired for 4 hours at 110 ℃ or for 6 hours under normal temperature trace solvent, and the repair efficiency can reach more than 85% or more than 90%; in addition, the solvent-repaired polyurethane elastomer has high elongation at break and no primary and secondary mechanical property and the original polyurethane elastomer.
Description
Technical Field
The invention belongs to the technical field of self-repairing materials, and particularly relates to a preparation method of a polyurethane elastomer.
Background
The application range of elastomer materials in the world is more and more extensive nowadays, and polyurethane materials are excellent elastomers with light weight, high strength and high ductility, and have wider application prospects in the aspects of medical instruments, electronic skins, military materials, coatings, household appliances and the like. The amount of polyurethane materials used in recent years has been increasing due to their excellent mechanical properties. However, polyurethane materials suffer irreversible damage over time, resulting in a large number of microcracks and even fractures, which not only present a safety hazard in some areas, but also result in the production of large amounts of waste polyurethane every year. Therefore, how to repair the crack in time while finding the crack, prolong the service life of the material and reduce the generation of waste is an important problem to be solved at present.
Polyurethane self-healing materials have made significant research progress in recent years. Researchers introduce repairable microcapsules, reversible covalent bonds (such as disulfide bonds, amide bonds, diselenide bonds and the like), hydrogen bonds, coordination bonds and the like into a polymer matrix or a molecular chain, and repair the damaged parts of the polyurethane material under the stimulation of an external environment (such as light, heat, a solvent and the like). The patent CN 113831493A discloses a self-repairing polyurethane elastomer containing six-fold intermolecular hydrogen bonds, the preparation process of the polyurethane elastomer is simple, 2,6-diaminopyridine or 2,6-diaminopyridine derivatives are used as chain extenders, and the prepared polyurethane elastomer has good mechanical properties, but the elastomer has large toxicity due to the fact that a large amount of solvents such as tetrahydrofuran, N-dimethylformamide or methanol are used in the preparation process. The patent CN 110698635B discloses a polyurethane elastomer with high toughness and high mechanical strength and a recyclable and self-repairing function and a preparation method thereof, and the elasticity and the repairing performance of polyurethane are improved through hydrogen bonds and coordination bonds. Although the synthesized polyurethane has higher mechanical strength and healing property, the reaction time is long (> 48 h), the energy consumption is high, and the preparation process is complicated.
Disclosure of Invention
The invention aims to solve the problems of large amount of toxic organic solvents, long reaction time, high energy consumption and complex preparation process of the polyurethane self-repairing material prepared by the existing method, and provides a preparation method of a self-repairable waterborne polyurethane elastomer.
A preparation method of a self-repairable waterborne polyurethane elastomer is specifically completed according to the following steps:
1. under the protection of inert gas, diisocyanate and deoxythymidine react at 25-50 ℃ to obtain a reaction product I;
2. adding polyether polyol into the reaction product I, heating to 70-85 ℃, reacting for a period of time at 70-85 ℃, adding 2,2-dimethylolpropionic acid and a solvent, and continuously reacting for a period of time at 70-85 ℃ to obtain a polyurethane prepolymer;
3. reducing the temperature of the polyurethane prepolymer to 40-45 ℃, then adding triethylamine, and continuously reacting at 40-45 ℃ for a period of time to obtain the prepolymer;
4. firstly, dispersing a chain extender in distilled water, and then dispersing the prepolymer obtained in the third step in distilled water to obtain a waterborne polyurethane emulsion;
5. and (3) putting the waterborne polyurethane emulsion into a polytetrafluoroethylene mold, curing at room temperature, and drying after curing to obtain the self-repairable waterborne polyurethane elastomer.
The invention has the beneficial effects that:
1. the preparation method of the high-tensile high-strength repairable bionic aqueous polyurethane elastomer (the self-repairable aqueous polyurethane elastomer) realized by multiple hydrogen bonds, disclosed by the invention, has the advantages that the preparation process is simple, only a small amount of organic solvent is needed in the synthesis process, the residual rate of the solvent in the product is reduced, and the preparation method is green and environment-friendly; the synthesized waterborne polyurethane has high mechanical strength and repairability, and also has good elasticity, thermal stability and the like;
2. the invention discloses a preparation method of a high-tensile high-strength repairable bionic aqueous polyurethane elastomer (a self-repairable aqueous polyurethane elastomer) realized by multiple hydrogen bonds, wherein the polyurethane still has good resilience after repeated stretching, and the repaired polyurethane also has good stretchability and resilience;
3. the invention discloses a preparation method of a high-tensile high-strength repairable bionic waterborne polyurethane elastomer (a self-repairable waterborne polyurethane elastomer) realized by multiple hydrogen bonds, which is characterized in that polyurethane is repaired for 4 hours at 110 ℃ or for 6 hours under normal-temperature trace solvent, and the repair efficiency can reach more than 85% or more than 90%; in addition, the solvent-repaired polyurethane elastomer has high elongation at break and no primary and secondary mechanical properties with the original polyurethane elastomer;
4. the invention discloses a preparation method of a high-tensile high-strength repairable bionic waterborne polyurethane elastomer (a self-repairable waterborne polyurethane elastomer) realized by multiple hydrogen bonds, wherein the glass transition temperature (Tg) of the polyurethane elastomer is less than-30 ℃, so that the polyurethane elastomer can keep high elasticity even in an environment at the temperature of less than 0 ℃;
5. the invention discloses a preparation method of a high-tensile high-strength repairable bionic waterborne polyurethane elastomer (a self-repairable waterborne polyurethane elastomer) realized by multiple hydrogen bonds.
Drawings
FIG. 1 is a reaction mechanism diagram of a self-repairable aqueous polyurethane elastomer prepared in example 1;
FIG. 2 is a stress-strain curve diagram of the self-repairable aqueous polyurethane elastomer prepared in example 1 before and after high-temperature repair, wherein 1 is before repair and 2 is after repair;
FIG. 3 is a stress-strain curve before and after solvent repair of the self-repairable aqueous polyurethane elastomer prepared in example 1, wherein 1 is before repair, and 2 is after repair;
FIG. 4 is an infrared ray graph of the self-repairable aqueous polyurethane elastomer prepared in example 1;
fig. 5 is a polarization microscope image of the self-repairable aqueous polyurethane elastomer prepared in example 1 before and after high-temperature repair and solvent repair.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of a self-repairable waterborne polyurethane elastomer, which is specifically completed by the following steps:
1. under the protection of inert gas, diisocyanate and deoxythymidine react at 25-50 ℃ to obtain a reaction product I;
2. adding polyether glycol into the reaction product I, heating to 70-85 ℃, reacting for a period of time at 70-85 ℃, adding 2,2-dimethylolpropionic acid and a solvent, and continuously reacting for a period of time at 70-85 ℃ to obtain a polyurethane prepolymer;
3. reducing the temperature of the polyurethane prepolymer to 40-45 ℃, adding triethylamine, and continuously reacting at 40-45 ℃ for a period of time to obtain the prepolymer;
4. firstly, dispersing a chain extender in distilled water, and then dispersing the prepolymer obtained in the third step in distilled water to obtain a waterborne polyurethane emulsion;
5. and (3) putting the waterborne polyurethane emulsion into a polytetrafluoroethylene mold, curing at room temperature, and drying after curing to obtain the self-repairable waterborne polyurethane elastomer.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the diisocyanate in the first step is aromatic isocyanate, aliphatic isocyanate or alicyclic isocyanate. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the molar ratio of diisocyanate to deoxythymidine in the first step is (6-20) to 1; the reaction time in the step one is 1-3 h. The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the solvent in the step two is acetone, butanone or N-methyl pyrrolidone; the molar ratio of the polyether polyol in the second step to the deoxythymidine in the first step is (1-5) to 1; the molar ratio of the polyether glycol to 2,2-dimethylolpropionic acid in the second step is 1 (0.5-1); the molar ratio of the solvent to 2,2-dimethylolpropionic acid in the second step is (10-60): 1. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and step two, adding polyether polyol into the reaction product I, heating to 70-85 ℃, reacting for 1-4 h at 70-85 ℃, adding 2,2-dimethylolpropionic acid, and continuing to react for 1-3 h at 70-85 ℃ to obtain the polyurethane prepolymer. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is as follows: and (3) the molar ratio of the triethylamine in the third step to the 2,2-dimethylolpropionic acid in the second step is 1:1, the temperature of the polyurethane prepolymer is reduced to 40-45 ℃, then the triethylamine is added, and the reaction is continued at 40-45 ℃ for 20-30 min to obtain a reaction product II. The other steps are the same as those in the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is: the chain extender in the fourth step is 1,2-ethylenediamine, 1,4-butanediol, isophorone diamine or triethylene tetramine; the 2,2-dimethylolpropionic acid and polyether polyol are dried to remove water before use. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode eight: the difference between this embodiment and one of the first to seventh embodiments is: the molar ratio of the chain extender in the fourth step to the deoxythymidine in the first step is 1 (0.5-1.5); the solid content of the waterborne polyurethane emulsion in the fourth step is 30-40%. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the curing time in the step five is 12-48 h; and the drying temperature in the step five is 50-83 ℃, and the drying time is 8-24 h. The other steps are the same as those in the first to eighth embodiments.
The specific implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the self-repairable waterborne polyurethane elastomer in the step five comprises a hard segment and a soft segment, wherein the soft segment is polyether polyol, the molecular weight Mw = 2000-4500 g/mol, the hard segment is isophorone diisocyanate, and the molar ratio of the hard segment to the soft segment is (1-2): 1. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a self-repairable waterborne polyurethane elastomer is specifically completed according to the following steps:
1. under the protection of inert gas, 10.27g of isophorone diisocyanate (IPDI) and 1.02g of deoxythymidine (2-Td) react for 1.5h at 30 ℃ to obtain a reaction product I;
2. adding 30g of polyether glycol (PPG) into the reaction product I, heating to 80 ℃, reacting for 1h at 80 ℃, adding 1.87g of 2, 2-dimethylolpropionic acid (DMPA) and 10mL of 2-butanone, and continuously reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer;
3. reducing the temperature of the polyurethane prepolymer to 45 ℃, adding 1.42g of triethylamine, and continuously reacting at 45 ℃ for 30min to obtain the prepolymer;
4. firstly, 0.85g of isophorone diamine is dispersed in distilled water, and then the prepolymer obtained in the third step is dispersed in distilled water to obtain aqueous polyurethane emulsion with the solid content of 30%;
5. and (3) putting the waterborne polyurethane emulsion into a polytetrafluoroethylene mold, curing at room temperature for 48h, and then putting into a drying oven with the temperature of 70 ℃ for drying for 12h to obtain the self-repairable waterborne polyurethane elastomer.
FIG. 1 is a reaction mechanism diagram of a self-repairable aqueous polyurethane elastomer prepared in example 1;
the self-repairable waterborne polyurethane elastomer prepared in the example 1 is cut off by using scissors, then the sections are contacted, the contacted section is repaired for 4 hours at 110 ℃, and a stress-strain curve graph before and after high-temperature repair is shown in FIG. 2;
as can be seen from fig. 2: the self-repairable aqueous polyurethane elastomer prepared in example 1 has a maximum tensile stress of 25.2MPa, a maximum tensile strain of 1269%, and has a repair efficiency of 82% at high temperature repair.
The self-repairable waterborne polyurethane elastomer prepared in the embodiment 1 is cut off by using scissors, a layer of absolute ethyl alcohol is sprayed on the section, the polyurethane elastomer is placed at normal temperature for 6 hours, and the stress-strain curve chart before and after solvent repair is shown in FIG. 3;
FIG. 3 is a stress-strain curve before and after solvent repair of the self-repairable aqueous polyurethane elastomer prepared in example 1, wherein 1 is before repair, and 2 is after repair;
as can be seen from fig. 3: the repair efficiency was 95% after a small amount of solvent repair at room temperature.
FIG. 4 is an infrared ray graph of the self-repairable aqueous polyurethane elastomer prepared in example 1;
as can be seen from fig. 4: at 3500cm -1 And 2270cm -1 No peaks of-OH and-NCO were found at 3302cm -1 And 3377cm -1 To NH 2 The double peak of (c) disappears. 3327cm -1 Is at an absorption peak of-NH-1713 cm -1 Under C = O stretching vibration, 1640cm -1 The reaction of isocyanate is illustrated by the hydrogenated-C = O absorption peak. 1531cm -1 The bending vibration of the urethane or amide group N-H shows that the self-repairable waterborne polyurethane elastomer chain structure in the example 1 is successfully constructed.
FIG. 5 is a polarization microscope image of the self-repairable aqueous polyurethane elastomer prepared in example 1 before and after high-temperature repair and solvent repair;
as can be seen from fig. 5: the elastomer section can be repaired under the conditions of high temperature and solvent, and the section trace disappears after the repair.
Example 2: a preparation method of a self-repairable waterborne polyurethane elastomer is specifically completed according to the following steps:
1. under the protection of inert gas, 10.53g of 4,4' -dicyclohexyl methane diisocyanate (HMDI) and 1.47g of deoxythymidine (2-Td) react for 1.5h at 30 ℃ to obtain a reaction product I;
2. adding 30g of polyether glycol (PPG) into the reaction product I, heating to 80 ℃, reacting for 1h at 80 ℃, adding 1.87g of 2, 2-dimethylolpropionic acid (DMPA) and 10mL of acetone, and continuously reacting for 2h at 80 ℃ to obtain a polyurethane prepolymer;
3. reducing the temperature of the polyurethane prepolymer to 45 ℃, adding 1.42g of triethylamine, and continuously reacting at 45 ℃ for 30min to obtain the prepolymer;
4. firstly, dispersing 0.56g of triethylene tetramine in distilled water, and then dispersing the prepolymer obtained in the third step in the distilled water to obtain a waterborne polyurethane emulsion with the solid content of 30%;
5. and (3) putting the waterborne polyurethane emulsion into a polytetrafluoroethylene mold, curing at room temperature for 48h, and then putting into a drying oven with the temperature of 70 ℃ for drying for 12h to obtain the self-repairable waterborne polyurethane elastomer.
Example 3: a preparation method of a self-repairable waterborne polyurethane elastomer is specifically completed according to the following steps:
1. under the protection of inert gas, 9.58g of Hexamethylene Diisocyanate (HDI) and 0.80g of deoxythymidine (2-Td) react for 1.5h at 30 ℃ to obtain a reaction product I;
2. adding 30g of polyether glycol (PPG) into the reaction product I, heating to 80 ℃, reacting for 1h at 80 ℃, adding 1.87g of 2, 2-dimethylolpropionic acid (DMPA) and 10mL of N-methylpyrrolidone (NMP), and continuing to react for 2h at 80 ℃ to obtain a polyurethane prepolymer;
3. reducing the temperature of the polyurethane prepolymer to 45 ℃, adding 1.42g of triethylamine, and continuously reacting at 45 ℃ for 0.5h to obtain the prepolymer;
4. firstly, 0.13g of 1, 2-ethylenediamine is dispersed in distilled water, and then the prepolymer obtained in the third step is dispersed in distilled water to obtain aqueous polyurethane emulsion with the solid content of 30 percent;
5. and (3) putting the waterborne polyurethane emulsion into a polytetrafluoroethylene mold, curing at room temperature for 48h, and then putting into a drying oven with the temperature of 70 ℃ for drying for 12h to obtain the self-repairable waterborne polyurethane elastomer.
The self-repairable waterborne polyurethane elastomers prepared in the embodiments 2 and 3 can repair the cross section of the elastomer under the conditions of high temperature or solvent, and the cross section trace disappears after repair.
Claims (10)
1. A preparation method of a self-repairable waterborne polyurethane elastomer is characterized by comprising the following steps:
1. under the protection of inert gas, diisocyanate and deoxythymidine react at 25-50 ℃ to obtain a reaction product I;
2. adding polyether polyol into the reaction product I, heating to 70-85 ℃, reacting for a period of time at 70-85 ℃, adding 2,2-dimethylolpropionic acid and a solvent, and continuously reacting for a period of time at 70-85 ℃ to obtain a polyurethane prepolymer;
3. reducing the temperature of the polyurethane prepolymer to 40-45 ℃, then adding triethylamine, and continuously reacting at 40-45 ℃ for a period of time to obtain the prepolymer;
4. firstly, dispersing a chain extender in distilled water, and then dispersing the prepolymer obtained in the third step in distilled water to obtain a waterborne polyurethane emulsion;
5. and (3) putting the waterborne polyurethane emulsion into a polytetrafluoroethylene mold, curing at room temperature, and drying after curing to obtain the self-repairable waterborne polyurethane elastomer.
2. The preparation method of the self-repairable aqueous polyurethane elastomer according to claim 1, wherein the diisocyanate in the first step is aromatic isocyanate, aliphatic isocyanate or alicyclic isocyanate.
3. The preparation method of the self-repairable waterborne polyurethane elastomer as claimed in claim 1, wherein the molar ratio of diisocyanate to deoxythymidine in the step one is (6-20): 1; the reaction time in the step one is 1-3 h.
4. The preparation method of the self-repairable waterborne polyurethane elastomer as claimed in claim 1, wherein the solvent in the second step is acetone, butanone or N-methylpyrrolidone; the molar ratio of the polyether polyol in the second step to the deoxythymidine in the first step is (1-5) to 1; the molar ratio of the polyether glycol to 2,2-dimethylolpropionic acid in the second step is 1 (0.5-1); the molar ratio of the solvent to 2,2-dimethylolpropionic acid in the second step is (10-60): 1.
5. The preparation method of the self-repairable aqueous polyurethane elastomer according to claim 1, wherein in the second step, polyether polyol is added into the reaction product I, the temperature is raised to 70-85 ℃, the reaction lasts for 1-4 h at 70-85 ℃,2,2-dimethylolpropionic acid is added, and the reaction lasts for 1-3 h at 70-85 ℃, so as to obtain a polyurethane prepolymer.
6. The preparation method of the self-repairable aqueous polyurethane elastomer according to claim 1, wherein the molar ratio of the triethylamine in the third step to the 2,2-dimethylolpropionic acid in the second step is 1:1, the temperature of the polyurethane prepolymer is reduced to 40-45 ℃, then the triethylamine is added, and the reaction is continued at 40-45 ℃ for 20-30 min to obtain the reaction product II.
7. The preparation method of the self-repairable aqueous polyurethane elastomer according to claim 1, wherein the chain extender in the fourth step is 1,2-ethylenediamine, 1,4-butanediol, isophorone diamine or triethylene tetramine; the 2,2-dimethylolpropionic acid and polyether polyol are dried to remove water before use.
8. The preparation method of the self-repairable aqueous polyurethane elastomer according to claim 1, characterized in that the molar ratio of the chain extender in the fourth step to the deoxythymidine in the first step is 1 (0.5-1.5); the solid content of the waterborne polyurethane emulsion in the step four is 30-40%.
9. The preparation method of the self-repairable aqueous polyurethane elastomer according to claim 1, wherein the curing time in the fifth step is 12-48 hours; and the drying temperature in the step five is 50-83 ℃, and the drying time is 8-24 h.
10. The preparation method of the self-repairable aqueous polyurethane elastomer as claimed in claim 1, wherein the self-repairable aqueous polyurethane elastomer in the fifth step includes two parts, namely a hard segment and a soft segment, the soft segment is polyether polyol and has a molecular weight Mw = 2000-4500 g/mol, the hard segment is isophorone diisocyanate, and the molar ratio of the hard segment to the soft segment is (1-2): 1.
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