CN114349924A - Self-repairing polyurethane and preparation method thereof - Google Patents
Self-repairing polyurethane and preparation method thereof Download PDFInfo
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Abstract
The self-repairing polyurethane has a novel structure, a repeating unit contains a functional group, and the functional group can be reversibly broken under a certain ultrasonic wave or temperature condition, so that the stimulation response and the self-repairing of the polyurethane are realized. The tensile strength range of the polyurethane is 15-60MPa, the tensile strength range after stimulus response is 10-30MPa, the tensile strength range after self-repairing is 10-60MPa, and the self-repairing rate reaches 92% -97%. The synthesis method of the self-repairing polyurethane is simple and convenient, firstly, the polyester polyol containing functional groups is designed and synthesized, and then, the polyester polyol reacts with the commercial isocyanate to obtain a target product, and the stimulation response and self-repairing process has strong operability and wide application value.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to self-repairing polyurethane and a preparation method thereof.
Background
High molecular polymer materials have been widely used in various fields including daily life, transportation industry, textile industry, electronic industry, biomedicine, aerospace, and the like. However, such materials are susceptible to external factors and self service life during use, and thus, the materials are susceptible to cracking, damage and aging, and the performance and service life of the materials are reduced. Therefore, the polymer material capable of self-repairing after mechanical damage is designed, so that the service life of the material can be greatly prolonged, and the application range of the material is widened.
The self-repairing function of polyurethane becomes a hot point of research in recent years, the self-repairing property of the material is realized by introducing different dynamic keys with the self-repairing function into the polyurethane, the service cycle of the self-repairing high polymer material can be prolonged to ensure the stability and safety of the self-repairing high polymer material, the requirement of future development on higher durability of a novel material is met, and the material with high performance and high self-repairing rate becomes a challenge.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems in the prior art, the invention provides self-repairing polyurethane and a preparation method thereof, the designed and synthesized self-repairing polyurethane contains functional groups, and the functional groups can be reversibly broken under the condition of ultrasonic waves or temperature, so that the polyurethane is endowed with stimulus responsiveness and self-repairing property; the preparation method is simple and efficient, firstly polyester polyol containing functional groups is designed and synthesized, then the polyester polyol reacts with isocyanate to prepare self-repairing polyurethane, the functional groups can be fractured by ultrasonic stimulation, and the functional groups fractured under mild conditions can realize rapid self-repairing.
In order to achieve the purpose, the invention provides self-repairing polyurethane, which has the following repeating unit structural formula:
wherein n is more than or equal to 1 and less than or equal to 30, and P is polyester polyol containing Diels-Alder adduct;
r' is
Any one of them.
Specifically, the polyester polyol containing the Diels-Alder adduct is prepared by the following method:
route one: firstly, carrying out Diels-Alder reaction on furan alcohol and bismaleimide in an organic solvent, taking the formed Diels-Alder adduct as an initiator, taking cyclic ester as a monomer, respectively dissolving in the organic solvent, and carrying out ring-opening polymerization under a ring-opening polymerization reaction catalyst to prepare polyester polyol containing the Diels-Alder adduct;
or route two: under inert gas, furan alcohol is used as an initiator, cyclic ester is used as a monomer, the solvents are respectively dissolved in an organic solvent, ring-opening polymerization is carried out under the condition of a ring-opening polymerization reaction catalyst in the organic solvent, polyester polyol containing furyl is prepared, and then Diels-Alder reaction is carried out on the polyester polyol and bismaleimide, so that the polyester polyol containing Diels-Alder adduct is prepared.
Wherein the furanol is selected from any one of the following structures:
the bismaleimide is selected from any one of the following structures:
Any one of the following structures:
the invention further provides a preparation method of the self-repairing polyurethane, which comprises the following steps:
(1) preparation of functional group-containing polyester polyol:
route one: firstly, carrying out Diels-Alder reaction on furan alcohol and bismaleimide in an organic solvent, taking the formed Diels-Alder adduct as an initiator, taking cyclic ester as a monomer, respectively dissolving in the organic solvent, and carrying out ring-opening polymerization under a ring-opening polymerization reaction catalyst to prepare polyester polyol containing the Diels-Alder adduct;
or route two: under inert gas, furan alcohol is taken as an initiator, cyclic ester is taken as a monomer, the solvents are respectively dissolved in an organic solvent, ring-opening polymerization is carried out under the condition of a ring-opening polymerization reaction catalyst in the organic solvent, polyester polyol containing furyl is prepared, and then Diels-Alder reaction is carried out on the polyester polyol and bismaleimide, so as to prepare polyester polyol containing Diels-Alder adduct;
(2) preparation of self-repairing polyurethane: and (2) carrying out polyaddition reaction on the polyester polyol containing the Diels-Alder adduct prepared in the step (1) and isocyanate in the presence of a polyaddition reaction catalyst in an organic solvent under an inert gas to obtain polyurethane containing the Diels-Alder adduct. The reacted solution is typically cast into a teflon mold and cured in an oven to yield a cured polyurethane containing the Diels-Alder adduct.
Wherein the furanol is selected from any one of the following structures:
the bismaleimide is selected from any one of the following structures:
Any one of the following structures:
wherein the isocyanate is selected from any one of the following structures:
specifically, the inert gas in the step (1) or the step (2) is independently optionally argon or nitrogen; the organic solvent in the steps (1) - (2) is any one of toluene, acetone, dichloromethane, N-dimethylformamide, tetrahydrofuran, anhydrous acetonitrile or chloroform.
The ring-opening polymerization reaction catalyst in the step (1) is any one of diphenyl phosphate, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1, 8-diazohetero-bis spiro [5.4.0] undec-7-ene and 4-dimethylaminopyridine, and the polyaddition reaction catalyst in the step (2) is any one of triethylamine, triethylenediamine, dibutyltin dilaurate, stannous octoate, stannous chloride, dibutyltin diacetate or tetrabutyl titanate.
In particular, route one synthesis of Diels-Alder adduct: the feeding molar ratio of the furan alcohol to the bismaleimide is (2-4) to 1, the reaction temperature is 40-80 ℃, and the reaction time is 12-48 h; in the synthesis of the polyester polyol containing the Diels-Alder adduct, the feeding molar ratio of cyclic ester, the formed Diels-Alder adduct and a ring-opening polymerization catalyst is (10-100) to 1 (0.1-0.5), the concentration of cyclic ester monomer is 0.5-5mol/L, the reaction temperature is 0-50 ℃, and the reaction time is 10-600 min;
route two in the synthesis of furanyl-containing polyester polyols: the feeding molar ratio of the cyclic ester, the furan alcohol and the ring-opening polymerization reaction catalyst is (10-100) to 1 (0.1-0.5), the concentration of the cyclic ester monomer is 0.5-5mol/L, the reaction temperature is 0-50 ℃, and the reaction time is 10-600 min; in the synthesis of the polyester polyol containing the Diels-Alder adduct, the feeding molar ratio of the polyester polyol containing the furyl group to the bismaleimide is (2-4):1, the reaction temperature is 40-80 ℃, and the reaction time is 12-48 h.
In the step (2), the reaction molar ratio of the polyester polyol containing the Diels-Alder adduct to the isocyanate is 1 (1-10), the adding amount of the catalyst is 0.1-0.2 wt% of reactants, the reaction temperature is 60-70 ℃, and the reaction time is 1-24 h.
The invention further provides a method for breaking and repairing the self-repairing polyurethane, and specifically, the conditions for breaking the polyurethane containing the Diels-Alder adduct are as follows: the ultrasonic temperature is 25-100 ℃, the ultrasonic power is 150-; the self-repairing conditions are as follows: the temperature is 25-60 ℃, and the time is 0-10 h.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the invention successfully designs and synthesizes novel self-repairing polyurethane, the DA adduct is synthesized by the reaction of green furfuryl alcohol and various bismaleimides, and dynamic covalent bond bonds are introduced into the main chain of the polyurethane to prepare a series of novel self-repairing polyurethane, on one hand, the material is endowed with ultrasonic stimulation response, the DA reverse reaction is realized under the ultrasonic stimulation, on the other hand, the self-repairing performance is enabled to be possible, the DA reverse reaction is realized under the mild temperature, and the service life of the material is prolonged. The prepared polyurethane has high mechanical property and high self-repairing rate, the tensile strength range before ultrasonic wave is 15-60MPa, the tensile strength range after ultrasonic wave is 10-30MPa, and the tensile strength range after self-repairing is 10-60 MPa; the self-repairing rate reaches 92% -97%.
(2) The preparation method has reasonable route, is simple and efficient, and introduces DA adducts into polyester polyol through controllable ring-opening polymerization and DA reaction to prepare a series of polyester polyols containing DA adducts with different molecular weights; and then a series of polyurethane materials are prepared by adjusting and controlling the proportion of polyester polyol to isocyanate. The tensile strength range of the polyurethane is 15-60MPa, the tensile strength range after stimulus response is 10-30MPa, the tensile strength range after self-repairing is 10-60MPa, and the self-repairing rate reaches 92% -97%, so that the novel self-repairing polyurethane material with high mechanical property and high self-repairing rate is prepared under continuous experimental optimization.
Drawings
FIG. 1 is a schematic preparation scheme of example 1;
FIG. 2 is a nuclear magnetic results plot of the DA adduct-containing polycaprolactone polyol prepared in example 1;
FIG. 3 is a nuclear magnetic results plot of the polyurethane containing DA adducts prepared in example 1;
FIG. 4 is a schematic preparation scheme of example 2;
FIG. 5 is a nuclear magnetic map of the DA adduct-containing polylactone polyol prepared in example 2;
FIG. 6 is a nuclear magnetic results plot of the DA adduct containing polyurethane prepared in example 2;
FIG. 7 is a schematic representation of the preparation of example 3;
FIG. 8 is a nuclear magnetic results plot of the DA adduct-containing polycaprolactone polyol prepared in example 3;
FIG. 9 is a nuclear magnetic results plot of the polyurethane containing DA adducts prepared in example 3;
Detailed Description
The present invention will be described in further detail with reference to specific examples, which will help understanding the present invention, but the scope of the present invention is not limited to the following examples.
The reagents used in the following examples are commercially available reagents or reagents synthesized by conventional methods.
The molecular weight of the product was measured using a 400MHz Bruker NMR instrument in the following examples of the invention; and 6mg of a sample is taken in a nuclear magnetic tube, a deuterated reagent is added, and the sample is measured after the sample is completely dissolved by oscillation.
Example 1
FIG. 1 is a scheme for preparing example 1.
Into a 20ml ampoule, caprolactone (1.7121g, 15mmol), toluene 5.8ml, diphenyl phosphate DPP (0.0625g, 0.25mmol), Furanmethanol (0.098g, 1mmol) were charged, and N was added at 50 deg.C2Mechanically stir for 2h under protection. And after the reaction is finished, the triethylamine is used for stopping the reaction, the reaction solution is added into a cold methanol solution, a polymer is separated out, and the mixture is filtered, separated and dried in vacuum, so that 1.587g of the furyl polycaprolactone polyol is obtained. Mechanically stirring furan-based polycaprolactone polyol (1g, 0.553mmol), N' - (1, 4-phenylene) bismaleimide (0.098g, 0.276mmol) and toluene (50 ml) at 60 ℃ for 24 hours, removing the solvent by rotary evaporation after the reaction is finished, filtering, separating and drying in vacuum to obtain 1.093g of polycaprolactone polyol containing DA adduct. FIG. 2 is a nuclear magnetic results plot of the prepared DA adduct-containing polycaprolactone polyol.
Adding polycaprolactone polyol (1g, 0.132mmol) containing DA adduct, hexamethylene diisocyanate HDI (0.022g, 0.132mmol), 0.1 wt% dibutyltin dilaurate DBT and 5ml of N, N-dimethylformamide into a 10ml reaction bottle at 70 ℃ and N, N-dimethylformamide2The protection reaction is carried out for 24h, the product is cast in a polytetrafluoroethylene mould after the reaction is finished and is cured for 48h in an oven at the temperature of 80 ℃, 0.85g of polyurethane containing DA adduct is obtained, and FIG. 3 is a nuclear magnetic result chart of the polyurethane containing DA adduct prepared in example 1.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 15min at the temperature of 20 ℃, the power of 300W and the frequency of 25kHz, casting the mixture into a polytetrafluoroethylene mold, and curing the mixture in an oven at the temperature of 90 ℃ for 48h to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of the polyurethane subjected to the DA adduct breakage for 2 hours at the temperature of 50 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 2
FIG. 4 is a preparation route of example 2.
Furanmethanol (1.96g, 20mmol), N' - (1, 4-phenylene) bismaleimide (3.58g, 10mmol) and 400ml of acetone were placed in a 50ml reaction flask, and mechanically stirred at 60 ℃ for 24 hours. After the reaction, the solvent was removed by rotary evaporation and column separation to obtain 3.1g of pure DA adduct. Into a 20ml ampoule, valerolactone (1.653g, 15mmol), toluene 14.6ml, diphenyl phosphate (0.0625g, 0.25mmol), DA adduct (0.277g, 0.5mmol) were charged, N.degree.C.2Mechanically stir for 2h under protection. After the reaction is finished, triethylamine stops the reaction, and the reaction solution is added into a cold methanol solution to precipitate a polymer. After filtration and separation, vacuum drying was carried out to obtain 1.124g of polycaprolactone polyol containing DA adduct. FIG. 5 is a nuclear magnetic diagram of the prepared DA adduct-containing polylactone polyol.
The DA adduct-containing polypentanolide polyol (1g, 0.278mmol), hexamethylene diisocyanate HDI (0.046g, 0.278mmol), 0.1% by weight of dibutyltin dilaurate DBT, and 5ml of N, N-dimethylformamide were charged into a 10ml reaction flask at 70 ℃ under N2And (3) carrying out protection reaction for 24h, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.93g of polyurethane containing DA adduct. FIG. 6 is a nuclear magnetic results plot of the DA adduct containing polyurethane prepared in example 2.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 15min under the conditions of temperature of 20 ℃, power of 250W and frequency of 30kHz, casting in a polytetrafluoroethylene mold, and curing for 48h in an oven at 100 ℃ to obtain the polyurethane after DA adduct breakage.
And curing the 0.5g of the polyurethane subjected to the DA adduct breakage for 2 hours at the temperature of 50 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 3
FIG. 7 is a scheme for the preparation of example 3.
Into a 20ml ampoule, caprolactone (3.4242g, 30mmol), toluene 14.6ml, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD) (0.070g, 0.5mmol), and furfuryl alcohol (0.098g, 1mmol) were added, and mechanical stirring was carried out at 50 ℃ for 2 hours. After the reaction was completed, triethylamine terminated the reaction. And adding the reaction solution into a cold methanol solution, separating out a polymer, filtering, separating and then drying in vacuum to obtain 3.134g of the furyl polycaprolactone polyol. The preparation method comprises the steps of mechanically stirring furan-based polycaprolactone polyol (1g, 0.282mmol), N' - (1, 4-phenylene) bismaleimide (0.201g, 0.564mmol) and toluene (50 ml) at 60 ℃ for 24 hours, removing a solvent by rotary evaporation after the reaction is finished, filtering, separating and drying in vacuum to obtain 1.751g of polycaprolactone polyol containing a DA adduct. FIG. 8 is a nuclear magnetic results plot of the prepared DA adduct-containing polycaprolactone polyol.
Mixing 1g of DA adduct-containing polyhexanol polyol (0.120 mmol), 4' -methylenebis (phenyl isocyanate) MDI (0.030g, 0.120mmol), 0.1 wt% of stannous octoate Sn (Oct)2And 2ml of N, N-dimethylformamide are added into an ampoule bottle, the mixture reacts for 60min at the temperature of 60 ℃, the mixture is cast into a polytetrafluoroethylene mold after the reaction is finished, and the mixture is cured for 48h at the temperature of 80 ℃ in an oven, so that 0.97g of polyurethane containing the DA adduct is obtained. FIG. 9 is a nuclear magnetic results plot of the polyurethane containing DA adducts prepared in example 3.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 20min under the conditions of temperature of 20 ℃, power of 250W and frequency of 35kHz, casting in a polytetrafluoroethylene mold, and curing for 48h in an oven at 100 ℃ to obtain the polyurethane after DA adduct breakage.
And curing the 0.5g of polyurethane subjected to DA adduct breakage for 4 hours at the temperature of 45 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 4
In a 50ml reaction flask, 2, 5-furandimethanol (2.56g, 20mmol), N' - (1, 4-phenylene) bismaleimide (3.58g, 10mmol) and 400ml of acetone were added, followed by mechanical stirring at 60 ℃ for 24 hours. After the reaction, the solvent was removed by rotary evaporation and column separation was carried out to obtain 4.2g of pure DA adduct. Into a 20ml ampoule, caprolactone (1.7121g, 15mmol), toluene 14.6ml, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene (TBD) (0.035g, 0.25mmol), DA adduct (0.307g, 0.5mmol) were added, and mechanical stirring was carried out at 50 ℃ for 2 hours under protection of Ar. After the reaction is finished, triethylamine stops the reaction, and the reaction solution is added into a cold methanol solution to precipitate a polymer. Separated by filtration and dried under vacuum to obtain 1.123g of polycaprolactone polyol containing DA adduct.
Adding 1g of polycaprolactone polyol (1g, 0.248mmol) containing DA adduct, 0.112g of L-Lysine Diisocyanate (LDI), 0.1 wt% of triethylene diamine and 5ml of N, N-dimethylformamide into a 10ml reaction bottle, reacting for 24h at 70 ℃, casting into a polytetrafluoroethylene mold after the reaction is finished, and curing for 48h at 80 ℃ in an oven to obtain 0.95g of polyurethane containing DA adduct.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 20min at the temperature of 20 ℃, the power of 150W and the frequency of 40kHz, casting the mixture into a polytetrafluoroethylene mold, and curing the mixture in an oven at the temperature of 100 ℃ for 48h to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of the polyurethane subjected to the DA adduct breakage for 5 hours at the temperature of 50 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 5
In a 20ml ampoule valerolactone (3.306g, 30mmol), dichloromethane (14.6 ml), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD) (0.077g, 0.5mmol), 1- (furan-2-yl) -neopentane-1, 3-diol (0.170g, 1mmol) were added and stirred mechanically at 50 ℃ under Ar for 2 h. After the reaction was completed, triethylamine terminated the reaction. The reaction solution was added to a cold methanol solution, and a polymer was precipitated. The resulting mixture was separated by filtration and dried in vacuo to give 2.677g of a furanylpolypentane polyol. The furyl polypentanil polyol (1g, 0.315mmol) and N, N' - (1, 4-phenylene) bismaleimide (0.056g, 0.157mmol) are mechanically stirred for 24h at the temperature of 60 ℃ in 50ml of toluene, after the reaction is finished, the solvent is removed by rotary evaporation, and the filtrate is separated and dried in vacuum, thus obtaining 1.008g of polypentanil polyol containing DA adduct.
Adding 1g of poly-valerolactone polyol containing DA bonds (0.149 mmol), 0.186g of 4,4' -methylene bis (phenyl isocyanate) MDI (diphenyl diisocyanate), 0.745mmol, 0.1 wt% of stannous chloride and 2ml of toluene into an ampoule bottle, reacting for 60min at 60 ℃, casting into a polytetrafluoroethylene mold after the reaction is finished, and curing for 48h at 80 ℃ in an oven to obtain 0.66g of polyurethane containing DA adducts.
Dissolving 0.5g of polyurethane containing DA bonds in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 30min under the conditions of temperature of 20 ℃, power of 350W and frequency of 40kHz, casting in a polytetrafluoroethylene mold, and curing for 48h in an oven at 100 ℃ to obtain the polyurethane after the DA adduct is broken.
And curing the 0.4g of the polyurethane subjected to the DA adduct breakage for 4 hours at the temperature of 50 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 6
In a 50ml reaction flask, 2-methyl-3-furanmethanol (3.36g, 30mmol), tris (2-maleimidoethyl) amine (5.80g, 15mmol) and acetone (400 ml) were added, and mechanical stirring was carried out at 60 ℃ for 24 hours. After the reaction, the solvent was removed by rotary evaporation and column separation was carried out to obtain 3.8g of pure DA adduct. Into a 20ml ampoule, valerolactone (3.306g, 30mmol), toluene 14.6ml, diphenyl phosphate (0.0625g, 0.25mmol), DA adduct (0.305g, 0.5mmol) were charged, at 50 ℃ N2Mechanically stir for 2h under protection. After the reaction was completed, triethylamine terminated the reaction. The reaction solution was added to a cold methanol solution, and a polymer was precipitated. Separated by filtration and dried in vacuo to give 2.623g of a polyglutaric acid polyol containing DA adduct.
The DA adduct-containing polypentanolide polyol (1g, 0.233mmol), hexamethylene diisocyanate HDI (0.117g, 0.699mmol), 0.1% by weight of dibutyltin dilaurate DBT, and 5ml of N, N-dimethylformamide were charged into a 10ml reaction flask at 70 ℃ under N2And (3) carrying out protection reaction for 24h, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.94g of polyurethane containing DA adduct.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 30min at the temperature of 50 ℃, the power of 450W and the frequency of 45kHz, casting the mixture into a polytetrafluoroethylene mold, and curing the mixture in an oven at the temperature of 100 ℃ for 48h to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of polyurethane subjected to DA adduct breakage for 7 hours at the temperature of 40 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 7
Into a 20ml ampoule, propyl gum ester (4.328g, 30mmol), toluene 14.6ml, 1, 8-diazohetero-bis-spiro [5.4.0] were added]Undec-7-ene (DBU) (0.076g, 0.5mmol), (3-methylfuran-2-yl) methanol (0.112g, 1mmol), 50 ℃ N2Mechanically stir for 2h under protection. After the reaction was completed, triethylamine terminated the reaction. The reaction solution was added to a cold methanol solution, and a polymer was precipitated. The residue was separated by filtration and dried in vacuo to give 3.674g of furylpropylenegum ester. Furyl polypropylene gum ester (1g, 0.25mmol), N' - (1, 4-phenylene) bismaleimide (0.044g, 0.125mmol) and toluene (50 ml) are mechanically stirred for 24h at 60 ℃, after the reaction is finished, the solvent is removed by rotary evaporation, and after filtration and separation, vacuum drying is carried out, thus obtaining 1.004g of polypropylene gum ester polyol containing DA adduct.
Adding a DA adduct-containing polypropylene-gel ester polyol (1g, 0.108mmol), 4.4-diisocyanate dicyclohexylmethane HMDI (0.141g, 0.540mmol), 0.1 wt% stannous octoate Sn (Oct)22ml of N, N-dimethylformamide, and adding the mixture into an ampoule bottle at the temperature of 60 ℃ and N2And (3) carrying out protection reaction for 60min, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.84g of polyurethane containing DA adduct.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 40min under the conditions of 60 ℃ of temperature, 550W of power and 50kHz of frequency, casting in a polytetrafluoroethylene mold, and curing for 48h in an oven at 100 ℃ to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of the polyurethane subjected to DA adduct breakage for 10 hours at the temperature of 30 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 8
Into a 20ml ampoule, was added propyl gum ester (4.328g, 30mmol), tetrahydrofuran 5.8ml, 4-Dimethylaminopyridine (DMAP) (0.031g, 0.25mmol), ethylfuran-2-methanol (0.122g, 1mmol), N.degree.C.2Mechanically stir for 2h under protection. After the reaction was completed, triethylamine terminated the reaction. The reaction solution was added to a cold methanol solution, and a polymer was precipitated. The residue was separated by filtration and dried in vacuo to give 3.244g of furyl polypropylene gum ester. The mechanical stirring of furyl polypropylene gum ester (1g, 0.225mmol), 1, 8-bis (maleimide) octane (0.034g, 0.113mmol) and toluene (50 ml) at 60 ℃ for 24h, removing the solvent by rotary evaporation after the reaction is finished, filtering and separating, and then drying in vacuum to obtain 1.014g of the polypropylene gum ester polyol containing DA adduct.
Adding the DA adduct-containing polypropylene-gel ester polyol (1g, 0.109mmol), trans-1, 4-cyclohexyl diisocyanate CHDI (0.038g, 0.227mmol), 0.1 wt% dibutyltin diacetate and 2ml of N, N-dimethylformamide into an ampoule at 60 deg.C2And (3) carrying out protection reaction for 60min, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.74g of polyurethane containing DA adduct.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 50min at the temperature of 60 ℃, the power of 550W and the frequency of 40kHz, casting the mixture into a polytetrafluoroethylene mold, and curing the mixture in an oven at the temperature of 100 ℃ for 48h to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of polyurethane subjected to DA adduct breakage for 6 hours at the temperature of 45 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 9
Into a 20ml ampoule, were charged trimethylene carbonate (3.062g, 30mmol), toluene (14.6 ml), toluene,Diphenyl phosphate (0.125g, 0.5mmol), 3,4 furan-dimethanol (0.128g, 1mmol), 50 ℃ N2Mechanically stir for 2h under protection. After the reaction was completed, triethylamine terminated the reaction. The reaction solution was added to a cold methanol solution, and a polymer was precipitated. The filtrate was separated and dried in vacuo to give 2.986g of a furyl polylactic acid. Furyl polylactic acid (1g, 0.315mmol), 1, 6-bismaleimide hexane (0.044g, 0.158mmol) and toluene (50 ml) are mechanically stirred for 24h at 60 ℃, after the reaction is finished, the solvent is removed by rotary evaporation, and after filtration and separation, vacuum drying is carried out, thus obtaining 1.212g of polylactic acid containing DA adduct.
Adding polylactic acid (1g, 0.150mmol) containing DA adduct, 4-toluene diisocyanate 2,4-TDI (0.053g, 0.304mmol), 0.1 wt% dibutyltin dilaurate DBT and 2ml toluene into an ampoule at 60 deg.C, and adding N2And (3) carrying out protection reaction for 60min, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.78g of polyurethane containing DA adduct.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 40min under the conditions of 60 ℃ of temperature, 350W of power and 65kHz of frequency, casting the mixture in a polytetrafluoroethylene mold, and curing the mixture for 48h in an oven at 100 ℃ to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of polyurethane subjected to DA adduct breakage for 7 hours at the temperature of 45 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 10
Into a 20ml ampoule, trimethylene carbonate (3.062g, 30mmol), toluene (14.6 ml), 4-Dimethylaminopyridine (DMAP) (0.031g, 0.25mmol), 1- (2-furyl) ethanol (0.112g, 1mmol) were charged, and the mixture was heated at 50 ℃ under reduced pressure, and N was added2Mechanically stir for 2h under protection. After the reaction was completed, triethylamine terminated the reaction. The reaction solution was added to a cold methanol solution, and a polymer was precipitated. The filtrate was separated and dried in vacuo to give 2.994g of a furyl-containing polylactic acid. The furyl polylactic acid (1g, 0.315mmol) and 1, 2-bismaleimidoethane (0.034g, 0.158mmol) were mixed with toluene (50 ml) and mechanically stirred at 60 deg.CAnd (3) after 24h, removing the solvent by rotary evaporation after the reaction is finished, filtering and separating, and drying in vacuum to obtain 1.002g of polylactic acid containing the DA adduct.
Adding polylactic acid (1g, 0.151mmol) containing DA adduct, toluene 2, 6-diisocyanate 2,6-TDI (0.026g, 0.151mmol), 0.1 wt% tetrabutyl titanate and 2ml toluene into an ampoule at 60 deg.C, and adding N2And (3) carrying out protection reaction for 60min, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.98g of polyurethane containing DA adduct.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 20min at the temperature of 60 ℃, the power of 550W and the frequency of 75kHz, casting the mixture in a polytetrafluoroethylene mold, and curing the mixture in an oven at the temperature of 100 ℃ for 48h to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of the polyurethane subjected to the DA adduct breakage for 8 hours at the temperature of 50 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 11
Furfuryl alcohol (0.98g, 10mmol), 4,4' -diphenyl ether bismaleimide (1.80g, 5mmol) and chloroform (10 ml) were added to a 50ml reaction flask, and reacted at 45 ℃ for 24 hours, followed by isolation and purification to obtain 0.5g of DA adduct. Into a 20ml ampoule, trimethylene carbonate (3.062g, 30mmol), toluene 14.6ml, diphenyl phosphate (0.0625g, 0.25mmol), DA adduct (0.556g, 1mmol) were charged, N.degree.C.2Mechanically stir for 2h under protection. After the reaction was completed, triethylamine terminated the reaction. The reaction solution was added to a cold methanol solution, and a polymer was precipitated. The mixture was separated by filtration and dried in vacuo to obtain 2.990g of polylactic acid containing DA adduct.
Adding polylactic acid (1g, 0.276mmol) containing DA adduct, 4' -diisocyanate MDI (0.404g, 1.616mmol), 0.1 wt% dibutyltin dilaurate DBT and 2ml toluene into an ampoule at 60 deg.C and N2And (3) carrying out protection reaction for 60min, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.97g of polyurethane containing DA adduct.
Dissolving 0.8g of polyurethane containing DA bonds in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 30min under the conditions of 50 ℃ of temperature, 1250W of power and 35kHz of frequency, casting the solution in a polytetrafluoroethylene mold, and curing the solution in an oven at 100 ℃ for 48h to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of polyurethane subjected to DA adduct breakage for 7 hours at the temperature of 60 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 12
Furfuryl alcohol (0.981g, 10mmol), N, N' - (1, 4-phenylene) bismaleimide (1.7918g, 5mmol) and anhydrous acetonitrile (10 ml) are added into a 50ml reaction bottle, and the mixture reacts for 24 hours at 45 ℃ to obtain 0.5g of DA adduct after separation and purification. Into a 20ml ampoule, propyl gum ester (4.328g, 30mmol), tetrahydrofuran 5.8ml, diphenyl phosphate (0.0625g, 0.25mmol), DA adduct (0.554g, 1mmol) were charged, N.degree.C.2Mechanically stir for 2h under protection. After the reaction is finished, triethylamine stops the reaction, and the reaction solution is added into a cold methanol solution to precipitate a polymer. The mixture was separated by filtration and dried in vacuo to obtain 3.634g of a polypropylene-base polyol containing DA adduct.
Adding DA adduct-containing polypropylene-gel ester polyol (1g, 0.281mmol), norbornane diisocyanate NBDI (0.187g, 0.843mmol), 0.1 wt% stannous octoate Sn (Oct)22ml of N, N-dimethylformamide and 2ml of toluene are added into an ampoule bottle at the temperature of 60 ℃ and N2And (3) carrying out protection reaction for 60min, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.78g of polyurethane containing DA adduct.
Dissolving 0.7g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 60min under the conditions of 50 ℃ of temperature, 1050W of power and 75kHz of frequency, casting the mixture in a polytetrafluoroethylene mold, and curing the mixture in an oven at 100 ℃ for 48h to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of the polyurethane subjected to the DA adduct breakage for 8 hours at the temperature of 50 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
Example 13
Furfuryl alcohol (0.981g, 10mmol), N, N' - (1, 4-phenylene) bismaleimide (1.7918g, 5mmol) and anhydrous acetonitrile (10 ml) are added into a 50ml reaction bottle, and the mixture reacts for 24 hours at 45 ℃ to obtain 0.5g of DA adduct after separation and purification. Into a 20ml ampoule, valerolactone (3.306g, 30mmol), toluene 14.6ml, diphenyl phosphate (0.0625g, 0.25mmol), DA adduct (0.554g, 1mmol) were charged, N at 50 deg.C2Mechanically stir for 2h under protection. After the reaction was completed, triethylamine terminated the reaction. The reaction solution was added to a cold methanol solution, and a polymer was precipitated. Separated by filtration and dried in vacuo to give 2.974g of a polyglutaric lactone polyol containing a DA adduct.
Mixing poly valerolactone polyol containing DA adduct (1g, 0.279mmol), p-phenylene diisocyanate PPDI (0214g, 1.336mmol), 0.1 wt% stannous octoate Sn (Oct)22ml of N, N-dimethylformamide and 2ml of toluene are added into an ampoule bottle at the temperature of 60 ℃ and N2And (3) carrying out protection reaction for 60min, casting the obtained product in a polytetrafluoroethylene mold after the reaction is finished, and curing the product in an oven at 80 ℃ for 48h to obtain 0.91g of polyurethane containing DA adduct.
Dissolving 0.8g of polyurethane containing DA adduct in 5ml of tetrahydrofuran, carrying out ultrasonic treatment for 40min at the temperature of 50 ℃, the power of 950W and the frequency of 75kHz, casting the mixture into a polytetrafluoroethylene mold, and curing the mixture in an oven at the temperature of 100 ℃ for 48h to obtain the polyurethane after the DA adduct is broken.
And curing the 0.5g of polyurethane subjected to DA adduct breakage for 9 hours at the temperature of 55 ℃ to obtain the self-repaired polyurethane.
The molecular weight characteristics of the prepared polyester polyol and polyurethane, as well as the mechanical properties and self-repairing rate results of the polyurethane before and after the ultrasound treatment are shown in tables 1 and 2.
TABLE 1 molecular weight characteristics of polyester polyol and polyurethane prepared in the examples of the present invention
TABLE 2 mechanical properties and self-repairing rate before and after ultrasound of the polymer prepared by the embodiment of the invention
(self-repairing efficiency: ratio of post-repair tensile strength to original tensile strength under a certain condition)
The invention introduces dynamic covalent bonds into a polyurethane main chain to prepare a novel self-repairing polyurethane material, wherein a repeating unit contains Diels-Alder (DA) reaction adduct, reversible conversion of DA can be realized under the action of ultrasonic stimulation, and the product can realize repairing depending on self-repairing property at a mild temperature. The tensile strength range of the self-repairing polyurethane before ultrasonic fracture is 15-60MPa, the tensile strength range after fracture is 10-30MPa, the tensile strength range after self-repairing is 10-60MPa, and the self-repairing rate reaches 92% -97%. The self-repairing material improves the mechanical property and the self-repairing rate, and can be applied to various fields of medical materials, aerospace, sensors and the like.
The present invention provides a preparation idea and a method of an ultrasonic-responsive self-repairing polyurethane containing a DA adduct, and a method and a way for implementing the technical scheme are many, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. The self-repairing polyurethane is characterized in that the structural formula of a repeating unit is as follows:
wherein n is more than or equal to 1 and less than or equal to 30, and P is polyester polyol containing Diels-Alder adduct;
r' is
Any one of them.
2. The self-healing polyurethane of claim 1, wherein the polyester polyol containing the Diels-Alder adduct is prepared by the process of:
route one: firstly, carrying out Diels-Alder reaction on furan alcohol and bismaleimide in an organic solvent, taking the formed Diels-Alder adduct as an initiator, taking cyclic ester as a monomer, respectively dissolving in the organic solvent, and carrying out ring-opening polymerization under a ring-opening polymerization reaction catalyst to prepare polyester polyol containing the Diels-Alder adduct;
or route two: under inert gas, furan alcohol is used as an initiator, cyclic ester is used as a monomer, the solvents are respectively dissolved in an organic solvent, ring-opening polymerization is carried out under the condition of a ring-opening polymerization reaction catalyst in the organic solvent, polyester polyol containing furyl is prepared, and then Diels-Alder reaction is carried out on the polyester polyol and bismaleimide, so that the polyester polyol containing Diels-Alder adduct is prepared.
3. The self-healing polyurethane of claim 2, wherein the furanol is selected from any one of the following structures:
the bismaleimide is selected from any one of the following structures:
4. the method for preparing the self-repairing polyurethane of any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) preparation of functional group-containing polyester polyol:
route one: firstly, carrying out Diels-Alder reaction on furan alcohol and bismaleimide in an organic solvent, taking the formed Diels-Alder adduct as an initiator, taking cyclic ester as a monomer, respectively dissolving in the organic solvent, and carrying out ring-opening polymerization under a ring-opening polymerization reaction catalyst to prepare polyester polyol containing the Diels-Alder adduct;
or route two: under inert gas, furan alcohol is taken as an initiator, cyclic ester is taken as a monomer, the solvents are respectively dissolved in an organic solvent, ring-opening polymerization is carried out under the condition of a ring-opening polymerization reaction catalyst in the organic solvent, polyester polyol containing furyl is prepared, and then Diels-Alder reaction is carried out on the polyester polyol and bismaleimide, so as to prepare polyester polyol containing Diels-Alder adduct;
(2) preparation of self-repairing polyurethane: and (2) carrying out polyaddition reaction on the polyester polyol containing the Diels-Alder adduct prepared in the step (1) and isocyanate in the presence of a polyaddition reaction catalyst in an organic solvent under an inert gas to obtain polyurethane containing the Diels-Alder adduct.
5. The method according to claim 4, wherein the isocyanate is selected from any one of the following structures:
6. the self-healing polyurethane of claim 4, wherein the inert gas of step (1) or step (2) is independently optionally argon or nitrogen; the organic solvent in the steps (1) to (4) is any one of toluene, acetone, dichloromethane, N-dimethylformamide, tetrahydrofuran, anhydrous acetonitrile or chloroform.
7. The method according to claim 4, wherein the ring-opening polymerization catalyst in the step (1) is any one of diphenyl phosphate, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1, 8-diazohetero-bis [5.4.0] undec-7-ene, and 4-dimethylaminopyridine, and the polyaddition catalyst in the step (2) is any one of triethylamine, triethylenediamine, dibutyltin dilaurate, stannous octoate, stannous chloride, dibutyltin diacetate, or tetrabutyl titanate.
8. The process according to claim 4, characterized in that in the synthesis route-the Diels-Alder adduct: the feeding molar ratio of the furan alcohol to the bismaleimide is (2-4) to 1, the reaction temperature is 40-80 ℃, and the reaction time is 12-48 h; in the synthesis of the polyester polyol containing the Diels-Alder adduct, the feeding molar ratio of cyclic ester, the formed Diels-Alder adduct and a ring-opening polymerization catalyst is (10-100) to 1 (0.1-0.5), the concentration of cyclic ester monomer is 0.5-5mol/L, the reaction temperature is 0-50 ℃, and the reaction time is 10-600 min;
route two in the synthesis of furanyl-containing polyester polyols: the feeding molar ratio of the cyclic ester, the furan alcohol and the ring-opening polymerization reaction catalyst is (10-100) to 1 (0.1-0.5), the concentration of the cyclic ester monomer is 0.5-5mol/L, the reaction temperature is 0-50 ℃, and the reaction time is 10-600 min; in the synthesis of the polyester polyol containing the Diels-Alder adduct, the feeding molar ratio of the polyester polyol containing the furyl group to the bismaleimide is (2-4):1, the reaction temperature is 40-80 ℃, and the reaction time is 12-48 h.
9. The preparation method according to claim 2, wherein in the step (2), the molar ratio of the polyester polyol containing the Diels-Alder adduct to the isocyanate is 1 (1-10), the amount of the catalyst is 0.1-0.2 wt% of the reactants, the reaction temperature is 60-70 ℃, and the reaction time is 1-24 h.
10. The method of fracturing and healing of a self-healing polyurethane according to any of claims 1 to 3, wherein said Diels-Alder adduct-containing polyurethane is fractured under conditions selected from the group consisting of: the ultrasonic temperature is 25-100 ℃, the ultrasonic power is 150-; the polyurethane self-repairing conditions containing the Diels-Alder adduct are as follows: the temperature is 25-60 ℃, and the time is 0-10 h.
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