CN112694587B - Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof - Google Patents

Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof Download PDF

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CN112694587B
CN112694587B CN201911011994.6A CN201911011994A CN112694587B CN 112694587 B CN112694587 B CN 112694587B CN 201911011994 A CN201911011994 A CN 201911011994A CN 112694587 B CN112694587 B CN 112694587B
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polyurethane
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CN112694587A (en
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唐瀚滢
解希铭
杜影
王丽静
王丽丽
赵丽娜
赵青松
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract

The invention relates to the field of self-repairing photocuring materials, and discloses self-repairing polyurethane based on a bidirectional repairing structure, and a preparation method and application thereof 1 、R 2 、R 3 、R 4 、R 5 、R 6 And R 7 Structural unit of provided, and R 1 Is polyethylene glycol, R 2 Is isophorone diisocyanate, R 3 Is terephthalaldehyde, R 4 Is oxalyl dihydrazide, R 5 Is resorcinol diglycidyl ether, R 6 Is furfuryl amine, R7 is N, N '- (4,4' -methylene diphenyl) bismaleimide. The polyurethane provided by the invention has excellent self-repairing capability and high self-repairing efficiency, can prolong the service life of materials, and reduces the hidden danger of microcracks caused by mechanical damage.

Description

Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof
Technical Field
The invention relates to the field of self-repairing polyurethane, in particular to self-repairing polyurethane based on a bidirectional repairing structure, a method for preparing the self-repairing polyurethane based on the bidirectional repairing structure, the self-repairing polyurethane based on the bidirectional repairing structure prepared by the method, and application of the self-repairing polyurethane based on the bidirectional repairing structure in at least one product selected from coatings, electronic products and packaging materials.
Background
The polyurethane material has excellent mechanical performance and good chemical stability, and is widely applied to the fields of traffic, electronics, packaging, buildings, biological materials and the like.
However, these products are often exposed to the environment during use, and may be subjected to collision, scratch, kink, chemical corrosion, UV photolysis aging or combination thereof caused by external force, such that the interior of the product develops micro-cracks and cracks, thereby losing the use efficiency and directly affecting the service life of the product.
At present, self-repairing polyurethane has been reported, but all the reports adopt a unidirectional repairing structure, and no self-repairing polyurethane material for constructing a bidirectional repairing structure is reported at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a self-repairing polyurethane with bidirectional repairability, which is helpful for accelerating the repairing rate of the self-repairing polyurethane, so as to prolong the service life of the self-repairing polyurethane and meet the requirements of the self-repairing polyurethane in application.
In order to achieve the above object, a first aspect of the present invention provides a self-repairing polyurethane based on a bidirectional repaired structure, the polyurethaneThe urethane contains a compound represented by the formula R 1 、R 2 、R 3 、R 4 、R 5 And R 6 Structural unit provided, and R 1 Is polyethylene glycol, R 2 Is isophorone diisocyanate, R 3 Is p-hydroxybenzaldehyde, R 4 Is oxalyl dihydrazide, R 5 Is resorcinol diglycidyl ether, R 6 Is furfuryl amine, R 7 Is N, N '- (4,4' -methylene diphenyl) bismaleimide, wherein R is the total weight of the polyurethane 1 The content of the structural units provided is from 30.8 to 87.9% by weight, based on R 2 The content of the structural units provided is 6.9 to 43.2 wt.%, based on R 3 The content of the structural units provided is from 0.2 to 11.7% by weight, from R 4 The content of the structural units provided is from 0.1 to 4.9% by weight, based on R 5 The content of the structural units provided is from 0.1 to 6.9% by weight, based on R 6 The content of the structural units provided is 0.2 to 6.6% by weight, represented by R 7 The content of the structural unit is 0.8-24.6 wt%, and the number average molecular weight of the polyurethane is 5000-120000, and the molecular weight distribution is 1.88-2.32.
A second aspect of the invention provides a method of making a bi-directional repair structure based self-healing polyurethane, the method comprising:
(1) under the condition of the first solution, adding R 3 And R 4 Carrying out a first reaction to obtain a solid product A1; under the condition of a second solution, adding R 5 And R 6 Carrying out a second reaction to obtain a solid product A2; and under the condition of the third solution, enabling R to react 2 And R 1 Carrying out a third reaction to obtain a polyurethane prepolymer B;
(2) under the condition of a fourth solution, carrying out a fourth reaction on the polyurethane prepolymer B, the solid product A1 and the solid product A2 to obtain linear polyurethane C;
(3) under the condition of a fifth solution, adding R 7 Carrying out a fifth reaction with the linear polyurethane C;
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 And R 7 In such an amount as to produceIn the polyurethane from R 1 The content of the structural unit is 30.8-87.9 wt%, and R is 2 The content of the structural units provided is 6.9 to 43.2 wt.%, based on R 3 The content of the structural units provided is from 0.2 to 11.7% by weight, based on R 4 The content of the structural units provided is from 0.1 to 4.9% by weight, based on R 5 The content of the structural units provided is from 0.1 to 6.9% by weight, based on R 6 The content of the structural units provided is 0.2 to 6.6% by weight, represented by R 7 The content of the provided structural unit is 0.8-24.6 wt%, and the number average molecular weight of the polyurethane is 5000-120000, and the molecular weight distribution is 1.88-2.32;
and, R 1 Is polyethylene glycol, R 2 Is isophorone diisocyanate, R 3 Is p-hydroxybenzaldehyde, R 4 Is oxalyl dihydrazide, R 5 Is resorcinol diglycidyl ether, R 6 Is furfuryl amine, R 7 Is N, N '- (4,4' -methylene diphenyl) bismaleimide.
The third aspect of the invention provides self-repairing polyurethane based on a bidirectional repairing structure, which is prepared by the method of the second aspect.
A fourth aspect of the present invention provides a use of the self-healing polyurethane based on a bi-directional repair structure according to the first aspect and/or the third aspect in at least one product selected from the group consisting of coatings, electronic products, and packaging materials.
Compared with the prior art, the self-repairing polyurethane based on the bidirectional repairing structure provided by the invention has a remarkably superior repairing rate.
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The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a nuclear magnetic hydrogen spectrum of a solid product A1 obtained in production example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of solid product A2 obtained in production example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As mentioned above, the first aspect of the invention provides a self-repairing polyurethane based on a bidirectional repairing structure, and the polyurethane contains R 1 、R 2 、R 3 、R 4 、R 5 And R 6 Structural unit of provided, and R 1 Is polyethylene glycol, R 2 Is isophorone diisocyanate, R 3 Is p-hydroxybenzaldehyde, R 4 Is oxalyl dihydrazide, R 5 Is resorcinol diglycidyl ether, R 6 Is furfuryl amine, R 7 Is N, N '- (4,4' -methylene diphenyl) bismaleimide, wherein R is the total weight of the polyurethane 1 The content of the structural units provided is from 30.8 to 87.9% by weight, based on R 2 The content of the structural units provided is 6.9 to 43.2% by weight, from R 3 The content of the structural units provided is from 0.2 to 11.7% by weight, based on R 4 The content of the structural units provided is from 0.1 to 4.9% by weight, based on R 5 The content of the structural units provided is from 0.1 to 6.9% by weight, based on R 6 The content of the structural units provided is 0.2 to 6.6% by weight, represented by R 7 The content of the structural unit is 0.8-24.6 wt%, and the number average molecular weight of the polyurethane is 5000-120000, and the molecular weight distribution is 1.88-2.32.
Preferably, R 1 Is a compound of formula (1R1) wherein n is such that R is 1 The average molecular weight of (b) is preferably 200-.
Figure BDA0002244475270000041
Preferably, R 2 Is a compound represented by the formula (1R 2):
Figure BDA0002244475270000042
preferably, R 3 Is a compound represented by the formula (1R 3):
Figure BDA0002244475270000043
preferably, R 4 Is a compound represented by the formula (1R 4):
Figure BDA0002244475270000044
preferably, R 5 Is a compound represented by the formula (1R 5):
Figure BDA0002244475270000045
preferably, R 6 Is a compound represented by the formula (1R 6):
Figure BDA0002244475270000051
preferably, R 7 Is a compound represented by the formula (1R 7):
Figure BDA0002244475270000052
as previously mentioned, a second aspect of the present invention provides a method of making a self-healing polyurethane based on a bi-directional repair structure, the method comprising:
(1) under the condition of the first solution, adding R 3 And R 4 Carrying out a first reaction to obtain a solid product A1; under the condition of a second solution, adding R 5 And R 6 Carrying out a second reaction to obtain a solid product A2; and under the condition of third solution, the first solution and the second solution are mixedR 2 And R 1 Carrying out a third reaction to obtain a polyurethane prepolymer B;
(2) under the condition of a fourth solution, carrying out a fourth reaction on the polyurethane prepolymer B, the solid product A1 and the solid product A2 to obtain linear polyurethane C;
(3) under the condition of a fifth solution, adding R 7 Carrying out a fifth reaction with the linear polyurethane C;
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 And R 7 In such an amount that the polyurethane obtained is made up of R 1 The content of the structural units provided is from 30.8 to 87.9% by weight, based on R 2 The content of the structural units provided is 6.9 to 43.2 wt.%, based on R 3 The content of the structural units provided is from 0.2 to 11.7% by weight, from R 4 The content of the structural units provided is 0.1 to 4.9% by weight, represented by R 5 The content of the structural units provided is from 0.1 to 6.9% by weight, based on R 6 The content of the structural units provided is from 0.2 to 6.6% by weight, based on R 7 The content of the provided structural unit is 0.8-24.6 wt%, and the number average molecular weight of the polyurethane is 5000-120000, and the molecular weight distribution is 1.88-2.32;
and, R 1 Is polyethylene glycol, R 2 Is isophorone diisocyanate, R 3 Is p-hydroxybenzaldehyde, R 4 Is oxalyl dihydrazide, R 5 Is resorcinol diglycidyl ether, R 6 Is furfuryl amine, R 7 Is N, N '- (4,4' -methylene diphenyl) bismaleimide.
More preferably, in the preparation method of the present invention, the polyethylene glycol has an average molecular weight of 200-.
In order to achieve better results, several preferred embodiments are provided below for each step in the method for preparing self-repairing polyurethane based on a bidirectional repairing structure provided by the invention.
Preferably, in step (1), the conditions of the first reaction include: the reaction temperature is 35-80 ℃, and the reaction time is 0.5-4 h.
Preferably, in step (ii)In step (1), R of the first reaction is carried out 3 And R 4 The molar ratio of the used amount of (2-2.3): 1.
preferably, in step (1), the first reaction is carried out under stirring conditions, preferably at a speed of 150rpm to 500 rpm.
According to a preferred embodiment, in step (1), the method of the present invention further comprises: washing the solid crude product obtained after the first reaction by using ethanol and/or water at 35-80 ℃, and drying the substance obtained after washing to obtain the solid product A1.
Preferably, the first solution conditions are provided by a solvent comprising isopropanol and/or acetic acid. For example, in the first reaction of the present invention, R may be reacted 3 Mixing with isopropanol to form solution I, and mixing R 4 Mixed with acetic acid to form a solution II, and then the solution I and the solution II are mixed to perform a first reaction.
Preferably, in step (1), the conditions of the second reaction include: the reaction temperature is 40-70 ℃, and the reaction time is 3-24 h.
Preferably, R of the second reaction is carried out 5 And R 6 The molar ratio of the used amount of 1: (2-2.2).
Preferably, in step (1), the second reaction is carried out under stirring conditions, preferably at a speed of 100rpm to 500 rpm.
In the present invention, the second solution conditions may be provided by, for example, diglycidyl ether and/or methanol.
Preferably, in step (1), the conditions of the third reaction include: the reaction temperature is 30-70 ℃, and the reaction time is 0.5-4 h.
Preferably, in step (1), R of the third reaction is carried out 1 And R 2 The molar ratio of the used amount of the compound is 1: (2-2.3).
In the step (1), the third reaction is carried out under stirring conditions, and the stirring speed may be, for example, 50rpm to 500 rpm.
According to a preferred embodiment, in the step (1), the third reaction is carried out in the presence of at least one catalyst selected from the group consisting of triethylamine, dibutyltin dilaurate, dimethylcyclohexylamine, organobismuth and pentamethyldiethylenetriamine.
More preferably, in step (1), with said R 2 And R 1 The amount of catalyst used in the third reaction is from 50ppm to 3000ppm, based on the total weight of the catalyst.
The third solution condition of the present invention may be provided by containing at least one solvent selected from the group consisting of absolute ethanol, acetone, methyl ethyl ketone, methylene chloride, chloroform, dichloroethane, toluene, xylene, N-dimethylformamide, tetrahydrofuran, and dimethylsulfoxide. For example, the third reaction may be carried out by reacting R 2 With R dissolved in a solvent 1 The contact is made.
Preferably, in step (2), the conditions of the fourth reaction include: the reaction temperature is 30-80 ℃, and the reaction time is 4-24 h.
Preferably, in the step (2), the molar ratio of the total molar amount of the solid product a1 and the solid product a2 subjected to the fourth reaction to the amount of the polyurethane prepolymer B is 1: (2-2.3).
Preferably, in step (2), the molar ratio of the solid product a1 subjected to the fourth reaction to the total amount of the solid product a1 and the solid product a2 is (0.1-0.9): 1.
preferably, in step (2), the fourth reaction is carried out under stirring conditions, and the stirring speed is preferably 50rpm to 300 rpm.
According to a preferred embodiment, in the step (2), the fourth solution condition is provided by containing at least one solvent selected from the group consisting of dichloromethane, chloroform, dichloroethane, toluene, xylene, N-dimethylformamide, tetrahydrofuran, and dimethylsulfoxide.
Preferably, in step (3), the conditions of the fifth reaction include: the reaction temperature is 40-70 ℃, and the reaction time is 3-24 h.
Preferably, in step (3), in the fifth reaction, to form a wireLinear polyurethanes C and R based on the amount of solid product A2 used in polyurethane C 7 The molar ratio of the used amount of 1: (1.1-1.3).
The fifth solution condition of the present invention may be provided by containing at least one solvent selected from the group consisting of dichloromethane, chloroform, dichloroethane, toluene, xylene, N-dimethylformamide, tetrahydrofuran, and dimethylsulfoxide.
According to a preferred embodiment, in step (3), R is added 7 The step of performing a fifth reaction with the linear polyurethane C comprises: under the condition of a fifth solution, adding R 7 Mixed with the linear polyurethane C and the resulting mixture is transferred to a teflon mould, the solvent is removed first by more than 50% by volume and then dried.
The temperature and time for drying in the method of the present invention are not particularly limited, and the drying in the present invention is only for removing the solvent possibly present on the solid surface, and those skilled in the art can determine the suitable drying temperature and drying time according to the purpose by combining with the common knowledge in the art.
As mentioned above, the third aspect of the present invention provides the self-repairing polyurethane based on the bidirectional repairing structure prepared by the method described in the second aspect.
As previously mentioned, a fourth aspect of the present invention provides the use of the self-healing polyurethane based on a bi-directional healing structure as described in the first and third aspects above in at least one product selected from the group consisting of coatings, electronics, and packaging materials.
The self-repairing polyurethane based on the bidirectional repairing structure, the preparation method and the application thereof provided by the invention also have the following specific advantages:
(1) the self-repairing polyurethane based on the bidirectional repairing structure can realize quick self-repairing.
(2) The method for preparing the self-repairing polyurethane based on the bidirectional repairing structure has the advantages of easily obtained raw materials, strong controllability of material performance, low cost and capability of being used for industrial production.
The present invention will be described in detail below by way of examples. The starting materials used, unless otherwise specified, are all commercially available and are in analytical purity. The room temperatures referred to in the examples below all represent 25. + -. 3 ℃.
P-hydroxybenzaldehyde, available from alatin.
Oxalyl dihydrazide, available from alatin corporation.
Furfuryl amine, available from alatin.
N, N '- (4,4' -methylenediphenyl) bismaleimide available from Aladdin.
Isophorone diisocyanate, available from molebec chemical.
Polyethylene glycol, average molecular weight 600, available from Tianjin Mao Chemicals, Inc.
Polyethylene glycol, average molecular weight 1000, available from Tianjin Mao Chemicals, Inc.
Polyethylene glycol, average molecular weight 1500, available from Tianjin Mao Chemicals, Inc.
Dibutyl tin dilaurate, available from alatin corporation.
1, 4-butanediol, available from Aladdin.
Preparation example 1: preparation of solid product A1 and solid product A2
1.1mol of a p-hydroxybenzaldehyde solution in isopropanol (300mL) was added to a 0.5mol oxalyl dihydrazide solution in glacial acetic acid (250mL) at 40 ℃ and reacted for 4h with stirring at 300 rpm. After the reaction, the reaction mixture was filtered under reduced pressure, washed three times with ethanol and then three times with water at 50 ℃, and the washed product was dried to obtain a solid product a 1.
At 60 ℃ 0.2mol of furfuryl amine was added to a solution of resorcinol diglycidyl ether (0.1mol) in methanol (50mL) and reacted for 6h with stirring at 500 rpm. After the reaction is finished, the mixture is distilled under reduced pressure, washed by secondary water and dried to obtain a solid product A2.
And, the nuclear magnetic hydrogen spectra of the solid product a1 and the solid product a2 are shown in fig. 1 and fig. 2, respectively.
Example 1: preparation of polyurethanes
At 50 ℃, 0.1mol of isophorone diiso-butyl etherCyanate ester was slowly added to a molecular weight M dissolved in N, N-dimethylformamide (300mL) n To 600 parts by weight of polyethylene glycol (PEG 600, 0.05mol), 500ppm (based on the total weight of isophorone diisocyanate and polyethylene glycol) of dibutyltin dilaurate was added, and the mixture was reacted with rapid stirring for 3 hours to obtain a polyurethane prepolymer pre-600.
0.22mol of the polyurethane prepolymer pre-600 was mixed with 0.1mol of a mixture A (0.05mol of the solid product A1 of preparation example 1 and 0.05mol of the solid product A2 of preparation example 1) dissolved in N, N-dimethylformamide (total 200mL) at 50 ℃ and reacted with stirring at 200rpm for 12 hours to give a linear polyurethane l-600.
0.06mol of N, N '- (4,4' -methylenediphenyl) bismaleimide was added to a dispersion of linear polyurethane l-600 (the entire amount obtained in the previous step) in N, N-dimethylformamide at 55 ℃, mixed and stirred uniformly, transferred to a polytetrafluoroethylene mold, first evaporated at room temperature to remove most of the solvent, and dried in a vacuum oven at 80 ℃ overnight, and the obtained sample was designated as DNEPU-600.
Example 2: preparation of polyurethanes
At 35 ℃ 0.1mol of isophorone diisocyanate was slowly added to a molecular weight M dissolved in N, N-dimethylformamide (300mL) n To 1000 parts by weight of polyethylene glycol (PEG 1000, 0.05mol), 500ppm (based on the total weight of isophorone diisocyanate and polyethylene glycol) of dibutyltin dilaurate was added, and the mixture was reacted for 4 hours with rapid stirring to obtain a polyurethane prepolymer pre-1000.
0.22mol of polyurethane prepolymer pre-1000 was mixed with 0.1mol of mixture A (0.05mol of solid product A1 from preparation example 1 and 0.05mol of solid product A2 from preparation example 1) dissolved in dimethyl sulfoxide (total 200mL) at 40 ℃ and reacted with stirring at 200rpm for 20 hours to give linear polyurethane l-1000.
0.06mol of N, N '- (4,4' -methylenediphenyl) bismaleimide was added to a dispersion of linear polyurethane l-1000 (the entire amount obtained in the previous step) in N, N-dimethylformamide at 60 ℃, mixed and stirred uniformly, transferred to a polytetrafluoroethylene mold, first evaporated at room temperature to remove most of the solvent, and dried in a vacuum oven at 90 ℃ overnight, and the obtained sample was designated as DNEPU-1000.
Example 3: preparation of polyurethanes
0.1mol of isophorone diisocyanate was slowly added to a molecular weight M dissolved in N, N-dimethylformamide (300mL) at 70 deg.C n To 1500 parts by weight of polyethylene glycol (PEG 1500, 0.05mol), 500ppm (based on the total weight of isophorone diisocyanate and polyethylene glycol) of dibutyltin dilaurate was added, and the mixture was reacted with rapid stirring for 1.5 hours to obtain a polyurethane prepolymer pre-1500.
0.22mol of the polyurethane prepolymer pre-1500 was mixed with 0.1mol of a mixture A (0.05mol of the solid product A1 of preparation example 1 and 0.05mol of the solid product A2 of preparation example 1) dissolved in dimethyl sulfoxide (total 200mL) at 60 ℃ and reacted with stirring at 200rpm for 10 hours to give a linear polyurethane l-1500.
0.06mol of N, N '- (4,4' -methylenediphenyl) bismaleimide was added to a dispersion of linear polyurethane l-1500 (the entire amount obtained in the previous step) in N, N-dimethylformamide at 45 ℃ and mixed well before being transferred to a polytetrafluoroethylene mold, most of the solvent was evaporated at room temperature first, and the mixture was dried overnight in a vacuum oven at 80 ℃ to obtain a sample designated DNEPU-1500.
Comparative example 1
This comparative example was carried out in a similar manner to example 1, except that in this comparative example, the solid product A1 in example 1 was replaced by the same molar amount of 1, 4-butanediol. Specifically, the method comprises the following steps:
at 50 ℃ 0.1mol of isophorone diisocyanate was slowly added to a molecular weight M dissolved in N, N-dimethylformamide (300mL) n To 600 parts by weight of polyethylene glycol (PEG 600, 0.05mol), 500ppm (based on the total weight of isophorone diisocyanate and polyethylene glycol) of dibutyltin dilaurate was added, and the mixture was reacted with rapid stirring for 3 hours to obtain a polyurethane prepolymer pre-600.
0.22mol of polyurethane prepolymer pre-600 was mixed with 0.1mol of a mixture A (0.05mol of 1, 4-butanediol and 0.05mol of the solid product A2 from preparation example 1) dissolved in N, N-dimethylformamide (total 200mL) at 50 ℃ and reacted with stirring at 200rpm for 12 hours to give a linear polyurethane D-l-600.
At 55 ℃, 0.06mol of N, N '- (4,4' -methylenediphenyl) bismaleimide is added into the N, N-dimethylformamide dispersion of the linear polyurethane D-l-600 (the whole amount obtained in the previous step), the mixture is uniformly mixed and stirred, then the mixture is transferred into a polytetrafluoroethylene mold, most of the solvent is volatilized at room temperature, and the mixture is dried in a vacuum oven at 80 ℃ for one night, and the obtained sample is recorded as SNEPU-600.
Comparative example 2
This comparative example was carried out in a similar manner to example 2, except that in this comparative example, the solid product A1 of example 2 was replaced by the same molar amount of 1, 4-butanediol.
The final product obtained was SNEPU-1000.
Comparative example 3
This comparative example was carried out in a similar manner to example 3, except that in this comparative example, the solid product A1 of example 3 was replaced by the same molar amount of 1, 4-butanediol.
The final product obtained was SNEPU-1500.
Comparative example 4
The final product was prepared in the same manner as in example 3.1 of CN107236106A and was named SNEPU-DD.
Test example
The product polyurethane prepared in the foregoing is subjected to a self-repairing performance test, and the repairing performance is characterized, and the results are listed in tables 1 and 2.
(1) Thermal repair Performance test
The polyurethane was cut into dumbbell standard pieces according to a type 1 dumbbell cutter prescribed in GB/T528-92, the samples were divided into four groups, the first group was used as a raw sample, the remaining three groups were cut at the middle position of the sample, and then the cut samples were butted together: the second group is insulated in a vacuum drying oven at 120 ℃ for 3 hours, and then the temperature is reduced to 60 ℃ and is insulated for 12 hours; and the third group is insulated in a vacuum drying oven at 120 ℃ for 12 hours, and then the temperature is reduced to 60 ℃ and insulated for 12 hours. And keeping the temperature of the fourth group in a vacuum drying oven at 120 ℃ for 24 hours, reducing the temperature to 60 ℃ and keeping the temperature for 12 hours. And then, carrying out tensile property test on the original sample and the three groups of samples, and calculating self-repairing efficiency, wherein the self-repairing efficiency is the tensile strength after repairing/the tensile strength before repairing.
(2) Room temperature repair Performance test
The polyurethane was cut into dumbbell standard pieces according to the type 1 dumbbell cutter prescribed in GB/T528-92, the test specimens were divided into three groups, the first group being the original specimen and the remaining two groups being cut at the middle of the test specimen, and then the cut test specimens were butted together, and glacial acetic acid was applied at the interface: the second group was allowed to stand at room temperature for 24h, and the third group was allowed to stand at room temperature for 48 h. And then, carrying out tensile property test on the original sample and the three groups of samples, and calculating self-repairing efficiency, wherein the self-repairing efficiency is the tensile strength after repairing/the tensile strength before repairing.
Table 1: tensile strength and repairing efficiency before and after thermal repairing of material
Figure BDA0002244475270000131
Table 2: tensile strength and repair efficiency of material before and after room temperature self-repair
Figure BDA0002244475270000132
Figure BDA0002244475270000141
The results show that the self-repairing polyurethane based on the bidirectional repairing structure provided by the invention has excellent self-repairing capability and efficiency.
In addition, the self-repairing polyurethane based on the bidirectional repairing structure provided by the invention has obvious advantages under the room-temperature repairing condition.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (25)

1. Self-repairing polyurethane based on bidirectional repairing structure, wherein R is contained in polyurethane 1 、R 2 、R 3 、R 4 、R 5 And R 6 Structural unit of provided, and R 1 Is polyethylene glycol, R 2 Is isophorone diisocyanate, R 3 Is p-hydroxybenzaldehyde, R 4 Is oxalyl dihydrazide, R 5 Is resorcinol diglycidyl ether, R 6 Is furfuryl amine, R 7 Is N, N '- (4,4' -methylene diphenyl) bismaleimide, wherein R is the total weight of the polyurethane 1 The content of the structural units provided is from 30.8 to 87.9% by weight, based on R 2 The content of the structural units provided is 6.9 to 43.2% by weight, from R 3 The content of the structural units provided is from 0.2 to 11.7% by weight, based on R 4 The content of the structural units provided is 0.1 to 4.9% by weight, represented by R 5 The content of the structural units provided is from 0.1 to 6.9% by weight, based on R 6 The content of the structural units provided is 0.2 to 6.6% by weight, represented by R 7 The content of the structural unit is 0.8-24.6 wt%, and the number average molecular weight of the polyurethane is 5000-120000, and the molecular weight distribution is 1.88-2.32.
2. The polyurethane as claimed in claim 1, wherein the polyethylene glycol has an average molecular weight of 200-.
3. A method of making a bi-directional repair structure based self-healing polyurethane, the method comprising:
(1) under the condition of the first solution, adding R 3 And R 4 Carrying out a first reaction to obtain a solid product A1; under the condition of a second solution, adding R 5 And R 6 Carrying out a second reaction to obtain a solid product A2; and under the condition of the third solution, adding R 2 And R 1 Carrying out a third reaction to obtain a polyurethane prepolymer B;
(2) under the condition of a fourth solution, carrying out a fourth reaction on the polyurethane prepolymer B, the solid product A1 and the solid product A2 to obtain linear polyurethane C;
(3) under the condition of a fifth solution, adding R 7 Carrying out a fifth reaction with the linear polyurethane C;
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 And R 7 In such an amount that the polyurethane obtained is made up of R 1 The content of the structural units provided is from 30.8 to 87.9% by weight, based on R 2 The content of the structural units provided is 6.9 to 43.2% by weight, from R 3 The content of the structural units provided is from 0.2 to 11.7% by weight, from R 4 The content of the structural units provided is from 0.1 to 4.9% by weight, based on R 5 The content of the structural units provided is from 0.1 to 6.9% by weight, based on R 6 The content of the structural units provided is from 0.2 to 6.6% by weight, based on R 7 The content of the provided structural unit is 0.8-24.6 wt%, the number average molecular weight of the polyurethane is 120000-5000, and the molecular weight distribution is 1.88-2.32;
and, R 1 Is polyethylene glycol, R 2 Is isophorone diisocyanate, R 3 Is p-hydroxybenzaldehyde, R 4 Is oxalyl dihydrazide, R 5 Is resorcinol diglycidyl ether, R 6 Is furfuryl amine, R 7 Is N, N '- (4,4' -methylene diphenyl) bismaleimide.
4. The method as claimed in claim 3, wherein the polyethylene glycol has an average molecular weight of 200-.
5. The method of claim 3, wherein, in step (1), the conditions of the first reaction comprise: the reaction temperature is 35-80 ℃, and the reaction time is 0.5-4 h.
6. The method according to any one of claims 3 to 5, wherein, in step (1), R of the first reaction is carried out 3 And R 4 The molar ratio of the used amount is (1-2.3): 1.
7. the process according to any one of claims 3 to 5, wherein, in step (1), the first reaction is carried out under stirring conditions at a speed of 150rpm to 500 rpm.
8. The method according to any one of claims 3-5, wherein in step (1), the method further comprises: washing the solid crude product obtained after the first reaction by using ethanol and/or water at 35-80 ℃, and drying the substance obtained after washing to obtain the solid product A1.
9. The method of claim 3, wherein, in step (1), the conditions of the second reaction comprise: the reaction temperature is 40-70 ℃, and the reaction time is 3-24 h.
10. The process according to claim 3 or 9, wherein, in step (1), R of the second reaction is carried out 5 And R 6 The molar ratio of the used amount is 1: (2-2.2).
11. The process according to claim 3 or 9, wherein, in step (1), the second reaction is carried out under stirring conditions at a speed of 100rpm to 500 rpm.
12. The method of claim 3, wherein, in step (1), the conditions of the third reaction comprise: the reaction temperature is 30-70 ℃, and the reaction time is 0.5-4 h.
13. The process according to claim 3 or 12, wherein, in step (1), R of the third reaction is carried out 1 And R 2 The molar ratio of the used amount of the compound is 1: (2-2.3).
14. The process according to claim 3 or 12, wherein, in step (1), the third reaction is carried out in the presence of at least one catalyst selected from the group consisting of triethylamine, dibutyltin dilaurate, dimethylcyclohexylamine, organobismuth and pentamethyldiethylenetriamine.
15. The method according to claim 3 or 12, wherein in step (1), R is 2 And R 1 The catalyst is used in the third reaction in an amount of 50ppm to 3000ppm based on the total weight of the catalyst.
16. The method of claim 3, wherein, in step (2), the conditions of the fourth reaction comprise: the reaction temperature is 30-80 ℃, and the reaction time is 4-24 h.
17. The method of claim 3 or 16, wherein in the step (2), the molar ratio of the total molar amount of the solid product a1 and the solid product a2 subjected to the fourth reaction to the amount of the polyurethane prepolymer B used is 1: (2-2.3).
18. The process according to claim 3 or 16, wherein, in step (2), the molar ratio of the solid product a1 to the total amount of the solid product a1 and the solid product a2 subjected to the fourth reaction is (0.1-0.9): 1.
19. the process according to claim 3 or 16, wherein, in step (2), the fourth reaction is carried out under stirring conditions at a speed of 50rpm to 300 rpm.
20. The method according to claim 3 or 16, wherein, in step (2), the fourth solution condition is provided by containing at least one solvent selected from dichloromethane, trichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, tetrahydrofuran, dimethylsulfoxide.
21. The method of claim 3, wherein, in step (3), the conditions of the fifth reaction comprise: the reaction temperature is 40-70 ℃, and the reaction time is 3-24 h.
22. The process according to claim 3 or 21, wherein, in step (3), in the fifth reaction, the linear polyurethanes C and R are metered in relation to the amount of solid product A2 used in the formation of the linear polyurethane C 7 The molar ratio of the used amount of 1: (1.1-1.3).
23. The method of claim 3 or 21, wherein in step (3), R is 7 The step of performing a fifth reaction with the linear polyurethane C comprises: under the condition of a fifth solution, adding R 7 Mixed with the linear polyurethane C and the resulting mixture is transferred to a teflon mould, the solvent is removed first by more than 50% by volume and then dried.
24. Self-healing polyurethane based on bi-directional healing structures, obtainable by the process according to any one of claims 3 to 23.
25. Use of the self-healing polyurethane based on bi-directional repair structures of any one of claims 1, 2 and 24 in at least one product selected from the group consisting of coatings, electronics and packaging materials.
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