CN112694587A - 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

Info

Publication number
CN112694587A
CN112694587A CN201911011994.6A CN201911011994A CN112694587A CN 112694587 A CN112694587 A CN 112694587A CN 201911011994 A CN201911011994 A CN 201911011994A CN 112694587 A CN112694587 A CN 112694587A
Authority
CN
China
Prior art keywords
reaction
polyurethane
content
weight
repairing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911011994.6A
Other languages
Chinese (zh)
Other versions
CN112694587B (en
Inventor
唐瀚滢
解希铭
杜影
王丽静
王丽丽
赵丽娜
赵青松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201911011994.6A priority Critical patent/CN112694587B/en
Publication of CN112694587A publication Critical patent/CN112694587A/en
Application granted granted Critical
Publication of CN112694587B publication Critical patent/CN112694587B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3834—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/833—Chemically modified polymers by nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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 thereof1、R2、R3、R4、R5、R6And R7Structural unit of provided, and R1Is polyethylene glycol, R2Is isophorone diisocyanate, R3Is terephthalaldehyde, R4Is oxalyl dihydrazide, R5Is resorcinol diglycidyl ether, R6Is furfuryl amine, R7 is N,n '- (4,4' -methylenediphenyl) bismaleimide. The polyurethane provided by the invention has excellent self-repairing capability and high self-repairing efficiency, can prolong the service life of the material, 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 the reports all 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 repairing structure, wherein the polyurethane contains a polyurethane represented by formula R1、R2、R3、R4、R5And R6Structural unit of provided, and R1Is polyethylene glycol, R2Is isophorone diisocyanate, R3Is p-hydroxybenzaldehyde, R4Is oxalyl dihydrazide, R5Is resorcinol diglycidyl ether, R6Is furfuryl amine, R7Is N, N '- (4,4' -methylene diphenyl) bismaleimide, wherein R is the total weight of the polyurethane1The content of the structural units provided is from 30.8 to 87.9% by weight, based on R2The content of the structural units provided is 6.9 to 43.2 wt.%, based on R3The content of the structural units provided is from 0.2 to 11.7% by weight, based on R4The content of the structural units provided is from 0.1 to 4.9% by weight, based on R5The content of the structural units provided is from 0.1 to 6.9% by weight, based on R6The content of the structural units provided is from 0.2 to 6.6% by weight, based on R7The 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 R3And R4Carrying out a first reaction to obtain a solid product A1; under the condition of a second solution, adding R5And R6Carrying out a second reaction to obtain a solid product A2; and under the condition of the third solution, adding R2And R1Carrying 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 R7Carrying out a fifth reaction with the linear polyurethane C;
wherein R is1、R2、R3、R4、R5、R6And R7In such an amount that the polyurethane obtained is made up of R1The content of the structural units provided is from 30.8 to 87.9% by weight, based on R2The content of the structural units provided is 6.9 to 43.2 wt.%, based on R3The content of the structural units provided is from 0.2 to 11.7% by weight, based on R4The content of the structural units provided is from 0.1 to 4.9% by weight, based on R5The content of the structural units provided is from 0.1 to 6.9% by weight, based on R6The content of the structural units provided is from 0.2 to 6.6% by weight, based on R7The 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, R1Is polyethylene glycol, R2Is isophorone diisocyanate, R3Is p-hydroxybenzaldehyde, R4Is oxalyl dihydrazide, R5Is resorcinol diglycidyl ether, R6Is furfuryl amine, R7Is N, N '- (4,4' -methylene diphenyl) bismaleimide.
The third aspect of the invention provides self-repairing polyurethane based on the bidirectional repairing structure prepared by the method of the second aspect.
A fourth aspect of the present invention provides the use of the self-healing polyurethane based on a bidirectional healing structure according to the first and/or third aspect in at least one product selected from the group consisting of coatings, electronics, 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.
Drawings
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 such ranges or values should be understood to encompass values close to those 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 R1、R2、R3、R4、R5And R6Structural unit of provided, and R1Is polyethylene glycol, R2Is isophorone diisocyanate, R3Is p-hydroxybenzaldehyde, R4Is oxalyl dihydrazide, R5Is resorcinol diglycidyl ether, R6Is furfuryl amine, R7Is N, N '- (4,4' -methylene diphenyl) bismaleimide, wherein R is the total weight of the polyurethane1The content of the structural units provided is from 30.8 to 87.9% by weight, based on R2The content of the structural units provided is 6.9 to 43.2 wt.%, based on R3The content of the structural units provided is from 0.2 to 11.7% by weight, based on R4The content of the structural units provided is from 0.1 to 4.9% by weight, based on R5The content of the structural units provided is from 0.1 to 6.9% by weight, based on R6The content of the structural units provided is from 0.2 to 6.6% by weight, based on R7The 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, R1Is a compound of formula (1R1) wherein n is such that R is1The average molecular weight of (A) is preferably 200-6000.
Figure BDA0002244475270000041
Preferably, R2Is a compound represented by the formula (1R 2):
Figure BDA0002244475270000042
preferably, R3Is a compound represented by the formula (1R 3):
Figure BDA0002244475270000043
preferably, R4Is a compound represented by the formula (1R 4):
Figure BDA0002244475270000044
preferably, R5Is a compound represented by the formula (1R 5):
Figure BDA0002244475270000045
preferably, R6Is a compound represented by the formula (1R 6):
Figure BDA0002244475270000051
preferably, R7Is 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 R3And R4Carrying out a first reaction to obtain a solid product A1; under the condition of a second solution, adding R5And R6Carrying out a second reaction to obtain a solid product A2; and under the condition of the third solution, adding R2And R1Carrying 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 R7Carrying out a fifth reaction with the linear polyurethane C;
wherein R is1、R2、R3、R4、R5、R6And R7In such an amount that the polyurethane obtained is made up of R1The content of the structural units provided is from 30.8 to 87.9% by weight, based on R2The content of the structural units provided is 6.9 to 43.2 wt.%, based on R3The content of the structural units provided is from 0.2 to 11.7% by weight, based on R4The content of the structural units provided is from 0.1 to 4.9% by weight, based on R5The content of the structural units provided is from 0.1 to 6.9% by weight, based on R6The content of the structural units provided is from 0.2 to 6.6% by weight, based on R7The 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, R1Is polyethylene glycol, R2Is isophorone diisocyanate, R3Is p-hydroxybenzaldehyde, R4Is oxalyl dihydrazide, R5Is resorcinol diglycidyl ether, R6Is furfuryl amine, R7Is 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 (1), R of the first reaction is carried out3And R4The molar ratio of the used amount is (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 reacted3Mixing with isopropanol to form solution I, and mixing R4Mixed 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 out5And R6The molar ratio of the used amount of the compound is 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 out1And R2The 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 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 R2And R1The catalyst is used in the third reaction in an amount of 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 R2With R dissolved in a solvent1The 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 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, the linear polyurethanes C and R are used in an amount corresponding to the amount of the solid product A2 used for the formation of the linear polyurethane C7The molar ratio of the used amount of the compound is 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 added7The step of performing a fifth reaction with the linear polyurethane C comprises: under the condition of a fifth solution, adding R7Mixed 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 and low cost, and can be 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 corporation.
N, N '- (4,4' -methylenediphenyl) bismaleimide available from Aladdin.
Isophorone diisocyanate, available from Moebel 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 metallocene chemical reagent, 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 0.5mol of 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
0.1mol of isophorone diisocyanate was slowly added to a molecular weight M dissolved in N, N-dimethylformamide (300mL) at 50 deg.CnTo 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
0.1mol of isophorone diisocyanate was slowly added to a molecular weight M dissolved in N, N-dimethylformamide (300mL) at 35 deg.CnTo 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.CnTo 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 polyurethane prepolymer pre-1500 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 60 ℃ and reacted with stirring at 200rpm for 10 hours to give 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:
0.1mol of isophorone diisocyanate was slowly added to a molecular weight M dissolved in N, N-dimethylformamide (300mL) at 50 deg.Cn600 mer ofAdding 500ppm (based on the total weight of isophorone diisocyanate and polyethylene glycol) of dibutyltin dilaurate into ethylene glycol (PEG 600, 0.05mol), and reacting for 3h under rapid stirring 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, named SNEPU-DD, was prepared in CN107236106A in the same way as in example 3.1.
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 as specified in GB/T528-92, the samples were divided into four groups, the first group being the original sample, the remaining three groups being 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 then 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.
Moreover, 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 (14)

1. Self-repairing polyurethane based on bidirectional repairing structure, wherein R is contained in polyurethane1、R2、R3、R4、R5And R6Structural unit of provided, and R1Is polyethylene glycol, R2Is isophorone diisocyanate, R3Is p-hydroxybenzaldehyde, R4Is oxalyl dihydrazide, R5Is resorcinol diglycidyl ether, R6Is furfuryl amine, R7Is N, N '- (4,4' -methylene diphenyl) bismaleimide, wherein R is the total weight of the polyurethane1The content of the structural units provided is from 30.8 to 87.9% by weight, based on R2The content of the structural units provided is 6.9 to 43.2 wt.%, based on R3The content of the structural units provided is from 0.2 to 11.7% by weight, based on R4The content of the structural units provided is from 0.1 to 4.9% by weight, based on R5The content of the structural units provided is from 0.1 to 6.9% by weight, based on R6The content of the structural units provided is from 0.2 to 6.6% by weight, based on R7The 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 R3And R4Carrying out a first reaction to obtain a solid product A1; under the condition of a second solution, adding R5And R6Carrying out a second reaction to obtain a solid product A2; and under the condition of the third solution, adding R2And R1Carrying 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 R7Carrying out a fifth reaction with the linear polyurethane C;
wherein R is1、R2、R3、R4、R5、R6And R7In such an amount that the polyurethane obtained is made up of R1The content of the structural units provided is from 30.8 to 87.9% by weight, based on R2The content of the structural units provided is 6.9 to 43.2 wt.%, based on R3The content of the structural units provided is from 0.2 to 11.7% by weight, based on R4The content of the structural units provided is from 0.1 to 4.9% by weight, based on R5The content of the structural units provided is from 0.1 to 6.9% by weight, based on R6The content of the structural units provided is from 0.2 to 6.6% by weight, based on R7The 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, R1Is polyethylene glycol, R2Is isophorone diisocyanate, R3Is p-hydroxybenzaldehyde, R4Is oxalyl dihydrazide, R5Is resorcinol diglycidyl ether, R6Is furfuryl amine, R7Is N, N '- (4,4' -methylene diphenyl) bismaleimide,
preferably, the polyethylene glycol has an average molecular weight of 200-.
4. 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;
preferably, in step (1), R of the first reaction is carried out3And R4The molar ratio of the used amount is (1-2.3): 1;
preferably, in step (1), the first reaction is carried out under stirring conditions, preferably at a speed of 150rpm to 500 rpm.
5. The method of claim 3 or 4, 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.
6. 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;
preferably, R for carrying out the second reaction5And R6The molar ratio of the used amount is 1: (2-2.2);
preferably, the second reaction is carried out under stirring conditions, the stirring speed being from 100rpm to 500 rpm.
7. 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;
preferably, in step (1), R of the third reaction is carried out1And R2The molar ratio of the used amount of the compound is 1: (2-2.3).
8. The process according to claim 3 or 7, 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;
preference is given toIn step (1), with said R2And R1The catalyst is used in the third reaction in an amount of 50ppm to 3000ppm based on the total weight of the catalyst.
9. 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;
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, preferably at a speed of 50rpm to 300 rpm.
10. The method according to claim 3 or 9, 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.
11. 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;
preferably, in step (3), in the fifth reaction, the linear polyurethanes C and R are used in an amount corresponding to the amount of the solid product A2 used for the formation of the linear polyurethane C7The molar ratio of the used amount of the compound is 1: (1.1-1.3).
12. The method of claim 3 or 11, wherein in step (3), R is7The step of performing a fifth reaction with the linear polyurethane C comprises: under the condition of a fifth solution, adding R7Mixed 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.
13. Self-healing polyurethane based on a bidirectional healing structure, prepared by the process according to any one of claims 3 to 12.
14. Use of the self-healing polyurethane based on bi-directional repair structures of any one of claims 1, 2 and 13 in at least one product selected from the group consisting of coatings, electronics and packaging materials.
CN201911011994.6A 2019-10-23 2019-10-23 Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof Active CN112694587B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911011994.6A CN112694587B (en) 2019-10-23 2019-10-23 Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911011994.6A CN112694587B (en) 2019-10-23 2019-10-23 Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112694587A true CN112694587A (en) 2021-04-23
CN112694587B CN112694587B (en) 2022-08-19

Family

ID=75505413

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911011994.6A Active CN112694587B (en) 2019-10-23 2019-10-23 Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112694587B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260446A (en) * 2022-07-29 2022-11-01 华南理工大学 Recyclable high-strength scratch-resistant self-repairing transparent polyurethane film and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034717A1 (en) * 2006-09-21 2008-03-27 Clariant International Ltd Aqueous polyurethane/polyurea dispersions
CN105348474A (en) * 2015-12-07 2016-02-24 南昌航空大学 Preparation method for UV-curing self-healing polyurethane based on furan-maleimide structure
CN106117486A (en) * 2016-06-27 2016-11-16 青岛科技大学 Dihydroxylic alcohols containing acylhydrazone key, the dihydroxylic alcohols containing acylhydrazone key and cystine linkage, selfreparing polyurethane elastomer and preparation method thereof
CN107236106A (en) * 2017-06-13 2017-10-10 青岛科技大学 The aromatic series terminal hydroxy group chain extender of the key containing acylhydrazone, selfreparing polyurethane and preparation method thereof
CN110343054A (en) * 2019-07-19 2019-10-18 西南科技大学 The preparation method of parahydroxyben-zaldehyde benzoyl hydrazone

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034717A1 (en) * 2006-09-21 2008-03-27 Clariant International Ltd Aqueous polyurethane/polyurea dispersions
CN105348474A (en) * 2015-12-07 2016-02-24 南昌航空大学 Preparation method for UV-curing self-healing polyurethane based on furan-maleimide structure
CN106117486A (en) * 2016-06-27 2016-11-16 青岛科技大学 Dihydroxylic alcohols containing acylhydrazone key, the dihydroxylic alcohols containing acylhydrazone key and cystine linkage, selfreparing polyurethane elastomer and preparation method thereof
CN107236106A (en) * 2017-06-13 2017-10-10 青岛科技大学 The aromatic series terminal hydroxy group chain extender of the key containing acylhydrazone, selfreparing polyurethane and preparation method thereof
CN110343054A (en) * 2019-07-19 2019-10-18 西南科技大学 The preparation method of parahydroxyben-zaldehyde benzoyl hydrazone

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DU, PENGFEI ET AL: "Diels-Alder-Based Crosslinked Self-Healing Polyurethane/Urea from Polymeric Methylene Diphenyl Diisocyanate", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *
曹建诚等: "基于D-A反应的光固化自修复聚氨酯涂料及其性能研究", 《影像科学与光化学》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260446A (en) * 2022-07-29 2022-11-01 华南理工大学 Recyclable high-strength scratch-resistant self-repairing transparent polyurethane film and preparation method thereof
CN115260446B (en) * 2022-07-29 2023-11-24 华南理工大学 Recyclable high-strength scratch-resistant self-repairing transparent polyurethane film and preparation method thereof

Also Published As

Publication number Publication date
CN112694587B (en) 2022-08-19

Similar Documents

Publication Publication Date Title
CN109021287B (en) Phosphorus-nitrogen-sulfur type flame retardant and application thereof in epoxy resin
CN113788853B (en) Sexek derivative and application thereof as additive flame retardant
CN111187428B (en) Lignin-based polyol, modified lignin-based polyurethane material, modified lignin-based polyurethane film, and preparation method and application thereof
WO2020136599A1 (en) A chain extender and a process for preparing a self-healing polyurethane and polyurethane thereof
CN115558400B (en) Polyurethane flame-retardant coating for building outer wall and preparation process thereof
CN109251293B (en) Triazine polyurethane charring agent containing furan ring side group and synthesis method thereof
CN112694587B (en) Self-repairing polyurethane based on bidirectional repairing structure and preparation method and application thereof
CN113336898A (en) Preparation method of styrene-free flame-retardant unsaturated polyester resin
CN112010833B (en) Bisphthalonitrile compound containing acetal structure, polymer, preparation method and application thereof
CN105085324A (en) Betaine type amphoteric ioncompound containing isocyanate groups and preparation method thereof
CN114350232A (en) Flame-retardant epoxy resin floor coating and preparation method thereof
CN114634458A (en) Oxazolidine latent curing agent, preparation method thereof and method for preparing polyurethane material
JP2023520281A (en) Chlorosulfonated poly(propylene carbonate) and method of making and using same
CN109438673B (en) Low-hydroxyl phosphorus-containing epoxy resin, composition for copper-clad plate and preparation method of composition
CN109776746B (en) Bio-based flame-retardant polyurethane and preparation method thereof
CN111334025A (en) Corrosion-resistant packaging material and preparation method thereof
CN108395512B (en) Bio-based polyurethane containing carbonate structure as well as preparation method and application thereof
CN114524912B (en) Side chain piperidine cation grafted poly biphenyl alkaline membrane and preparation method thereof
CN112409557B (en) Vegetable oil-based polyurethane film and preparation thereof
KR20110111844A (en) Transparent and highly heat resistant epoxy curing resin and preparation method thereof
CN112442212A (en) Phosphorus-containing reactive flame retardant and preparation method and application thereof
CN113845640A (en) Polyether polyol for polyurethane foam plastic and preparation method and application thereof
CN106626640A (en) Polyester film and preparation method thereof
CN110591132B (en) Carbon fiber prepreg
CN107325276A (en) Polymer, preparation method and application with both hole and electron migration

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant