CN111363119B - Preparation method of self-repairable polyurethane - Google Patents
Preparation method of self-repairable polyurethane Download PDFInfo
- Publication number
- CN111363119B CN111363119B CN202010262151.XA CN202010262151A CN111363119B CN 111363119 B CN111363119 B CN 111363119B CN 202010262151 A CN202010262151 A CN 202010262151A CN 111363119 B CN111363119 B CN 111363119B
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- self
- diisocyanate
- hydrogen bond
- chain extender
- 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.)
- Active
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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/4825—Polyethers containing two hydroxy 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of self-repairing polyurethane. The invention obtains the chain extender containing the hydrogen bond group by reacting the diimidazole compound with diamine, introduces the hydrogen bond groups such as thiourea group and urea group in the polyurethane high molecular chain segment by adopting the way of reacting the chain extender containing the hydrogen bond group with the polyurethane prepolymer, realizes the self-repair of the material by the breakage and the recombination of the hydrogen bond in the molecule or between the molecules in the high molecular chain segment, and simply and efficiently obtains the polyurethane material with better self-repair function. The self-repairing efficiency of the self-repairable polyurethane is high, the preparation process is simple, and the cost is low.
Description
Technical Field
The invention belongs to the field of polyurethane and preparation thereof, and particularly relates to a preparation method of self-repairable polyurethane.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Polyurethane is one of the most widely used polymer resins, and has been widely used in the fields of home furnishing, construction, daily necessities, traffic, home appliances, and the like. The polyurethane product mainly comprises foamed plastics, elastomers, fiber plastics, fibers, leather and shoe resins, paint, adhesives, sealants and the like. With the rapid development of national construction and the continuous emergence of new fields, higher requirements are put forward on the functional development of polyurethane. However, the polyurethane material is still inevitably vulnerable to external mechanical damage during use, which shortens the service life thereof and greatly increases the maintenance and replacement costs of the material. To solve this problem, it is a very effective solution to make the polyurethane material have self-repairing capability.
At present, self-repairing polyurethane materials have been reported. Generally, the introduction of a structural unit with reversible dynamic reversible covalent bond or reversible noncovalent bond interaction in a polyurethane chain is a main method for constructing self-repairing polyurethane. However, the introduction mode of introducing self-repairing groups into polyurethane chain segments and the preparation process are complex, high in cost and low in universality; in addition, most of the existing self-repairing polyurethanes have the problems of long repairing time, low repairing efficiency and the like. These problems limit the application of self-repairing polyurethane materials.
Disclosure of Invention
The invention aims to: provides a preparation method of self-repairing polyurethane. The polyurethane obtained by the method has the characteristics of high self-repairing efficiency, simple preparation process and low cost. The invention adopts the chain extender containing the hydrogen bond group to introduce the hydrogen bond structure with high self-repairability into the polyurethane chain segment, is suitable for various polyurethane systems, and has strong universality.
The object of the invention is achieved by:
a preparation method of self-repairable polyurethane is characterized by comprising the following steps:
(1) Mixing diisocyanate, polymer polyol and a catalyst, and reacting to obtain a polyurethane prepolymer;
(2) Adding a chain extender containing a hydrogen bond group into the polyurethane prepolymer obtained in the step (1), and stirring for reaction to obtain self-repairing polyurethane;
the molecular structure of the chain extender containing the hydrogen bond group is as follows:
wherein R is 1 Is S or O;
R 2 is composed of
And &>
At least one of (a); />
n is an integer of 1 to 500; m is an integer of 1 to 10; k is an integer of 1 to 10.
Further, the dosage of the catalyst in the step (1) is 0ppm to 1000ppm;
the molar ratio of the diisocyanate to the polymer polyol to the chain extender containing the hydrogen bond group is 2: (0.1 to 1.9): (0.1 to 1.9);
further, the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, naphthalene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate;
further, the polymer polyol in the step (1) is at least one of polyester polyol having a number average molecular weight of 1000 to 4000g/mol, polyether polyol having a number average molecular weight of 600 to 3000g/mol, and polycarbonate polyol having a number average molecular weight of 800 to 4000 g/mol;
the catalyst in the step (1) is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecyl sulfide and dibutyltin diacetate;
further, in the step (1), the reaction temperature is 20-100 ℃, and the reaction time is 0.5-10 h.
In the step (2), the temperature of the stirring reaction is 20-90 ℃, and the time of the stirring reaction is 2-4 h
Further, the chain extender containing the hydrogen bond group is prepared by the following steps:
(A) Mixing diamine, a diimidazole compound and a solvent A, and reacting for 1 to 48h at the temperature of 20 to 40 ℃ to obtain a reaction solution;
(B) Adding the reaction solution obtained in the step (A) into a solvent B to separate out a precipitate; purifying and drying to obtain a chain extender containing hydrogen bond groups;
in the step (A), the solvent A is at least one of dimethylformamide, dimethyl sulfoxide, methanol, ethanol, ethyl acetate, dichloromethane, dichloroethane and chloroform; the diimidazole compound is at least one of N, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole;
the molecular structure of the diamine is shown as follows:
wherein R is 2 Is composed of
And &>
At least one of (a);
m is an integer of 1 to 10; k is an integer of 1 to 10;
the molar ratio of the diamine to the diimidazole compound is (1.005-2) to 1;
the dosage of the solvent A is 50 to 500 wt% of the total amount of the diamine and the diimidazole compound;
in the step (B), the solvent B is at least one of diethyl ether, acetone, petroleum ether, cyclohexane, n-hexane, cyclopentane, pentane, n-heptane, n-octane and isooctane.
In order to realize the self-repairing function of the polyurethane, the invention comprises the following steps:
the reaction ratio of diamine and N, N' -thiocarbonyl diimidazole is controlled, and thiourea-containing groups can be introduced into the chain extender containing hydrogen bond groups, as shown in the following;
wherein:
represents a diamine.
The reaction ratio of diamine and N, N' -carbonyl diimidazole is controlled, and urea-containing groups can be introduced into the chain extender containing hydrogen bond groups, as shown in the following;
wherein:
represents a diamine.
The reaction ratio of diamine, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole is controlled, and urea-containing groups and thiourea groups can be simultaneously introduced into the chain extender containing the hydrogen bond groups, as shown in the following;
wherein:
represents a diamine.
The chain extender containing thiourea group and urea group and hydrogen bond group obtained by reacting the diimidazole compound with diamine is further reacted with the polyurethane prepolymer, so that the hydrogen bond groups such as thiourea group and urea group are introduced into the polyurethane high molecular chain segment, and self-repair of the material is realized by breaking and recombining the hydrogen bond in the molecule or between the molecules, so that the polyurethane material has better self-repair function. The principle of the hydrogen bond action inside the polyurethane material containing the thiourea group, the urea group and other hydrogen bond groups is as follows:
meanwhile, the formed hydrogen bond groups such as thiourea-containing groups and urea groups can also form hydrogen bond structures with hydrogen bond donors/acceptors (such as urethane bonds and urea bonds) of the polyurethane, so that the hydrogen bond function of the system is further enhanced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention obtains the chain extender containing the hydrogen bond group by reacting the diimidazole compound with diamine, introduces the hydrogen bond groups such as thiourea group and urea group in the polyurethane high molecular chain segment by adopting the way of reacting the chain extender containing the hydrogen bond group with the polyurethane prepolymer, realizes the self-repair of the material by the breakage and the recombination of the hydrogen bond in the molecule or between the molecules in the high molecular chain segment, and simply and efficiently obtains the polyurethane material with better self-repair function.
2. The self-repairing efficiency of the self-repairable polyurethane is high, the preparation process is simple, and the cost is low.
Drawings
Fig. 1 is a self-healing process diagram of the self-healing polyurethane of example 4.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings and examples, but the embodiments of the present invention are not limited thereto.
Example 1
(A) Mixing 150g of 1,2-bis (2-aminoethoxy) ethane, 162g of N, N' -carbonyldiimidazole and dimethylformamide, and reacting at 30 ℃ for 12 hours to obtain a reaction solution;
(B) Adding the reaction solution obtained in the step (A) into acetone to separate out a precipitate; purifying and drying to obtain a chain extender containing hydrogen bond groups;
the molecular structure of the obtained chain extender containing the hydrogen bond group is as follows:
the number average molecular weight was determined to be about 20000g/mol.
Example 2
(A) Mixing 155g of 1,2-bis (2-aminoethoxy) ethane, 178g of N, N' -thiocarbonyldiimidazole and dimethylformamide, and reacting at 40 ℃ for 1h to obtain a reaction solution;
(B) Adding the reaction solution obtained in the step (A) into acetone to separate out a precipitate; purifying and drying to obtain a chain extender containing hydrogen bond groups;
the molecular structure of the obtained chain extender containing the hydrogen bond group is as follows:
the number average molecular weight was determined to be about 10000g/mol.
Example 3
(A) Mixing 120g of hexamethylene diamine, 81g of N, N '-carbonyldiimidazole, 89g of N, N' -thiocarbonyldiimidazole and dimethyl sulfoxide, and reacting at 30 ℃ for 24 hours to obtain a reaction solution;
(B) Adding the reaction liquid obtained in the step (A) into petroleum ether to separate out a precipitate; purifying and drying to obtain a chain extender containing hydrogen bond groups;
the molecular structure of the obtained chain extender containing the hydrogen bond group is as follows:
the number average molecular weight was determined to be about 15000g/mol.
Example 4
(1) Mixing 222g of isophorone diisocyanate, 500g of polytetrahydrofuran glycol with the number average molecular weight of 1000g/mol and a catalyst dibutyltin dilaurate, controlling the using amount of the catalyst to be 50ppm, and reacting at 80 ℃ for 8 hours to obtain a polyurethane prepolymer;
(2) 7000g of the chain extender containing the hydrogen bond group prepared in the example 1 is added into the polyurethane prepolymer obtained in the step (2), and the self-repairing polyurethane is obtained after stirring reaction for 3 hours at the temperature of 60 ℃.
The resulting self-repairable polyurethane was broken and re-contacted as shown in fig. 1, and the material healed within 12 minutes. Therefore, efficient healing and repair can be realized under the condition of room temperature in a short time.
Example 5
(1) 188.2g of m-xylylene diisocyanate, 1600g of polycaprolactone diol with the number average molecular weight of 2000g/mol and stannous octoate catalyst are mixed, the dosage of the catalyst is controlled to be 1000ppm, and after the reaction is carried out for 5 hours at the temperature of 40 ℃, a polyurethane prepolymer is obtained;
(2) And (2) adding 1000g of the chain extender containing the hydrogen bond group prepared in the example 2 into the polyurethane prepolymer obtained in the step (1), and stirring and reacting for 3 hours at the temperature of 60 ℃ to obtain the self-repairing polyurethane.
The obtained self-repairable polyurethane is scratched and contacted again, and the material can be healed and repaired within 50 minutes. Therefore, efficient healing and repair can be realized under the condition of room temperature in a short time.
Example 6
(1) 262.35g of dicyclohexylmethane diisocyanate, 1200g of polytetrahydrofuran diol with the number average molecular weight of 2000g/mol and dibutyltin dilaurate catalyst are mixed, the dosage of the catalyst is controlled to be 20ppm, and the mixture reacts for 5 hours at the temperature of 70 ℃ to obtain a polyurethane prepolymer;
(2) 4500g of the chain extender containing the hydrogen bond group prepared in the example 3 is added into the polyurethane prepolymer obtained in the step (2), and the self-repairing polyurethane is obtained after stirring reaction for 2 hours at the temperature of 70 ℃.
The obtained self-repairable polyurethane is scratched and contacted again, and the material can be healed and repaired within 1 minute. Therefore, efficient healing and repair can be realized under the condition of room temperature in a short time.
Example 7
(1) Mixing 250.24 g diphenylmethane diisocyanate and 100g of polyoxypropylene glycol with the number average molecular weight of 2000g/mol, and reacting at 20 ℃ for 10h to obtain a polyurethane prepolymer;
(2) 19000g of the chain extender containing the hydrogen bond group prepared in the example 1 is added into the polyurethane prepolymer obtained in the step (1), and the self-repairing polyurethane is obtained after stirring reaction for 2 hours at the temperature of 90 ℃.
The obtained self-repairable polyurethane is scratched and contacted again, and the material can be healed and repaired within 30 minutes. Therefore, efficient healing and repair can be realized under the condition of room temperature in a short time.
Example 8
(1) 174.15g toluene diisocyanate, 950g polycarbonate diol (manufacturer: japan, type: UH-CARB 100) with number average molecular weight of 1000g/mol and dibutyltin diacetate as a catalyst are mixed, the dosage of the catalyst is controlled to be 500ppm, and the mixture reacts for 0.5 hour at the temperature of 100 ℃ to obtain a polyurethane prepolymer;
(2) And (2) adding 250g of the chain extender containing the hydrogen bond group prepared in the example 2 and 375g of the chain extender containing the hydrogen bond group prepared in the example 2 into the polyurethane prepolymer obtained in the step (1), and stirring and reacting for 4 hours at 20 ℃ to obtain the self-repairing polyurethane.
The obtained self-repairable polyurethane is scratched and contacted again, and the material can be healed and repaired within 10 minutes. Therefore, efficient healing and repair can be realized under the condition of room temperature in a short time.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. The self-repairing polyurethane is characterized by being prepared by the following steps:
(1) Mixing diisocyanate, polymer polyol and a catalyst, and reacting to obtain a polyurethane prepolymer;
(2) Adding a chain extender containing a hydrogen bond group into the polyurethane prepolymer obtained in the step (1), and stirring for reaction to obtain self-repairing polyurethane;
the chain extender containing the hydrogen bond group is prepared by the following method:
(A) Mixing 120g of hexamethylenediamine, 81g of N, N '-carbonyldiimidazole, 89g of N, N' -thiocarbonyldiimidazole and dimethyl sulfoxide, and reacting at 30 ℃ for 24 hours to obtain a reaction solution;
(B) Adding the reaction liquid obtained in the step (A) into petroleum ether to separate out a precipitate; purifying and drying to obtain a chain extender containing hydrogen bond groups;
the molecular structure of the obtained chain extender containing the hydrogen bond group is as follows:
a and n are positive integers and have a number average molecular weight of 15000g/mol.
2. The self-repairable polyurethane of claim 1, wherein:
the dosage of the catalyst in the step (1) is more than 0ppm and less than or equal to 1000ppm;
the molar ratio of the diisocyanate to the polymer polyol to the chain extender containing the hydrogen bond group is 2: (0.1 to 1.9): (0.1-1.9).
3. The self-healing polyurethane according to claim 1, wherein:
the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, naphthalene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate;
the polymer polyol in the step (1) is at least one of polyester polyol with the number average molecular weight of 1000-4000 g/mol, polyether polyol with the number average molecular weight of 600-3000 g/mol and polycarbonate polyol with the number average molecular weight of 800-4000 g/mol;
in the step (1), the catalyst is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecyl sulfide and dibutyltin diacetate.
4. The self-repairable polyurethane of claim 1, wherein:
in the step (1), the reaction temperature is 20-100 ℃, and the reaction time is 0.5-10 h;
in the step (2), the temperature of the stirring reaction is 20-90 ℃, and the time of the stirring reaction is 2-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010262151.XA CN111363119B (en) | 2020-04-06 | 2020-04-06 | Preparation method of self-repairable polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010262151.XA CN111363119B (en) | 2020-04-06 | 2020-04-06 | Preparation method of self-repairable polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111363119A CN111363119A (en) | 2020-07-03 |
| CN111363119B true CN111363119B (en) | 2023-03-28 |
Family
ID=71203050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010262151.XA Active CN111363119B (en) | 2020-04-06 | 2020-04-06 | Preparation method of self-repairable polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111363119B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280056A (en) * | 2020-11-06 | 2021-01-29 | 湖南科技大学 | Preparation method of repairable graphene oxide material based on hydrogen bond effect |
| CN115073688A (en) * | 2021-08-25 | 2022-09-20 | 南京理工大学 | Super-ductility room-temperature intrinsic self-repairing elastomer material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524697A (en) * | 2013-10-28 | 2014-01-22 | 苏州大学 | Polyurethaneurea hydrogel and preparation methods therefor |
| CN107325256A (en) * | 2017-08-04 | 2017-11-07 | 中国科学院过程工程研究所 | Self-healing polymers material and preparation method thereof |
| CN108659188A (en) * | 2018-06-01 | 2018-10-16 | 南京理工大学 | A kind of polyureas selfreparing thermoplastic elastomer (TPE) and preparation method thereof |
| CN109942773A (en) * | 2019-03-18 | 2019-06-28 | 四川大学 | A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic |
| CN110790888A (en) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | High-strength room-temperature self-repairing polyurethane elastomer based on multiple dynamic reversible effects and preparation and application thereof |
-
2020
- 2020-04-06 CN CN202010262151.XA patent/CN111363119B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524697A (en) * | 2013-10-28 | 2014-01-22 | 苏州大学 | Polyurethaneurea hydrogel and preparation methods therefor |
| CN107325256A (en) * | 2017-08-04 | 2017-11-07 | 中国科学院过程工程研究所 | Self-healing polymers material and preparation method thereof |
| CN108659188A (en) * | 2018-06-01 | 2018-10-16 | 南京理工大学 | A kind of polyureas selfreparing thermoplastic elastomer (TPE) and preparation method thereof |
| CN109942773A (en) * | 2019-03-18 | 2019-06-28 | 四川大学 | A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic |
| CN110790888A (en) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | High-strength room-temperature self-repairing polyurethane elastomer based on multiple dynamic reversible effects and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Tailoring biomimetic polymer networks towards an unprecedented combination of versatile mechanical characteristics";Eun Jung Cha et al.;《The Royal Society of Chemistry》;20190521;15780-15784 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111363119A (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111234154B (en) | Preparation method of self-repairable waterborne polyurethane | |
| US3640967A (en) | Process for the preparation of polyurethanes | |
| US4960849A (en) | Polyurethane from a copolyether of tetrahydrofuran and 3-alkyl tetrahydrofuran | |
| CN111363119B (en) | Preparation method of self-repairable polyurethane | |
| US5077371A (en) | Low free toluene diisocyanate polyurethanes | |
| CN109337043B (en) | Solvent-free self-repairing polyurethane and preparation method thereof | |
| US3385829A (en) | Polyurethane elastomers | |
| US3483167A (en) | Viscosity control in the chain extension of linear polyurethanes using a combination of chain extenders and a chain-stopper | |
| US5070172A (en) | Process for producing polyurethane | |
| EP0194452A1 (en) | Polyester-polyurethane and process for producing it | |
| US4551518A (en) | Process for production of polyurethane | |
| KR20010052359A (en) | Polyurethane/polyurethane-urea resin and process for producing the same | |
| US3718624A (en) | Method of curing polyurethane prepolymers with liquid extender comprising 4,4{40 -methylenebis (2-chloroaniline) and low molecular weight polytetramethylene ether glycol | |
| JPS60195117A (en) | Manufacture of polyurethane | |
| US20020161137A1 (en) | Melt spun thermoplastic polyurethanes useful as textile fibers | |
| JP2003113237A (en) | Polycarbonate and method for producing polyurethane using the same | |
| US3503934A (en) | Manufacture of polyurethane solutions | |
| JP2003113237A5 (en) | ||
| US3897400A (en) | Polyurethane cured with an aromatic monosulfide diamine | |
| US2987504A (en) | Polyurethane rubber via storable intermediates | |
| DE4311923A1 (en) | Two-component coating composition for the production of PUR elastomers | |
| US3661862A (en) | Process for the preparation of polyurethane mastics | |
| JPH072824B2 (en) | Polyurethane manufacturing method | |
| JPH09286835A (en) | Two-package casting polyurethane elastomer composition and production of polyurethane elastomer therefrom | |
| JPS58118815A (en) | Urethane elastomer with improved heat resistance |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230227 Address after: No. 18, Dingsheng Road, Liuyang High tech Industrial Development Zone, Changsha, Hunan 410300 (in Hunan Dulida Paint Technology Co., Ltd.) Applicant after: Hunan Xinzhenbang New Materials Co.,Ltd. Address before: 362801 Hou Hou 187, Hou Village, Hou Long Town, Quangang District, Quanzhou, Fujian Applicant before: Liu Yunhui |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |