CN111499833B - Polyurethane type self-repairing resin - Google Patents
Polyurethane type self-repairing resin Download PDFInfo
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- CN111499833B CN111499833B CN201910101409.5A CN201910101409A CN111499833B CN 111499833 B CN111499833 B CN 111499833B CN 201910101409 A CN201910101409 A CN 201910101409A CN 111499833 B CN111499833 B CN 111499833B
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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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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a polyurethane type self-repairing resin which comprises the following raw materials in parts by weight: 100 parts of hydroxyl-terminated polyether or polyester, 5-30 parts of diisocyanate, 6-20 parts of polyisocyanate, 5-40 parts of polythiol, 1-5 parts of polyol cross-linking agent and 0.05-0.15 part of catalyst; the invention also provides a preparation method of the self-repairing resin, a coating prepared from the resin and a self-repairing coating obtained by coating the coating on a substrate. The polyurethane material disclosed by the invention can prolong the service life of the polyurethane material by introducing the self-repairing functional group into the polyurethane material, and ensure the working stability of the polyurethane material by self-repairing microcracks.
Description
Technical Field
The invention belongs to the field of polyurethane materials, and relates to a self-repairing polyurethane resin and application thereof.
Background
The disulfide bond self-repairing belongs to thermoreversible self-repairing, and because the disulfide bond is a weak covalent bond, the energy required for generating the disulfide bond is low, the repairing temperature is also low, and the temperature is generally lower than 60 ℃. The report of using disulfide bond as self-repairing group is more at present, and foreign countries and domestic countries comprise Huazhongji university capacity-sensitive intelligence and chapter-sensitive autumn teams, and the disulfide bond adopts disulfide component comprising: 4, 4' -diaminodiphenyl disulfide, hydroxyethyl disulfide, and the like, small molecule diol, diamine, or dithiol monomers containing disulfide linkages.
In order to improve the self-repairing efficiency and mechanical strength, aromatic pinacol is further introduced into a system containing a disulfide component, for example, patent CN 106589311A discloses an intrinsic self-repairing and recyclable polyurethane polymer, and a preparation method and application thereof.
However, no report that the self-repairing efficiency is improved by introducing a polymer containing a disulfide bond is found, and the invention obtains a polyurethane resin with self-repairing property by introducing the disulfide-containing self-repairing functional poly-thiol into polyurethane, and further prepares the self-repairing coating, thereby having a certain application prospect.
Disclosure of Invention
The invention aims to disclose a polyurethane type self-repairing resin.
The purpose of the invention is realized by adopting the following technical scheme:
the self-repairing resin comprises the following raw materials in parts by weight: 100 parts of hydroxyl-terminated polyether or polyester, 5-30 parts of diisocyanate, 6-20 parts of polyisocyanate, 5-40 parts of polythiol, 1-5 parts of polyol cross-linking agent and 0.05-0.15 part of catalyst.
Furthermore, the hydroxyl-terminated polyether comprises one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol; the polyester comprises: one or more of polyethylene glycol adipate, polycaprolactone and hydroxyl-terminated polybutadiene; the diisocyanate comprises: 4, 4' -dimethyl diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the polycyanate comprises: at least one of triphenylmethane triisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and isophorone diisocyanate adduct, wherein the mass ratio of the hydroxyl-terminated polyether or polyester to the polyisocyanate is 100: 6-20; the polyalcohol crosslinking agent is trimethylolpropane or triethanolamine; the catalyst comprises dibutyltin dilaurate, triphenyl bismuth, triethylene diamine and dimethyl ethanolamine.
Further, the self-repairing polythiol has a structural formula shown in the specification:
n, the value of n varies from 15 to 30. Wherein the mass ratio of the hydroxyl-terminated polyether or polyester to the polythiol is 100: 5 to 40.
A self-repairing resin is prepared by the following preparation method: by reacting hydroxyl-terminated polyethers or polyesters
With diisocyanates NCOR1NCO, polyisocyanates
Trifunctional cross-linking agents
Polythiols having self-healing properties
And catalyst are stirred evenly at 50-80 ℃, and then are placed in an oven at 50-80 ℃ for solidification for 1-3d for molding.
Further, the hydroxyl-terminated polyether comprises one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol; the polyester comprises: one or more of polyethylene glycol adipate, polycaprolactone and hydroxyl-terminated polybutadiene, wherein the number average molecular weight of the hydroxyl-terminated polyether and the polyester is 1000-plus-5000; the diisocyanate comprises: 4, 4' -dimethyl diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate, wherein the mass ratio of the hydroxyl-terminated polyether or polyester to the diisocyanate is 100: 5-30; the polycyanate comprises: at least one of triphenylmethane triisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and isophorone diisocyanate adduct, wherein the mass ratio of the hydroxyl-terminated polyether or polyester to the polyisocyanate is 100: 6-20; the polyol crosslinking agent is trimethylolpropane or triethanolamine, and the mass ratio of the hydroxyl-terminated polyether or polyester to the polyol crosslinking agent is 100: 1-5; the catalyst comprises dibutyltin dilaurate, triphenyl bismuth, triethylene diamine and dimethyl ethanolamine, and the mass ratio of the hydroxyl-terminated polyether or polyester to the catalyst is 100: 0.05-0.15.
Further, the self-repairing polythiol has a structural formula shown in the specification:
n, the value of n varies from 15 to 30. Wherein the mass ratio of the hydroxyl-terminated polyether or polyester to the polythiol is 100: 5 to 40.
The invention protects a preparation method of the self-repairing resin.
A self-repairing coating is prepared by adding a solvent and a defoaming agent into the self-repairing resin.
Further, the solvent includes ethyl acetate, butyl acetate, 2-butanone, propylene glycol monomethyl ether, toluene, xylene, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, or tetrahydrofuran; the mass ratio of the self-repairing resin to the solvent in the coating is 100: 10-40.
Further, the defoaming agent is hydrophobic siloxane, and the mass ratio of the self-repairing resin to the defoaming agent in the coating is 100: 0.05-0.8.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the polyurethane type self-repairing resin prepared by the invention obviously improves the content of disulfide bonds by introducing polythiol, reaches 2-20 wt%, has adjustable range, and can carry out high-efficiency self-repairing on microcracks.
(2) The self-repairing resin prepared by the invention utilizes the hydrogen bond and the disulfide bond of the polyurethane to realize self-repairing and prolong the service life of the resin and the coating thereof.
Drawings
FIG. 1 is a diagram of a polyurethane type self-repairing coating entity.
Fig. 2 is a stress-strain curve before and after self-repairing of the polyurethane type self-repairing resin.
FIG. 3 is a photograph of the appearance of the self-repairing coating on a stainless steel plate before and after self-repairing, wherein a is a shape chart before repairing, and b is a shape chart after repairing.
Fig. 4 is a photograph of the appearance of the self-repairing coating before and after self-repairing on a polypropylene (PP) plate, wherein a is a graph of the appearance before repairing, and b is a graph of the appearance after repairing.
Detailed Description
The invention is further explained below with reference to the drawings and the embodiments.
The preparation process of the self-repairing resin comprises the following steps:
example 1
100 parts of polyethylene glycol, 20 parts of toluene diisocyanate, 6 parts of hexamethylene diisocyanate trimer, 15 parts of polythiol with the molecular weight of 1000, 2 parts of triethanolamine and 0.05 part of dibutyltin dilaurate are uniformly mixed at room temperature, poured into a polytetrafluoroethylene mold, placed in a vacuum drying oven at 60 ℃ for defoaming, and cured for 2 days at 60 ℃ to obtain the self-repairing resin 1 with self-repairing property.
Example 2
Firstly, 100 parts of polytetrahydrofuran ether glycol, 15 parts of isophorone diisocyanate, 15 parts of hexamethylene diisocyanate trimer, 20 parts of polythiol with the molecular weight of 4000, 3 parts of trimethylolpropane and 0.05 part of triphenyl bismuth are mixed uniformly at room temperature, poured into a polytetrafluoroethylene mold, finally placed in a vacuum drying oven at 60 ℃ for defoaming, and cured for 2 days at 60 ℃ to obtain the self-repairing resin 2 with self-repairing property.
Example 3
Firstly, 100 parts of polycaprolactone, 25 parts of hexamethylene diisocyanate, 12 parts of isophorone diisocyanate trimer, 30 parts of polythiol with the molecular weight of 1000, 3 parts of trimethylolpropane and 0.10 part of dibutyltin dilaurate are uniformly mixed at room temperature, poured into a polytetrafluoroethylene mold, finally placed in a vacuum drying oven at the temperature of 60 ℃ for defoaming, and cured for 1d at the temperature of 80 ℃ to obtain the self-repairing resin 3 with self-repairing property.
Example 4
Firstly, 100 parts of polytetrahydrofuran ether glycol, 18 parts of 4, 4' -dimethyl diisocyanate, 23 parts of polythiol with the molecular weight of 3000, 2.6 parts of trimethylolpropane and 0.08 part of dibutyltin dilaurate are uniformly mixed at room temperature, poured into a polytetrafluoroethylene mold, finally placed in a vacuum drying oven at the temperature of 60 ℃ for defoaming, and cured for 2 days at the temperature of 70 ℃ to obtain the self-repairing resin 4 with self-repairing property.
Example 5
Firstly, 100 parts of hydroxyl-terminated polybutadiene, 23 parts of 4, 4' -dimethyl diisocyanate, 16 parts of polythiol with the molecular weight of 3000, 2 parts of trimethylolpropane and 0.16 part of dibutyltin dilaurate are uniformly mixed at room temperature, then the mixture is poured into a polytetrafluoroethylene mold, finally the polytetrafluoroethylene mold is placed in a vacuum drying oven at the temperature of 60 ℃ for deaeration, and then the mixture is cured for 1d at the temperature of 80 ℃ to obtain the self-repairing resin 5 with self-repairing property.
The preparation process of the self-repairing coating comprises the following steps:
example 6
Adding 40 parts of butyl acetate solvent and 0.2 part of defoaming agent hydrophobic siloxane into 100 parts of the self-repairing resin 1, coating the mixture on the surface of phosphatized stainless steel, and curing for 1d at 60 ℃ to obtain the self-repairing coating 1.
Example 7
Adding 30 parts of solvent xylene and 0.5 part of defoaming agent hydrophobic siloxane into 100 parts of the self-repairing resin 2, coating the mixture on the surface of phosphatized stainless steel, and curing for 1d at 60 ℃ to obtain the self-repairing coating 2.
And comparing the mechanical properties of the self-repairing resin. The prepared self-repairing resin is subjected to a tensile test, and stress-strain curves before and after repairing are examined and are shown in fig. 2.
Appearance observation of the self-repairing coating: the self-repairing process of the prepared self-repairing coating on the stainless steel plate is observed, and the self-repairing coating is cut by a blade and then placed into an oven at 80 ℃ for self-repairing as shown in figures 3 and 4. And taking out after 12h to observe the self-repairing condition of the cracks.
The performance test results of the self-healing resin and the self-healing coating are shown in table 1.
TABLE 1 self-healing resin and self-healing coating Properties
Claims (5)
1. The polyurethane type self-repairing resin is characterized by comprising the following raw materials in parts by weight: 100 parts of hydroxyl-terminated polyether or polyester, 5-30 parts of diisocyanate, 6-20 parts of polyisocyanate, 5-40 parts of polythiol, 1-5 parts of trifunctional cross-linking agent and 0.05-0.15 part of catalyst; the self-repairing resin is prepared by the following preparation method: hydroxyl-terminated polyether or polyester, diisocyanate, polyisocyanate, trifunctional cross-linking agent, polythiol with self-repairability and catalyst are stirred uniformly at 50-80 ℃, and then are placed in an oven at 50-80 ℃ for curing for 1-3d for forming; the hydroxyl-terminated polyether comprises one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol; the polyester comprises: one or more of polyethylene glycol adipate and polycaprolactone; the diisocyanate comprises: one or more of toluene diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate; the polycyanate comprises: at least one of triphenylmethane triisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and isophorone diisocyanate adduct, wherein the mass ratio of the hydroxyl-terminated polyether or polyester to the polyisocyanate is 100: 6-20; the cross-linking agent with three functional groups is trimethylolpropane or triethanolamine; the catalyst comprises dibutyltin dilaurate, triphenyl bismuth, triethylene diamine and dimethyl ethanolamine; the self-repairing polythiol has a structural formula shown in the specification:
n, wherein the value of n ranges from 15 to 30, and the mass ratio of the hydroxyl-terminated polyether or polyester to the polythiol is 100: 5-40.
2. The polyurethane-based self-repairing resin of claim 1, wherein the hydroxyl-terminated polyether comprises one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol; the polyester comprises: one or more of polyethylene glycol adipate and polycaprolactone, and the number average molecular weight of the hydroxyl-terminated polyether and the polyester is 1000-5000-; the diisocyanate comprises: one or more of toluene diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate, wherein the mass ratio of hydroxyl-terminated polyether or polyester to diisocyanate is 100: 5-30; the polycyanate comprises: at least one of triphenylmethane triisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and isophorone diisocyanate adduct, wherein the mass ratio of the hydroxyl-terminated polyether or polyester to the polyisocyanate is 100: 6-20; the trifunctional cross-linking agent is trimethylolpropane or triethanolamine, and the mass ratio of the hydroxyl-terminated polyether or polyester to the trifunctional cross-linking agent is 100: 1-5; the catalyst comprises dibutyltin dilaurate, triphenyl bismuth, triethylene diamine and dimethyl ethanolamine, and the mass ratio of the hydroxyl-terminated polyether or polyester to the catalyst is 100: 0.05-0.15.
3. A self-repairing coating is characterized in that a solvent and a defoaming agent are added into the polyurethane type self-repairing resin in any one of claims 1-2 to prepare the self-repairing coating.
4. The self-healing coating of claim 3, wherein the solvent comprises ethyl acetate, butyl acetate, 2-butanone, propylene glycol monomethyl ether, toluene, xylene, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, or tetrahydrofuran; the mass ratio of the self-repairing resin to the solvent in the coating is 100: 10-40.
5. The self-repairing coating of claim 4, wherein the defoaming agent is hydrophobic siloxane, and the mass ratio of the self-repairing resin to the defoaming agent in the coating is 100: 0.05-0.8.
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| CN112239530A (en) * | 2020-08-31 | 2021-01-19 | 济南大学 | Novel method for preparing hydrophobic self-healing super-elastic polyurethane elastomer |
| CN112521573B (en) * | 2020-11-25 | 2021-07-30 | 山东益丰生化环保股份有限公司 | Modified polythiol and metal anticorrosion UV (ultraviolet) coating using same |
| CN114479651A (en) * | 2021-11-08 | 2022-05-13 | 山东灵晓新材料有限公司 | Self-repairable UV (ultraviolet) photocureable coating and preparation method thereof |
| CN115651514A (en) * | 2022-09-28 | 2023-01-31 | 中国人民解放军陆军工程大学 | Infrared and laser compatible stealth coating with self-repairing function and good mechanical property |
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