CN114560983A - Flame-retardant self-repairing waterborne polyurethane composite coating agent and preparation method and application thereof - Google Patents

Flame-retardant self-repairing waterborne polyurethane composite coating agent and preparation method and application thereof Download PDF

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CN114560983A
CN114560983A CN202210158953.5A CN202210158953A CN114560983A CN 114560983 A CN114560983 A CN 114560983A CN 202210158953 A CN202210158953 A CN 202210158953A CN 114560983 A CN114560983 A CN 114560983A
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flame
repairing
hbpc
reaction
waterborne polyurethane
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CN114560983B (en
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刘超
史炳瑞
张佳豪
汪义静
薛新
袁启明
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Shaanxi University of Science and Technology
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    • 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
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    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025—Polyphosphazenes
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    • 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
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Abstract

The invention discloses a flame-retardant self-repairing waterborne polyurethane composite coating agent and a preparation method and application thereof, belonging to the technical field of coating agent production. The method prepares aminated nanoparticles by reacting the nanoparticles with a coupling agent; the aminated nano particles react with hexachlorocyclotriphosphazene and diamine to prepare amino-terminated hyperbranched polyphosphazene modified nano particles (HBPC); then polyester diol, hydrophilic monomer and diisocyanate are mixed and reacted to prepare a prepolymer solution with end-capped isocyanate groups; adding a dynamic reversible covalent bond monomer, a dynamic reversible non-covalent bond monomer and HBPC (high-performance polyethylene) into the prepolymer solution for reaction to prepare a chain extension product solution; and adding a neutralizer into the chain extension product solution for reaction to prepare the HBPC waterborne polyurethane with the flame-retardant self-repairing function. The prepared flame-retardant self-repairing type waterborne polyurethane composite coating agent has hyperbranched and double reversible bond structures, can quickly and efficiently self-repair at high temperature, and can be applied to flame-retardant self-repairing coatings of wood paints.

Description

Flame-retardant self-repairing waterborne polyurethane composite coating agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of coating agent production, and particularly relates to a flame-retardant self-repairing waterborne polyurethane composite coating agent, and a preparation method and application thereof.
Background
Waterborne Polyurethane (WPU) has the characteristics of environmental protection, easy processing, high solid content, easy film forming, chemical corrosion resistance and the like, and is widely applied to the fields of leather finishing, building materials, coatings and the like. However, WPU has poor flame retardant property and low mechanical strength, is easy to generate macroscopic damage or crack under the action of external force, cannot ensure the service life and the protection life, and cannot meet the requirements of people in practical application.
At present, the flame retardant property of the reaction type flame retardant WPU can be improved by adding a flame retardant to obtain the reaction type flame retardant WPU. For example, the Chinese patent (CN108059913A) discloses a method for preparing a water-based phosphorus-silicon flame-retardant polyurethane coating material, which adopts phosphorus-containing polyol and polydimethylsiloxane as the soft segment of WPU to prepare a flame-retardant WPU. According to the vertical combustion test carried out by the national standard GB/T5455-2014, under the synergistic flame-retardant effect of phosphorus and nitrogen, the flame-retardant effect of the coating can reach the B1 level when the polyester fabric is increased by 30%, but the WPU prepared by the method has lower strength after film forming. In the aspect of improving the strength of the WPU, a method of adding the nanoparticles can be adopted, but the method has poor compatibility of the nanoparticles and the WPU, so that the nanoparticles need to be modified. In addition, the strength of the WPU can be improved by adding the nano particles, but the WPU is inevitably damaged in the processing or using process, and the mechanical property of the WPU is influenced, so that the attractiveness and the service life of the product are reduced. In order to solve the problems, self-repairing coatings are produced, wherein the intrinsic self-repairing material realizes self-repairing through reversible transformation of reversible covalent bonds or reversible non-covalent bonds in molecular chain structures or among molecular chains. For example, the Chinese invention patent (CN110028686A) discloses a cellulose nanocrystal reinforced self-repairing aqueous polyurethane material and a preparation method thereof, maleic amide groups are grafted on the surface of cellulose nanocrystals through esterification reaction, the mechanical property of the material is obviously enhanced by adding the cellulose nanocrystals, and then the WPU material is self-repaired under the heating condition through the combined action of reversible retro-DA reaction and DA reaction. The cellulose nanocrystal is a biological-based nanomaterial with excellent performance, is wide in source and high in strength, and can enhance the self-repairing performance and the mechanical performance of polyurethane. However, the method is complex to operate, the preparation process is not environment-friendly, and the obtained product only has gas barrier property and poor flame retardant effect.
Therefore, the development of the waterborne polyurethane coating agent which has excellent flame retardant property, high mechanical strength and good self-repairing function has become an urgent problem to be solved, and the waterborne polyurethane coating agent has important theoretical value and practical significance for protecting the life and property safety of people, and prolonging the service life and the protection life of a paint film.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a flame-retardant self-repairing type waterborne polyurethane composite coating agent, a preparation method and application thereof, and solves the problems of poor flame retardance, low mechanical strength and limited protection life of a paint film of the traditional waterborne polyurethane coating.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a flame-retardant self-repairing waterborne polyurethane composite coating agent, which comprises the following steps:
1) dissolving the nano particles, adding a coupling agent for reaction, washing and drying to prepare aminated nano particles;
2) dissolving the aminated nanoparticles prepared in the step 1), and adding hexachlorocyclotriphosphazene and diamine; adding an acid-binding agent, and introducing nitrogen for reaction to prepare HBPC;
3) mixing polyester diol, a hydrophilic monomer and diisocyanate for reaction to prepare a prepolymer solution terminated by isocyanate groups;
4) adding a dynamic reversible covalent bond monomer, a dynamic reversible noncovalent bond monomer and HBPC into the prepolymer solution obtained in the step 3), and carrying out chain extension reaction to prepare a chain extension product solution;
5) adding a neutralizer into the chain extension product solution obtained in the step 4) for reaction; cooling, adding water, stirring and emulsifying to obtain the HBPC waterborne polyurethane with the flame-retardant self-repairing function.
Preferably, in step 1), the nanoparticles are one of nano-silica, nano-titanium dioxide, graphene oxide, hydrotalcite, montmorillonite, two-dimensional metal organic framework film and nano-magnesium hydroxide; the coupling agent comprises one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, isopropoxytris (ethylenediamine-N-ethoxy) titanate and neoalkoxy tris (p-aminophenoxy) zirconate.
Preferably, in the step 1), 0.1-10 parts of the nano particles are used; 50-1000 parts of water/ethanol mixed solution; 0.01-2 parts of a coupling agent.
Preferably, in the step 1), the particle size of the nanoparticles is 50-1000 nm.
Preferably, in the step 1), the reaction is carried out for 5-8 h at a rotation speed of 300-500 r/min and a temperature of 60-80 ℃; in the step 2), the reaction is carried out for 4-8 h under the conditions that the rotating speed is 300-500 r/min and the temperature is 60-80 ℃.
Preferably, the diamine in step 2) is one or more of 1, 3-butanediamine, 1, 6-hexanediamine, 1, 8-octanediamine, 2-dimethyl-1, 3-propanediamine and polyoxyethylenediamine; the feeding ratio of the hexachlorocyclotriphosphazene to the diamine is (1-3) to (4-5).
Preferably, in the step 2), 0.1-10 parts of aminated nanoparticles and 50-1000 parts of tetrahydrofuran solution are added; 1-100 parts of hexachlorocyclotriphosphazene and diamine; the acid-binding agent is 0.1-1 part.
Further preferably, in the step 2), the acid-binding agent is triethylamine.
Preferably, in the step 3), the polyester diol is one of polytetramethylene glycol, polycaprolactone diol and polyethylene glycol; the hydrophilic monomer is 2, 2-dimethylolbutyric acid or 2, 2-dimethylolpropionic acid; the diisocyanate is one of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate and diphenylmethane diisocyanate.
Preferably, in the step 3), the feeding ratio of the polyester diol, the hydrophilic monomer and the diisocyanate is (20-25) to 1 (8-10).
Preferably, in the step 3), the total amount of the polyester diol, the hydrophilic monomer and the diisocyanate is 10 to 100 parts.
Preferably, in the step 4), the total amount of the dynamic reversible covalent bond compound, the dynamic reversible noncovalent bond compound and the HBPC is 1-20 parts.
Preferably, in step 4), the dynamic reversible covalent bond monomer comprises one or more of 2,2' -dihydroxybutane diselenide, 2' -diaminodiphenyl disulfide, 4' -diaminodiphenyl disulfide, 3, 5-dimethoxyphenylboronic acid and cystine; the dynamic reversible non-covalent bond monomer comprises one or more of 2-urea-4 [ H ] -pyrimidone, 5, 6-diamino-1, 3-dimethyl uracil, 2, 6-diaminopyridine, 2, 6-pyridinedicarboxylic acid and 4, 5-dimethylol-2-phenylimidazole; the feeding ratio of the dynamic reversible covalent bond monomer to the dynamic reversible non-covalent bond monomer to the HBPC is 1 (1-3) to 1-3; in the step 5), the neutralizing agent is one or more of triethylamine, zinc chloride, ferric chloride, terbium trifluoromethanesulfonate and zinc trifluoromethanesulfonate.
Preferably, in the step 3), the reaction condition is that the reaction is carried out for 5-7 hours at the temperature of 70-90 ℃; in the step 4), the reaction condition is that the reaction is carried out for 1-2 h at the temperature of 50-70 ℃; in the step 5), the reaction condition is that the reaction is carried out for 20-40 min at the temperature of 40-60 ℃.
Preferably, in the step 5), the neutralizing agent is 0.1-1 part; 50-1000 parts of water are added.
The invention also discloses a flame-retardant self-repairing waterborne polyurethane composite coating agent prepared by the preparation method of the flame-retardant self-repairing waterborne polyurethane composite coating agent.
The invention also discloses an application of the flame-retardant self-repairing type waterborne polyurethane composite finishing agent in a flame-retardant self-repairing coating of wood lacquer.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a flame-retardant self-repairing waterborne polyurethane composite coating agent, which is characterized in that amination nano particles (NP-NH)2) The modified nano particles (HBPC) are prepared by reacting with hexachlorocyclotriphosphazene and diamine, the HBPC contains a large amount of P, N elements, and the synergistic flame retardant effect of N-P can endow the coating with excellent flame retardant property; the content of the flame-retardant functional unit can be ensured by utilizing the abundant hyperbranched chain segments on the HBPC, so that the flame-retardant performance of the coating can be improved, and the coating and the polyurethane chain segments can form a chemical/physical cross-linked network structure, thereby obviously improving the mechanical strength of the coating; the abundant terminal amino groups on the HBPC surface can effectively improve the compatibility and the interface bonding property between the nano particles and the WPU matrix, so that the mechanical property of a paint film is effectively improved; meanwhile, the dynamic reversible covalent bond and the dynamic reversible noncovalent bond are introduced into the WPU chain segment structure, so that the mechanical property of the WPU can be further improved by utilizing the physical crosslinking effect of the reversible covalent bond and the reversible noncovalent bond, and the self-repairing efficiency of the material can be promoted by utilizing the mobility of the hyperbranched polymer chain segment. When the material is broken, the reversible non-covalent bond can be used as a sacrificial bond to absorb energy, so that the flexibility of the coating can be remarkably improved; when the WPU coating is damaged, reversible breakage and recombination of reversible covalent bonds and reversible non-covalent bonds at the damaged position can be realized, so that the coating can be rapidly self-repaired at room temperature. In addition, the preparation method has the advantages of simple and easily-controlled process, low cost, environmental protection and application rangeWide range, strong practicability and the like, and is suitable for industrial production.
Compared with the technical defects that the flame retardant performance, the mechanical strength and the self-repairing efficiency of the traditional waterborne polyurethane cannot be simultaneously considered, the flame retardant self-repairing waterborne polyurethane composite finishing agent prepared by the preparation method provided by the invention has the advantages that the reversible covalent bond, the reversible non-covalent bond, the nano particles and the nitrogen-phosphorus flame retardant are introduced into the WPU chain segment, so that the WPU is endowed with excellent flame retardant performance and self-repairing function, and the mechanical property of the WPU is ensured. The flame-retardant self-repairing type waterborne polyurethane composite coating agent has a hyperbranched and double reversible bond structure, can realize quick and efficient self-repairing at high temperature, and has the characteristics of good stability, excellent mechanical property, obvious repairing effect and the like, the Limiting Oxygen Index (LOI) is 20.07-26.98%, the self-repairing efficiency is 81.47-94.76%, the flame-retardant grade can reach UL-94V-0 grade, no flame dripping exists, and the flame-retardant property and the self-repairing property are realized. The flame-retardant self-repairing type waterborne polyurethane composite coating agent provided by the invention can be applied to various fields of buildings, aerospace, transportation, electronics and the like, and particularly can be applied to the fields of flame-retardant self-repairing coatings of wood paints and the like due to the flame-retardant and self-repairing properties.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below:
the invention discloses a preparation method of a flame-retardant self-repairing waterborne polyurethane composite coating agent, which comprises the following process steps:
1. preparation of amino-terminated hyperbranched polyphosphazene modified nanoparticles (HBPC)
1) Ultrasonically dispersing 0.1-10 parts of nanoparticles in 50-1000 parts of water/ethanol mixed solution, slowly adding 0.01-2 parts of coupling agent, reacting for 5-8 h at the rotating speed of 300-500 r/min and the reaction temperature of 60-80 ℃, centrifugally washing with deionized water and absolute ethyl alcohol after the reaction is finished, and then drying in vacuum to obtain aminated nanoparticles (NP-NH)2)；
Wherein the nano particles are nano silicon dioxide (SiO)2) Nano titanium dioxide (TiO)2) One of Graphene Oxide (GO), hydrotalcite (LDH), montmorillonite (MMT), two-dimensional Metal Organic Framework (MOF) and nano Magnesium Hydroxide (MH); the particle size of the nano particles is 50-1000 nm; the coupling agent comprises one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, isopropoxytris (ethylenediamine-N-ethoxy) titanate and neoalkoxy tris (p-aminophenoxy) zirconate;
2) adding 0.1-10 parts of NP-NH2Adding the mixture into 50-1000 parts of tetrahydrofuran solution, and adding 1-100 parts of hexachlorocyclotriphosphazene and diamine according to the feeding ratio of (1-3) to (4-5); then adding 0.1-1 part of triethylamine as an acid-binding agent, introducing nitrogen, and reacting for 4-8 hours at the rotating speed of 300-500 r/min and the temperature of 60-80 ℃ to obtain the amino-terminated hyperbranched polyphosphazene modified nanoparticles(HBPC)；
Wherein the diamine comprises one or more of 1, 3-butanediamine, 1, 6-hexanediamine, 1, 8-octanediamine, 2-dimethyl-1, 3-propanediamine and polyoxyethylene diamine.
2. Preparation of HBPC waterborne polyurethane (WPU/HBPC) with flame-retardant self-repairing function
3) Mixing 10-100 parts of polyester glycol, hydrophilic monomer and diisocyanate according to a feeding ratio of (20-25) to (1) (8-10), and carrying out prepolymerization reaction at 70-90 ℃ for 5-7 h to prepare an isocyanate group-terminated prepolymer solution;
wherein the polyester diol is one of polytetramethylene glycol, polycaprolactone diol and polyethylene glycol; the hydrophilic monomer is 2, 2-dimethylolbutyric acid or 2, 2-dimethylolpropionic acid; the diisocyanate is one of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate and diphenylmethane diisocyanate;
4) adding 1-20 parts of dynamic reversible covalent bond monomer, dynamic reversible noncovalent bond monomer and HBPC (high performance polycarbonate) in the total amount according to the feeding ratio of 1 (1-3) to (1-3) into the prepolymer solution obtained in the step 3), and carrying out chain extension reaction at the temperature of 50-70 ℃ for 1-2 h to prepare a chain extension product solution;
wherein the dynamic reversible covalent bond monomer is one or more of 2,2' -dihydroxy butane diselenide, 2' -diamino diphenyl disulfide, 4' -diamino diphenyl disulfide, 3, 5-dimethoxy phenylboronic acid and cystine; the dynamic reversible non-covalent bond monomer is one or more of 2-urea-4 [ H ] -pyrimidone, 5, 6-diamino-1, 3-dimethyl uracil, 2, 6-diaminopyridine, 2, 6-pyridinedicarboxylic acid and 4, 5-dihydroxymethyl-2-phenylimidazole;
5) adding 0.1-1 part of neutralizing agent into the chain extension product solution obtained in the step 4), and carrying out neutralization reaction at the temperature of 40-60 ℃ for 20-40 min; then cooling to room temperature, adding 50-1000 parts of water, and emulsifying for 1-3 h under high-speed stirring to obtain HBPC waterborne polyurethane (WPU/HBPC) with flame-retardant self-repairing function;
the neutralizing agent is one or more of triethylamine, zinc chloride, ferric chloride, terbium trifluoromethanesulfonate and zinc trifluoromethanesulfonate.
Taking silicon dioxide with the particle size of 1000nm as an example, HBPC-SiO is prepared by nano silicon dioxide, 3-aminopropyl trimethoxy silane, hexachlorocyclotriphosphazene and 1, 6-hexamethylene diamine2The reaction chemical formula of (1) is as follows:
Figure BDA0003513571300000081
taking the reaction of polytetramethylene glycol, isophorone diisocyanate and 2, 2-dimethylolbutyric acid as an example, by adding 2-urea-4 [ H ]]-pyrimidinone, 2' -dihydroxybutanediselenoether and HBPC-SiO2Preparation of WPU/HBPC-SiO2The reaction chemical formula of (1) is as follows:
Figure BDA0003513571300000091
the flame-retardant self-repairing waterborne polyurethane composite coating agent can be prepared by the preparation method, and has high application value in room-temperature self-repairing coatings.
The present invention is described in further detail below with reference to specific examples:
example 1
1. Amino-terminated hyperbranched polyphosphazene modified nano silicon dioxide (HBPC-SiO)2) Preparation of
1) 1 part of 50nm silicon dioxide (SiO)2) Ultrasonically dispersing in 100 parts of water/ethanol mixed solution, slowly adding 0.01 part of 3-aminopropyltrimethoxysilane as a coupling agent, reacting at the rotating speed of 300r/min at 74 ℃ for 6 hours, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then drying in vacuum to obtain aminated nano silicon dioxide (NP-SiO)2-NH2)；
2) 0.1 part of NP-SiO2-NH2Adding the mixture into 50 parts of tetrahydrofuran solution, and adding 5 parts of hexachlorocyclotriphosphazene and 1, 6-hexamethylenediamine according to the feeding ratio of 1: 4; then is added to0.5 part of triethylamine is used as an acid-binding agent, nitrogen is introduced into the triethylamine and reacts for 6 hours under the conditions that the rotating speed is 300r/min and the temperature is 65 ℃ to obtain the amino-terminated hyperbranched polyphosphazene modified nano silicon dioxide (HBPC-SiO)2)；
2. HBPC-SiO with flame-retardant self-repairing function2Waterborne polyurethane (WPU/HBPC-SiO)2) Preparation of
3) Mixing 10 parts of polytetramethylene glycol, 2-dimethylolbutyric acid and isophorone diisocyanate in a ratio of 21:1:10, and reacting at 75 ℃ for 6 hours to prepare a prepolymer solution terminated by isocyanate groups;
4) 1 part of 2-urea-4H]-pyrimidinone, 2' -dihydroxybutanediselenoether and HBPC-SiO2Adding the prepolymer solution obtained in the step 3) according to the ratio of 1:2:2, and reacting at 55 ℃ for 1.5h to obtain a chain extension product solution;
5) adding 0.1 part of triethylamine into the chain extension product solution obtained in the step 4), reacting for 40min at 40 ℃, cooling to room temperature, adding 50 parts of water, and emulsifying for 2h under high-speed stirring to obtain HBPC-SiO with flame-retardant self-repairing function2Waterborne polyurethane (WPU/HBPC-SiO)2)。
WPU/HBPC-SiO prepared in this example2The Limiting Oxygen Index (LOI) of the coating is 20.07 percent, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which indicates that the coating has good flame retardant property; WPU/HBPC-SiO2The tensile strength of the coating is 38.61MPa, the coating is completely cut off, the tensile strength is 31.49MPa after the coating is repaired for 8 hours at room temperature, and the repair efficiency of the coating is 81.56 percent by taking the tensile strength as an index.
Example 2
1. Amino-terminated hyperbranched polyphosphazene modified nano silicon dioxide (HBPC-SiO)2) Preparation of
1) 2 parts of 1000nm silicon dioxide (SiO)2) Ultrasonically dispersing in 200 parts of water/ethanol mixed solution, slowly adding 0.02 part of 3-aminopropyltriethoxysilane as a coupling agent, reacting at the rotating speed of 300r/min at 70 ℃ for 7 hours, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then drying in vacuum to obtain aminated nano silicon dioxide (NP-SiO)2-NH2)；
2) 0.1 part of NP-SiO2-NH2Adding the mixture into 50 parts of tetrahydrofuran solution, and adding 8 parts of hexachlorocyclotriphosphazene and 1, 8-octanediamine according to the feeding ratio of 3: 5; then 0.8 part of triethylamine is added as an acid-binding agent, nitrogen is introduced and the mixture reacts for 6 hours under the conditions that the rotating speed is 500r/min and the temperature is 70 ℃, and the amino-terminated hyperbranched polyphosphazene modified nano silicon dioxide (HBPC-SiO)2)；
2. HBPC-SiO with flame-retardant self-repairing function2Waterborne polyurethane (WPU/HBPC-SiO)2) Preparation of
3) 100 parts of polytetramethylene glycol, 2-dimethylolpropionic acid and toluene diisocyanate in a ratio of 23:1:8 are mixed and reacted for 6 hours at 80 ℃ to prepare a prepolymer solution of an isocyanate group end capping;
4) the total amount of 15 parts of 5, 6-diamino-1, 3-dimethyl uracil, 2' -diaminodiphenyl disulfide and HBPC-SiO2Adding the prepolymer solution obtained in the step 3) according to the ratio of 1:2:2, and reacting at 67 ℃ for 1h to obtain a chain extension product solution;
5) adding 0.3 part of triethylamine into the chain extension product solution obtained in the step 4), reacting for 35min at 44 ℃, cooling to room temperature, adding 100 parts of water, and emulsifying for 2h under high-speed stirring to obtain HBPC-SiO with flame-retardant self-repairing function2Waterborne polyurethane (WPU/HBPC-SiO)2)。
WPU/HBPC-SiO prepared in this example2The Limiting Oxygen Index (LOI) of the coating is 26.12 percent, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which indicates that the coating has good flame retardant property; WPU/HBPC-SiO2The tensile strength of the coating was 45.89MPa, and after the coating was completely cut and repaired at room temperature for 7 hours, the tensile strength was 43.27MPa, and the repair efficiency of the coating was 94.29% using the tensile strength as an index.
Example 3
1. Amino-terminated hyperbranched polyphosphazene modified nano titanium dioxide (HBPC-TiO)2) Preparation of (2)
1) 1 part of 1000nm titanium dioxide (TiO)2) Ultrasonically dispersing in 100 parts of water/ethanol mixed solution, slowly adding 0.0 part of the mixture1 part of N-2-aminoethyl-3-aminopropyltriethoxysilane as a coupling agent, reacting for 7 hours at the rotating speed of 350r/min at 68 ℃, centrifugally washing with deionized water and absolute ethyl alcohol after the reaction is finished, and then drying in vacuum to obtain aminated nano titanium dioxide (NP-TiO)2-NH2)；
2) 0.1 part of NP-TiO2-NH2Adding the mixture into 50 parts of tetrahydrofuran solution, and adding 1 part of hexachlorocyclotriphosphazene and 1, 3-butanediamine according to the feeding ratio of 1: 4; then 0.1 part of triethylamine is added as an acid-binding agent, nitrogen is introduced and the mixture reacts for 8 hours under the conditions that the rotating speed is 360r/min and the temperature is 60 ℃, and the amino-terminated hyperbranched polyphosphazene modified nano titanium dioxide (HBPC-TiO) is obtained2)；
2. HBPC-TiO with flame-retardant self-repairing function2Waterborne polyurethane (WPU/HBPC-TiO)2) Preparation of
3) Mixing 10 parts of polycaprolactone diol, 2-dimethylolbutyric acid and 1, 6-hexamethylene diisocyanate in a ratio of 22:1:9, and reacting at 74 ℃ for 6 hours to prepare isocyanate-terminated prepolymer solution;
4) 1 part of 2, 6-diaminopyridine, 4' -diaminodiphenyl disulfide and HBPC-TiO in total2Adding the prepolymer solution obtained in the step 3) according to the ratio of 1:2:2, and reacting at 60 ℃ for 1h to obtain a chain extension product solution;
5) dropwise adding 0.1 part of zinc chloride and 0.1 part of triethylamine into the chain extension product solution obtained in the step 4), reacting for 30min at 55 ℃, cooling to room temperature, adding 50 parts of water, and emulsifying for 3h under high-speed stirring to obtain the HBPC-TiO with the flame-retardant self-repairing function2Waterborne polyurethane (WPU/HBPC-TiO)2)。
WPU/HBPC-TiO prepared in this example2The Limiting Oxygen Index (LOI) of the coating is 20.83 percent, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which indicates that the coating has good flame retardant property; WPU/HBPC-TiO2The tensile strength of the coating is 37.99MPa, the coating is completely cut off, the tensile strength is 30.95MPa after the coating is repaired for 6 hours at room temperature, and the repair efficiency of the coating is 81.47 percent by taking the tensile strength as a research index.
Example 4
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano graphene oxide (HBPC-GO)
1) Ultrasonically dispersing 2 parts of 1000nm Graphene Oxide (GO) into 200 parts of water/ethanol mixed solution, slowly adding 0.02 part of isopropoxy tri (ethylenediamine-N-ethoxy) titanate serving as a coupling agent, reacting at the rotating speed of 350r/min at 70 ℃ for 8 hours, centrifugally washing with deionized water and absolute ethyl alcohol after the reaction is finished, and then drying in vacuum to obtain aminated nano graphene oxide (NP-GO-NH)2)；
2) Adding 0.1 part of NP-GO-NH2Adding the mixture into 50 parts of tetrahydrofuran solution, and adding 1.2 parts of hexachlorocyclotriphosphazene and 2, 2-dimethyl-1, 3-propanediamine according to the proportion of 1: 5; then adding 0.12 part of triethylamine as an acid-binding agent, introducing nitrogen, and reacting for 7 hours at the rotating speed of 400r/min and the temperature of 63 ℃ to obtain amino-terminated hyperbranched polyphosphazene modified nano graphene oxide (HBPC-GO);
2. preparation of HBPC-GO waterborne polyurethane (WPU/HBPC-GO) with flame-retardant self-repairing function
3) Mixing 100 parts of polycaprolactone diol, 2-dimethylolpropionic acid and diphenylmethane diisocyanate in a ratio of 23:1:8, and reacting at 80 ℃ for 6 hours to prepare isocyanate group-terminated prepolymer solution;
4) adding 20 parts of 2, 6-dipicolinic acid, 3, 5-dimethoxyphenylboronic acid and HBPC-GO in a ratio of 1:2:2 into the prepolymer solution obtained in the step 3), and reacting at 55 ℃ for 1.5h to obtain a chain extension product solution;
5) and (3) dropwise adding 0.7 part of ferric chloride and 0.3 part of triethylamine into the chain extension product solution obtained in the step 4), reacting for 40min at 40 ℃, cooling to room temperature, adding 100 parts of water, and emulsifying for 3h under high-speed stirring to obtain the HBPC-GO waterborne polyurethane (WPU/HBPC-GO) with the flame-retardant self-repairing function.
The Limited Oxygen Index (LOI) of the WPU/HBPC-GO coating prepared by the embodiment is 26.94%, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which indicates that the coating has good flame retardant property; the tensile strength of the WPU/HBPC-GO coating is 44.63MPa, the WPU/HBPC-GO coating is completely cut off, the tensile strength is 42.29MPa after the WPU/HBPC-GO coating is repaired for 8 hours at room temperature, the tensile strength is used as an investigation index, and the repair efficiency of the WPU/HBPC-GO coating is 94.76%.
Example 5
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano hydrotalcite (HBPC-LDH)
1) Ultrasonically dispersing 10 parts of 50nm hydrotalcite (LDH) into 1000 parts of water/ethanol mixed solution, slowly adding 0.1 part of neoalkoxy tri (p-aminophenoxy) zirconate as a coupling agent, reacting at the rotating speed of 400r/min at 70 ℃ for 6 hours, centrifugally washing with deionized water and absolute ethyl alcohol after the reaction is finished, and then drying in vacuum to obtain aminated nano hydrotalcite alkene (NP-LDH-NH)2)；
2) 10 parts of NP-LDH-NH2Adding the mixture into 1000 parts of tetrahydrofuran solution, and adding 100 parts of hexachlorocyclotriphosphazene and polyoxyethylene diamine according to the feeding ratio of 1: 4; adding 1 part of triethylamine as an acid-binding agent, introducing nitrogen, and reacting for 5 hours at the rotation speed of 350r/min and the temperature of 60 ℃ to obtain amino-terminated hyperbranched polyphosphazene modified nano hydrotalcite (HBPC-LDH);
2. preparation of HBPC-LDH waterborne polyurethane (WPU/HBPC-LDH) with flame-retardant self-repairing function
3) Mixing 10 parts of polyethylene glycol, 2-dimethylolbutyric acid and isophorone diisocyanate in a ratio of 21:1:10, and reacting at 70 ℃ for 7 hours to prepare a prepolymer solution with an isocyanate group end capping;
4) adding 1.8 parts of 4, 5-dihydroxymethyl-2-phenylimidazole, cystine and HBPC-LDH in a ratio of 1:3:2 into the prepolymer solution obtained in the step 3), and reacting at 55 ℃ for 1.5h to prepare a chain extension product solution;
5) and (3) dropwise adding 0.1 part of terbium trifluoromethanesulfonate and 0.1 part of triethylamine into the chain extension product solution obtained in the step 4), reacting for 40min at 40 ℃, cooling to room temperature, adding 1000 parts of water, and emulsifying for 3h under high-speed stirring to obtain the HBPC-LDH waterborne polyurethane (WPU/HBPC-LDH) with the flame-retardant self-repairing function.
The Limited Oxygen Index (LOI) of the WPU/HBPC-LDH coating prepared by the embodiment is 21.47%, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which indicates that the coating has good flame retardant property; the WPU/HBPC-LDH coating has the tensile strength of 36.42MPa, is completely cut off, has the tensile strength of 29.73MPa after being repaired for 6 hours at room temperature, and has the repair efficiency of 81.63 percent by taking the tensile strength as an investigation index.
Example 6
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano montmorillonite (HBPC-MMT)
1) Ultrasonically dispersing 10 parts of 1000nm montmorillonite (MMT) into 1000 parts of water/ethanol mixed solution, slowly adding 0.1 part of 3-aminopropyltrimethoxysilane as a coupling agent, reacting at the rotating speed of 300r/min at 60 ℃ for 6 hours, centrifugally washing with deionized water and absolute ethyl alcohol after the reaction is finished, and then drying in vacuum to obtain the aminated nano montmorillonite (NP-MMT-NH)2)；
2) Mixing 10 parts of NP-MMT-NH2Adding the mixture into 1000 parts of tetrahydrofuran solution, and adding 100 parts of hexachlorocyclotriphosphazene and 1, 6-hexanediamine according to the feeding ratio of 1: 4; adding 1 part of triethylamine as an acid-binding agent, introducing nitrogen, and reacting for 6 hours at the rotation speed of 500r/min and the temperature of 75 ℃ to obtain amino-terminated hyperbranched polyphosphazene modified nano montmorillonite (HBPC-MMT);
2. preparation of HBPC-MMT waterborne polyurethane (WPU/HBPC-MMT) with flame-retardant self-repairing function
3) Mixing 100 parts of polyethylene glycol, 2-dimethylolpropionic acid and toluene diisocyanate in a ratio of 22:1:9, and reacting at 80 ℃ for 7 hours to prepare a prepolymer solution with an isocyanate group end capping;
4) adding 18 parts of 2-urea-4 [ H ] -pyrimidone, 2' -dihydroxy butane diselenide and HBPC-MMT in a ratio of 1:3:2 into the prepolymer solution obtained in the step 3), and reacting at 60 ℃ for 2 hours to obtain a chain extension product solution;
5) and (3) adding 0.3 part of triethylamine into the chain extension product solution obtained in the step 4), reacting for 30min at 40 ℃, cooling to room temperature, adding 1000 parts of water, and emulsifying for 2h under high-speed stirring to obtain the HBPC-MMT waterborne polyurethane (WPU/HBPC-MMT) with the flame-retardant self-repairing function.
The Limited Oxygen Index (LOI) of the WPU/HBPC-MMT coating prepared by the embodiment is 26.28%, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which indicates that the coating has good flame retardant property; the WPU/HBPC-MMT coating has the tensile strength of 43.55MPa, is completely cut off, and has the tensile strength of 41.16MPa after being repaired for 8 hours at room temperature, and the repair efficiency of the coating is 94.51 percent by taking the tensile strength as an index.
Example 7
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano two-dimensional metal organic framework film (HBPC-MOF)
1) Ultrasonically dispersing 5 parts of 1000nm two-dimensional metal organic framework film (MOF) in 500 parts of water/ethanol mixed solution, slowly adding 0.05 part of 3-aminopropyltriethoxysilane as a coupling agent, reacting at the rotating speed of 450r/min at 60 ℃ for 6 hours, centrifugally washing with deionized water and absolute ethyl alcohol after the reaction is finished, and then drying in vacuum to obtain the aminated nano two-dimensional metal organic framework film (NP-MOF-NH)2)；
2) 5 parts of NP-MOF-NH2Adding the mixture into 500 parts of tetrahydrofuran solution, and adding 40 parts of hexachlorocyclotriphosphazene and 1, 8-octanediamine according to the feeding ratio of 1: 3; adding 1 part of triethylamine as an acid-binding agent, introducing nitrogen, and reacting for 6 hours at the rotating speed of 300r/min and the temperature of 65 ℃ to obtain an amino-terminated hyperbranched polyphosphazene modified nano two-dimensional metal organic framework film (HBPC-MOF);
2. preparation of HBPC-MOF waterborne polyurethane (WPU/HBPC-MOF) with flame-retardant self-repairing function
3) Mixing 30 parts of polytetramethylene glycol, 2-dimethylolbutyric acid and 1, 6-hexamethylene diisocyanate in a ratio of 20:1:9, and reacting at 75 ℃ for 6 hours to prepare a prepolymer solution terminated by isocyanate groups;
4) adding 10 parts of 5, 6-diamino-1, 3-dimethyl uracil, 3, 5-dimethoxyphenylboronic acid and HBPC-MOF in a ratio of 1:2:2 into the prepolymer solution obtained in the step 3), and reacting at 60 ℃ for 1h to obtain a chain extension product solution;
5) adding 0.1 part of triethylamine into the chain extension product solution obtained in the step 4), reacting for 30min at 40 ℃, cooling to room temperature, adding 700 parts of water, and emulsifying for 1h under high-speed stirring to obtain the HBPC-MOF waterborne polyurethane (WPU/HBPC-MOF) with the flame retardant self-repairing function.
The Limited Oxygen Index (LOI) of the WPU/HBPC-MOF coating prepared by the embodiment is 25.06%, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which indicates that the coating has good flame retardant property; the WPU/HBPC-MOF coating has the tensile strength of 37.93MPa, is completely cut off, and has the tensile strength of 33.55MPa after being repaired for 6 hours at room temperature, and the repair efficiency of the coating is 88.45 percent by taking the tensile strength as a research index.
Example 8
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano magnesium hydroxide (HBPC-MH)
1) Ultrasonically dispersing 1 part of 1000nm Magnesium Hydroxide (MH) in 100 parts of water/ethanol mixed solution, slowly adding 0.01 part of N-2-aminoethyl-3-aminopropyltriethoxysilane as a coupling agent, reacting for 8 hours at the temperature of 70 ℃ at the rotating speed of 500r/min, centrifugally washing with deionized water and absolute ethyl alcohol after the reaction is finished, and then drying in vacuum to obtain aminated nano magnesium hydroxide (NP-MH-NH)2)；
2) Mixing 0.5 part of NP-MH-NH2Adding the mixture into 500 parts of tetrahydrofuran solution, and adding 5 parts of hexachlorocyclotriphosphazene and polyoxyethylene diamine according to the feeding ratio of 1: 4; then 0.5 part of triethylamine is added as an acid-binding agent, nitrogen is introduced, and the mixture reacts for 7 hours at the rotation speed of 450r/min and the temperature of 75 ℃ to obtain amino-terminated hyperbranched polyphosphazene modified nano magnesium hydroxide (HBPC-MH);
2. preparation of HBPC-MH waterborne polyurethane (WPU/HBPC-MH) with flame-retardant self-repairing function
3) Mixing 15 parts of polycaprolactone diol, 2-dimethylolpropionic acid and diphenylmethane diisocyanate in a ratio of 21:1:8, and reacting at 85 ℃ for 6 hours to prepare an isocyanate-terminated prepolymer solution;
4) adding 3 parts of 2, 6-diaminopyridine, 2' -diaminodiphenyl disulfide and HBPC-MH in a ratio of 1:2:3 into the prepolymer solution obtained in the step 3), and reacting at 60 ℃ for 2 hours to obtain a chain extension product solution;
5) and (3) dropwise adding 0.3 part of zinc trifluoromethanesulfonate and 0.1 part of triethylamine into the chain extension product solution obtained in the step 4), reacting for 40min at 40 ℃, cooling to room temperature, adding 500 parts of water, and emulsifying for 2h under high-speed stirring to obtain the HBPC-MH waterborne polyurethane (WPU/HBPC-MH) with the flame-retardant self-repairing function.
The Limited Oxygen Index (LOI) of the WPU/HBPC-MH coating prepared by the embodiment is 24.27%, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which indicates that the coating has good flame retardant property; the tensile strength of the WPU/HBPC-MH coating is 34.05MPa, the WPU/HBPC-MH coating is completely cut off, the tensile strength is 28.64MPa after the WPU/HBPC-MH coating is repaired for 5 hours at room temperature, the tensile strength is taken as an investigation index, and the repairing efficiency of the WPU/HBPC-MH coating is 84.11%.
The flame-retardant self-repairing type waterborne polyurethane composite coating agent prepared by the invention has the characteristics of good mechanical property, strong adhesive force, obvious self-repairing effect, excellent flame-retardant property and the like, is a composite coating agent with excellent comprehensive performance, does not need external stimulation, has high strength and good repairing effect, can protect materials at high temperature and realize high-efficiency self-healing, can be applied to various fields of buildings, aerospace, traffic, electronics and the like, and particularly can be applied to the fields of flame-retardant self-repairing coatings of wood paints and the like due to the flame-retardant and self-repairing properties. The preparation method of the reversible self-repairing coating agent has the characteristics of strong applicability, and has the advantages of high self-repairing efficiency, simple and easily-controlled preparation method, low cost and the like, and is suitable for industrial production.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. A preparation method of a flame-retardant self-repairing waterborne polyurethane composite coating agent is characterized by comprising the following steps:
1) dissolving the nano particles, adding a coupling agent for reaction, washing and drying to prepare aminated nano particles;
2) dissolving the aminated nanoparticles prepared in the step 1), and adding hexachlorocyclotriphosphazene and diamine; adding an acid-binding agent, and introducing nitrogen for reaction to prepare HBPC;
3) mixing polyester diol, a hydrophilic monomer and diisocyanate for reaction to prepare a prepolymer solution terminated by isocyanate groups;
4) adding a dynamic reversible covalent bond monomer, a dynamic reversible noncovalent bond monomer and HBPC into the prepolymer solution obtained in the step 3), and carrying out chain extension reaction to prepare a chain extension product solution;
5) adding a neutralizer into the chain extension product solution obtained in the step 4) for reaction; cooling, adding water, stirring and emulsifying to obtain the HBPC waterborne polyurethane with the flame-retardant self-repairing function.
2. The method for preparing the flame-retardant self-repairing waterborne polyurethane composite coating agent according to claim 1, wherein in the step 1), the nanoparticles are one of nano-silica, nano-titanium dioxide, graphene oxide, hydrotalcite, montmorillonite, a two-dimensional metal-organic framework film and nano-magnesium hydroxide; the coupling agent comprises one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, isopropoxytris (ethylenediamine-N-ethoxy) titanate and neoalkoxy tris (p-aminophenoxy) zirconate.
3. The preparation method of the flame-retardant self-repairing waterborne polyurethane composite coating agent as claimed in claim 1, wherein in the step 1), the reaction is carried out for 5-8 h at a rotation speed of 300-500 r/min and a temperature of 60-80 ℃; in the step 2), the reaction is carried out for 4-8 h under the conditions that the rotating speed is 300-500 r/min and the temperature is 60-80 ℃.
4. The method for preparing the flame-retardant self-repairing aqueous polyurethane composite coating agent according to claim 1, wherein the diamine in the step 2) is one or more of 1, 3-butanediamine, 1, 6-hexanediamine, 1, 8-octanediamine, 2-dimethyl-1, 3-propanediamine and polyoxyethylene diamine; the feeding ratio of the hexachlorocyclotriphosphazene to the diamine is (1-3) to (4-5).
5. The method for preparing the flame-retardant self-repairing aqueous polyurethane composite coating agent according to claim 1, wherein in the step 3), the polyester diol is one of polytetramethylene glycol, polycaprolactone diol and polyethylene glycol; the hydrophilic monomer is 2, 2-dimethylolbutyric acid or 2, 2-dimethylolpropionic acid; the diisocyanate is one of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate and diphenylmethane diisocyanate.
6. The preparation method of the flame-retardant self-repairing waterborne polyurethane composite coating agent as claimed in claim 1, wherein in the step 3), the material ratio of the polyester glycol, the hydrophilic monomer and the diisocyanate is (20-25): 1 (8-10).
7. The method for preparing the flame-retardant self-repairing aqueous polyurethane composite coating agent according to claim 1, wherein in the step 4), the dynamic reversible covalent bond monomer comprises one or more of 2,2' -dihydroxy butane diselenide, 2' -diamino diphenyl disulfide, 4' -diamino diphenyl disulfide, 3, 5-dimethoxy phenylboronic acid and cystine; the dynamic reversible non-covalent bond monomer comprises one or more of 2-urea-4 [ H ] -pyrimidone, 5, 6-diamino-1, 3-dimethyl uracil, 2, 6-diaminopyridine, 2, 6-pyridinedicarboxylic acid and 4, 5-dimethylol-2-phenylimidazole; the charge ratio of the dynamic reversible covalent bond monomer to the dynamic reversible non-covalent bond monomer to the HBPC is 1 (1-3) to 1-3; in the step 5), the neutralizing agent is one or more of triethylamine, zinc chloride, ferric chloride, terbium trifluoromethanesulfonate and zinc trifluoromethanesulfonate.
8. The preparation method of the flame-retardant self-repairing waterborne polyurethane composite coating agent as claimed in claim 1, wherein in the step 3), the reaction condition is that the reaction is carried out at the temperature of 70-90 ℃ for 5-7 h; in the step 4), the reaction condition is that the reaction is carried out for 1-2 h at the temperature of 50-70 ℃; in the step 5), the reaction condition is that the reaction is carried out for 20-40 min at the temperature of 40-60 ℃.
9. The flame-retardant self-repairing waterborne polyurethane composite coating agent is prepared by the preparation method of the flame-retardant self-repairing waterborne polyurethane composite coating agent according to any one of claims 1 to 8.
10. The flame-retardant self-repairing waterborne polyurethane composite finishing agent of claim 9 is applied to a flame-retardant self-repairing coating of wood lacquer.
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