CN114560983B - Flame-retardant self-repairing type water-based polyurethane composite finishing agent and preparation method and application thereof - Google Patents

Flame-retardant self-repairing type water-based polyurethane composite finishing agent and preparation method and application thereof Download PDF

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CN114560983B
CN114560983B CN202210158953.5A CN202210158953A CN114560983B CN 114560983 B CN114560983 B CN 114560983B CN 202210158953 A CN202210158953 A CN 202210158953A CN 114560983 B CN114560983 B CN 114560983B
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flame
hbpc
repairing
retardant self
polyurethane composite
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CN114560983A (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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    • C08G79/025—Polyphosphazenes
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Abstract

The invention discloses a flame-retardant self-repairing type water-based polyurethane composite coating agent and a preparation method and application thereof, and belongs to the technical field of coating agent production. The method prepares aminated nano particles by reacting nano particles with a coupling agent; the amination nanometer particle reacts with hexachlorocyclotriphosphazene and diamine to prepare amino-terminated hyperbranched polyphosphazene modified nanometer particle (HBPC); then mixing polyester glycol, hydrophilic monomer and diisocyanate to react to prepare isocyanate group blocked prepolymer solution; then adding a dynamic reversible covalent bond monomer, a dynamic reversible non-covalent bond monomer and HBPC into the prepolymer solution to react to prepare a chain extension product solution; adding a neutralizing agent into the chain extension product solution to react, so as to prepare the HBPC water-based polyurethane with the flame-retardant self-repairing function. The prepared flame-retardant self-repairing type water-based polyurethane composite finishing agent has a hyperbranched structure and a double reversible bond structure, can be rapidly and efficiently self-repaired at high temperature, and can be applied to flame-retardant self-repairing paint of wood lacquer.

Description

Flame-retardant self-repairing type water-based polyurethane composite finishing 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 type aqueous polyurethane composite coating agent, and a preparation method and application thereof.
Background
The aqueous polyurethane (WPU) has the characteristics of environmental protection, easy processing, high solid content, easy film formation, chemical corrosion resistance and the like, and is widely applied to the fields of leather finishing, building materials, paint and the like. But WPU flame retardant property is poor, mechanical strength is low, macroscopic damage or fracture easily occurs under the action of external force, service life and protection life can not be ensured, and requirements of people can not be met in practical application.
Currently, reactive flame retardant WPUs can be obtained by adding flame retardants to improve their flame retardant properties. For example, chinese patent (CN 108059913A) discloses a preparation method of a water-based phosphorus-silicon flame-retardant polyurethane coating material, wherein phosphorus-containing polyol and polydimethylsiloxane are used as soft segments of the WPU, so that the flame-retardant WPU is prepared. According to the national standard GB/T5455-2014, the vertical combustion test is carried out, under the synergistic flame retardant effect of phosphorus and nitrogen, the flame retardant effect of the coating can reach the B1 level when the weight of the polyester fabric is increased by 30%, but the strength of the WPU prepared by the method after film formation is lower. In improving the strength of WPU, a method of adding nanoparticles may be used, but nanoparticles of this method have poor compatibility with WPU, and thus modification of nanoparticles is required. In addition, although the strength of the WPU can be improved by adding the nano particles, damage can be avoided in the processing or using process, and the mechanical properties of the WPU are affected, so that the attractiveness and the service life of the WPU are reduced. In view of the above problems, self-healing coatings have been developed in which intrinsic self-healing materials achieve self-healing through reversible covalent bonds or reversible transformations of reversible non-covalent bonds in their molecular chain structures or between molecular chains. As disclosed in chinese patent (CN 110028686 a), a "cellulose nanocrystalline reinforced self-repairing aqueous polyurethane material and a preparation method thereof", the maleic amide group is grafted on the surface of cellulose nanocrystalline through esterification reaction, the mechanical properties of the material are obviously enhanced by adding cellulose nanocrystalline, and then the WPU material is self-repaired under the heating condition by the combined action of reversible retro-DA reaction and DA reaction. The cellulose nanocrystalline is a biological-based nanomaterial with excellent performance, has wide sources and high strength, and can enhance the self-repairing performance and mechanical property 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, development of the water-based polyurethane coating agent with excellent flame retardant property, high mechanical strength and good self-repairing function has become a problem to be solved urgently, and the water-based polyurethane coating agent has important theoretical value and practical significance for protecting life and property safety of people and prolonging the service life and the protection life of a paint film of people.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a flame-retardant self-repairing type aqueous polyurethane composite finishing agent, a preparation method and application thereof, and solve the problems of poor flame retardance, low mechanical strength and limited protective life of a paint film of a traditional aqueous polyurethane coating.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a flame-retardant self-repairing type water-based polyurethane composite finishing agent, which comprises the following steps:
1) Dissolving the nano particles, adding a coupling agent for reaction, washing and drying to obtain the amination nano particles;
2) Dissolving the amination nano particles prepared in the step 1), and adding hexachlorocyclotriphosphazene and diamine; adding an acid binding agent, and introducing nitrogen to react to obtain HBPC;
3) Mixing polyester glycol, hydrophilic monomer and diisocyanate to react to prepare isocyanate group blocked prepolymer solution;
4) Adding a dynamic reversible covalent bond monomer, a dynamic reversible non-covalent bond monomer and HBPC into the prepolymer solution obtained in the step 3) to perform a chain extension reaction to obtain a chain extension product solution;
5) Adding a neutralizing agent into the chain extension product solution obtained in the step 4) for reaction; cooling, adding water, stirring and emulsifying to obtain the HBPC aqueous polyurethane with the flame-retardant self-repairing function.
Preferably, in step 1), the nanoparticle is one of nano silicon dioxide, 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-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-2-aminoethyl-3-aminopropyl triethoxysilane, isopropoxytri (ethylenediamine-N-ethoxy) titanate and neoalkoxy tri (p-aminophenoxy) zirconate.
Preferably, in the step 1), the nano particles are 0.1 to 10 parts; 50-1000 parts of water/ethanol mixed solution; the coupling agent is 0.01-2 parts.
Preferably, in step 1), the particle size of the nanoparticle is 50 to 1000nm.
Preferably, in the step 1), the reaction condition is that the reaction is carried out for 5 to 8 hours at the rotation speed of 300 to 500r/min and the temperature of 60 to 80 ℃; in the step 2), the reaction condition is that the reaction is carried out for 4 to 8 hours under the condition that the rotating speed is 300 to 500r/min and the temperature is 60 to 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 polyoxyethylene diamine; the feed ratio of the hexachlorocyclotriphosphazene to the diamine is (1-3) and (4-5).
Preferably, in the step 2), the amount of the aminated nano particles is 0.1 to 10 parts, and the amount of the tetrahydrofuran solution is 50 to 1000 parts; the total amount of hexachlorocyclotriphosphazene and diamine is 1 to 100 parts; 0.1 to 1 part of acid binding agent.
Further preferably, in step 2), the acid binding agent is triethylamine.
Preferably, in 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 glycol, the hydrophilic monomer and the diisocyanate is (20-25): 1 (8-10).
Preferably, in step 3), the total amount of polyester diol, hydrophilic monomer and diisocyanate is 10 to 100 parts.
Preferably, in step 4), the total amount of the dynamically reversible covalent compound, the dynamically reversible non-covalent compound and the HBPC is 1 to 20 parts.
Preferably, in step 4), the dynamically 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 ] -pyrimidinone, 5, 6-diamino-1, 3-dimethyluracil, 2, 6-diaminopyridine, 2, 6-dipicolinic acid and 4, 5-dihydroxymethyl-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); in the step 5), the neutralizer is one or more of triethylamine, zinc chloride, ferric chloride, terbium trifluoromethane sulfonate and zinc trifluoromethane sulfonate.
Preferably, in step 3), the reaction conditions are that the reaction is carried out for 5 to 7 hours at a temperature of 70 to 90 ℃; in the step 4), the reaction condition is that the reaction is carried out for 1 to 2 hours at the temperature of 50 to 70 ℃; in the step 5), the reaction condition is that the reaction is carried out for 20 to 40 minutes at the temperature of 40 to 60 ℃.
Preferably, in the step 5), the neutralizing agent is 0.1-1 part; the added water is 50-1000 parts.
The invention also discloses the flame-retardant self-repairing type aqueous polyurethane composite finishing agent prepared by the preparation method of the flame-retardant self-repairing type aqueous polyurethane composite finishing agent.
The invention also discloses application of the flame-retardant self-repairing aqueous polyurethane composite coating agent in flame-retardant self-repairing paint 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 aqueous polyurethane composite finishing agent, which is prepared by amination of nano particles (NP-NH) 2 ) And (3) withThe hexachlorocyclotriphosphazene and diamine react to prepare amino-terminated hyperbranched polyphosphazene modified nano particles (HBPC), wherein 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 units can be ensured by utilizing the rich hyperbranched chain segments on the HBPC, so that the flame-retardant performance of the coating is improved, and the coating and the polyurethane chain segments can form a chemical/physical crosslinking network structure, thereby remarkably improving the mechanical strength of the coating; the compatibility and interface combination between the nano particles and the WPU matrix can be effectively improved by utilizing rich terminal amino groups on the surface of the HBPC, so that the mechanical property of a paint film is effectively improved; meanwhile, the dynamic reversible covalent bond and the dynamic reversible non-covalent bond are introduced into the WPU chain segment structure, so that the physical crosslinking effect of the reversible covalent bond and the reversible non-covalent bond can be utilized, the mechanical performance of the WPU is further improved, the mobility of the hyperbranched polymer chain segment can be utilized, and the self-repairing efficiency of the material is promoted. When the material breaks, 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, the coating can be quickly self-repaired under the room temperature condition through reversible breaking and recombination of reversible covalent bonds and reversible non-covalent bonds at the damaged part. In addition, the preparation method has the advantages of simple and easy control of the process, low cost, environmental protection, wide application range and the like, has strong practicability, and is suitable for industrial production.
Compared with the technical defect that the traditional waterborne polyurethane has flame retardant property, mechanical strength and self-repairing efficiency which 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 excellent flame retardant property and the self-repairing function of the WPU are endowed, and meanwhile, the mechanical property of the WPU is ensured. The flame-retardant self-repairing type water-based polyurethane composite finishing agent has a hyperbranched and double reversible bond structure, can be quickly and efficiently self-repaired at high temperature, has the characteristics of good stability, excellent mechanical property, obvious repairing effect and the like, has a Limiting Oxygen Index (LOI) of 20.07-26.98 percent, has self-repairing efficiency of 81.47-94.76 percent, has flame retardant grade of UL-94V-0, and has flame-retardant property and self-repairing property. The flame-retardant self-repairing type water-based polyurethane composite finishing agent provided by the invention can be applied to various fields such as construction, aerospace, traffic, electronics and the like, and can be particularly applied to the fields such as flame-retardant self-repairing paint of wood lacquer due to the flame retardance and self-repairing performance.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and in the claims are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented 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 present invention is described in further detail below:
the invention discloses a preparation method of a flame-retardant self-repairing type water-based polyurethane composite finishing agent, which comprises the following process steps:
1. preparation of amino-terminated hyperbranched polyphosphazene modified nanoparticle (HBPC)
1) Dispersing 0.1-10 parts of nano particles in 50-1000 parts of water by ultrasonic methodSlowly adding 0.01-2 parts of coupling agent into the ethanol mixed solution, reacting for 5-8 hours at the rotation speed of 300-500 r/min and the reaction temperature of 60-80 ℃, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then drying in vacuum to obtain the aminated nano particles (NP-NH) 2 )；
Wherein the nanoparticle is a nanosilicon dioxide (SiO) 2 ) Nano titanium dioxide (TiO) 2 ) One of Graphene Oxide (GO), hydrotalcite (LDH), montmorillonite (MMT), two-dimensional metal organic framework film (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-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-2-aminoethyl-3-aminopropyl triethoxysilane, isopropoxytri (ethylenediamine-N-ethoxy) titanate and neoalkoxy tri (p-aminophenoxy) zirconate;
2) 0.1 to 10 parts of NP-NH 2 Adding the mixture into 50 to 1000 parts of tetrahydrofuran solution, and adding 1 to 100 parts of hexachlorocyclotriphosphazene and diamine according to the feeding ratio of (1 to 3) to (4 to 5); 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 amino-terminated hyperbranched polyphosphazene modified nano particles (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 (polyurethane) with flame-retardant self-repairing function (WPU/HBPC)
3) Mixing 10-100 parts of polyester glycol, hydrophilic monomer and diisocyanate according to the feed ratio of (20-25) 1 (8-10), and carrying out prepolymerization reaction at 70-90 ℃ for 5-7 h to obtain 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 non-covalent bond monomer and HBPC into the prepolymer solution obtained in the step 3) according to the feeding ratio of 1 (1-3), and carrying out chain extension reaction at 50-70 ℃ for 1-2 h to obtain a chain extension product solution;
wherein the dynamic reversible covalent bond monomer is one or more of 2,2' -dihydroxybutane diselenide, 2' -diaminodiphenyl disulfide, 4' -diaminodiphenyl disulfide, 3, 5-dimethoxyphenylboric acid and cystine; the dynamic reversible non-covalent bond monomer is one or more of 2-urea-4[H ] -pyrimidinone, 5, 6-diamino-1, 3-dimethyluracil, 2, 6-diaminopyridine, 2, 6-dipicolinic 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, emulsifying for 1-3 hours under high-speed stirring to obtain HBPC aqueous polyurethane (WPU/HBPC) with flame-retardant self-repairing function;
wherein the neutralizer is one or more of triethylamine, zinc chloride, ferric chloride, terbium trifluoromethane sulfonate and zinc trifluoromethane sulfonate.
Taking silicon dioxide with the particle size of 1000nm as an example, HBPC-SiO is prepared from nano silicon dioxide, 3-aminopropyl trimethoxy silane, hexachlorocyclotriphosphazene and 1, 6-hexamethylenediamine 2 The reaction chemical formula is as follows:
Figure BDA0003513571300000081
by way of example, the reaction of polytetramethylene glycol, isophorone diisocyanate and 2, 2-dimethylolbutyric acid is carried out by adding 2-urea-4[H]Pyrimidinone, 2' -dihydroxybutane diselenide and HBPC-SiO 2 Preparation of WPU/HBPC-SiO 2 The reaction chemical formula is as follows:
Figure BDA0003513571300000091
the flame-retardant self-repairing aqueous polyurethane composite coating agent can be prepared by adopting the preparation method, and has high application value in room temperature self-repairing coating.
The invention is described in further detail below in connection with specific examples:
example 1
1. Amino-terminated hyperbranched polyphosphazene modified nano silicon dioxide (HBPC-SiO) 2 ) Is prepared from
1) 1 part of 50nm silica (SiO 2 ) Dispersing in 100 parts of water/ethanol mixed solution by ultrasonic, slowly adding 0.01 part of 3-aminopropyl trimethoxy silane as a coupling agent, reacting at 74 ℃ for 6 hours at the rotating speed of 300r/min, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then drying in vacuum to obtain the aminated nano silicon dioxide (NP-SiO) 2 -NH 2 )；
2) 0.1 part of NP-SiO 2 -NH 2 Adding into 50 parts of tetrahydrofuran solution, and adding hexachlorocyclotriphosphazene and 1, 6-hexamethylenediamine with the total amount of 5 parts according to the feeding ratio of 1:4; adding 0.5 part of triethylamine as an acid binding agent, introducing nitrogen, and reacting for 6 hours at the temperature of 65 ℃ at the rotating speed of 300r/min to obtain the amino-terminated hyperbranched polyphosphazene modified nano silicon dioxide (HBPC-SiO) 2 )；
2. HBPC-SiO with flame-retardant self-repairing function 2 Waterborne polyurethane (WPU/HBPC-SiO) 2 ) Is prepared from
3) Mixing 10 parts by weight 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 an isocyanate group-terminated prepolymer solution;
4) 2-urea-4[H in a total amount of 1 part]Pyrimidinone, 2' -dihydroxybutane diselenide and HBPC-SiO 2 Adding the mixture into the prepolymer solution obtained in the step 3) according to the ratio of 1:2:2, and reacting for 1.5 hours at 55 ℃ 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, emulsifying for 2h under high-speed stirring to obtain the HBPC-SiO with flame-retardant self-repairing function 2 Waterborne polyurethane (WPU/HBPC-SiO) 2 )。
WPU/HBPC-SiO prepared in this example 2 The Limiting Oxygen Index (LOI) of the coating is 20.07%, 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-SiO 2 The tensile strength of the coating is 38.61MPa, the coating is completely cut off, the tensile strength of the coating is 31.49MPa after the coating is repaired for 8 hours at room temperature, the tensile strength is taken as an inspection index, and the repair efficiency of the coating is 81.56%.
Example 2
1. Amino-terminated hyperbranched polyphosphazene modified nano silicon dioxide (HBPC-SiO) 2 ) Is prepared from
1) 2 parts of 1000nm silica (SiO 2 ) Dispersing in 200 parts of water/ethanol mixed solution by ultrasonic, slowly adding 0.02 part of 3-aminopropyl triethoxysilane as a coupling agent, reacting for 7 hours at 70 ℃ at a rotating speed of 300r/min, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then drying in vacuum to obtain the aminated nano silicon dioxide (NP-SiO) 2 -NH 2 )；
2) 0.1 part of NP-SiO 2 -NH 2 Adding into 50 parts of tetrahydrofuran solution, and adding 8 parts of hexachlorocyclotriphosphazene and 1, 8-octanediamine according to a feeding ratio of 3:5; adding 0.8 part of triethylamine as an acid binding agent, introducing nitrogen, and reacting for 6 hours at the temperature of 70 ℃ at the rotation speed of 500r/min to obtain the amino-terminated hyperbranched polyphosphazene modified nano silicon dioxide (HBPC-SiO) 2 )；
2. HBPC-SiO with flame-retardant self-repairing function 2 Waterborne polyurethane (WPU/HBPC-SiO) 2 ) Is prepared from
3) Mixing 100 parts by weight of polytetramethylene glycol, 2-dimethylolpropionic acid and toluene diisocyanate according to the proportion of 23:1:8, and reacting at 80 ℃ for 6 hours to prepare an isocyanate group-terminated prepolymer solution;
4) The total amount is taken15 parts of 5, 6-diamino-1, 3-dimethyluracil, 2' -diaminodiphenyl disulfide and HBPC-SiO 2 Adding the mixture into 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, emulsifying for 2h under high-speed stirring to obtain the HBPC-SiO with flame-retardant self-repairing function 2 Waterborne polyurethane (WPU/HBPC-SiO) 2 )。
WPU/HBPC-SiO prepared in this example 2 The Limiting Oxygen Index (LOI) of the coating is 26.12%, 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-SiO 2 The tensile strength of the coating is 45.89MPa, the coating is completely cut off, the tensile strength of the coating is 43.27MPa after the coating is repaired for 7 hours at room temperature, the tensile strength is taken as an inspection index, and the repair efficiency of the coating is 94.29%.
Example 3
1. Amino-terminated hyperbranched polyphosphazene modified nano titanium dioxide (HBPC-TiO) 2 ) Is prepared from
1) 1 part of 1000nm titanium dioxide (TiO 2 ) Dispersing in 100 parts of water/ethanol mixed solution by ultrasonic, slowly adding 0.01 part of N-2-aminoethyl-3-aminopropyl triethoxysilane as a coupling agent, reacting for 7 hours at 68 ℃ at a rotating speed of 350r/min, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then vacuum drying to obtain the aminated nano titanium dioxide (NP-TiO) 2 -NH 2 )；
2) 0.1 part of NP-TiO 2 -NH 2 Adding into 50 parts of tetrahydrofuran solution, and adding 1 part of hexachlorocyclotriphosphazene and 1, 3-butanediamine according to a feeding ratio of 1:4; adding 0.1 part of triethylamine as an acid binding agent, introducing nitrogen, and reacting for 8 hours at the temperature of 60 ℃ at the rotation speed of 360r/min to obtain the amino-terminated hyperbranched polyphosphazene modified nano titanium dioxide (HBPC-TiO) 2 )；
2. HBPC-TiO with flame-retardant self-repairing function 2 Waterborne polyurethane (WPU/HBPC-TiO) 2 ) Is prepared from
3) 10 parts by weight of polycaprolactone diol, 2-dimethylolbutyric acid and 1, 6-hexamethylene diisocyanate are mixed according to the proportion of 22:1:9 and reacted for 6 hours at 74 ℃ to prepare an isocyanate group-terminated prepolymer solution;
4) 1 part of 2, 6-diaminopyridine, 4' -diaminodiphenyl disulfide and HBPC-TiO 2 Adding the mixture into the prepolymer solution obtained in the step 3) according to the ratio of 1:2:2, and reacting for 1h at 60 ℃ to obtain a chain extension product solution;
5) Dripping 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 flame-retardant self-repairing function 2 Waterborne polyurethane (WPU/HBPC-TiO) 2 )。
WPU/HBPC-TiO prepared in this example 2 The Limiting Oxygen Index (LOI) of the coating is 20.83%, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, which shows that the coating has good flame retardant property; WPU/HBPC-TiO 2 The tensile strength of the coating is 37.99MPa, the coating is completely cut off, the tensile strength of the coating is 30.95MPa after the coating is repaired for 6 hours at room temperature, the tensile strength is taken as an inspection index, and the repair efficiency of the coating is 81.47%.
Example 4
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano graphene oxide (HBPC-GO)
1) Dispersing 2 parts of 1000nm Graphene Oxide (GO) in 200 parts of water/ethanol mixed solution in an ultrasonic manner, slowly adding 0.02 part of isopropyl tri (ethylenediamine-N-ethoxy) titanate as a coupling agent, reacting at 70 ℃ for 8 hours at the rotating speed of 350r/min, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then vacuum drying to obtain the aminated nano graphene oxide (NP-GO-NH) 2 )；
2) 0.1 part of NP-GO-NH 2 Adding 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; adding 0.12 part of triethylamine as an acid binding agent, introducing nitrogen, reacting for 7 hours at the temperature of 63 ℃ under the rotation speed of 400r/min,obtaining amino-terminated hyperbranched polyphosphazene modified nano graphene oxide (HBPC-GO);
2. preparation of HBPC-GO aqueous polyurethane (WPU/HBPC-GO) with flame-retardant self-repairing function
3) Mixing 100 parts by weight 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 an isocyanate group-terminated prepolymer solution;
4) Adding 20 parts of total 2, 6-pyridine dicarboxylic acid, 3, 5-dimethoxy phenylboronic acid and HBPC-GO into the prepolymer solution obtained in the step 3) according to the proportion of 1:2:2, and reacting for 1.5 hours at 55 ℃ to obtain a chain extension product solution;
5) 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 aqueous polyurethane (WPU/HBPC-GO) with the flame-retardant self-repairing function.
The Limiting 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, so 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 of the WPU/HBPC-GO coating is 42.29MPa after the WPU/HBPC-GO coating is repaired for 8 hours at room temperature, the tensile strength is taken as an investigation index, and the repair efficiency of the coating is 94.76%.
Example 5
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano hydrotalcite (HBPC-LDH)
1) Dispersing 10 parts of 50nm hydrotalcite (LDH) in 1000 parts of water/ethanol mixed solution in an ultrasonic manner, slowly adding 0.1 part of new alkoxy tri (p-aminophenoxy) zirconate serving as a coupling agent, reacting for 6 hours at 70 ℃ at a rotating speed of 400r/min, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then vacuum drying to obtain the aminated nano hydrotalcite alkene (NP-LDH-NH) 2 )；
2) 10 parts of NP-LDH-NH 2 Adding the mixture into 1000 parts of tetrahydrofuran solution, and adding 100 parts of hexachlorocyclotriphosphazene and polyoxyethylene diamine according to a feeding ratio of 1:4; and thenAdding 1 part of triethylamine as an acid binding agent, introducing nitrogen, and reacting for 5 hours at the temperature of 60 ℃ at the rotating speed of 350r/min to obtain amino-terminated hyperbranched polyphosphazene modified nano hydrotalcite (HBPC-LDH);
2. preparation of HBPC-LDH aqueous polyurethane (WPU/HBPC-LDH) with flame-retardant self-repairing function
3) Mixing 10 parts by weight 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 an isocyanate group-terminated prepolymer solution;
4) Adding 1.8 parts of total amount of 4, 5-dihydroxymethyl-2-phenylimidazole, cystine and HBPC-LDH into the prepolymer solution obtained in the step 3) according to the ratio of 1:3:2, and reacting for 1.5 hours at 55 ℃ to obtain a chain extension product solution;
5) Dropwise adding 0.1 part of terbium trifluoromethane sulfonate 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 aqueous polyurethane (WPU/HBPC-LDH) with the flame-retardant self-repairing function.
The Limiting Oxygen Index (LOI) of the WPU/HBPC-LDH coating prepared in the embodiment is 21.47%, the flame retardant grade can reach UL-94V-0 grade, and no molten drop is generated, so that the coating has good flame retardant property; the tensile strength of the WPU/HBPC-LDH coating is 36.42MPa, the WPU/HBPC-LDH coating is completely cut off, the tensile strength of the WPU/HBPC-LDH coating is 29.73MPa after the WPU/HBPC-LDH coating is repaired for 6 hours at room temperature, the tensile strength is taken as an inspection index, and the repair efficiency of the coating is 81.63%.
Example 6
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano montmorillonite (HBPC-MMT)
1) Dispersing 10 parts of 1000nm montmorillonite (MMT) in 1000 parts of water/ethanol mixed solution in an ultrasonic manner, slowly adding 0.1 part of 3-aminopropyl trimethoxy silane as a coupling agent, reacting at a speed of 300r/min at 60 ℃ for 6 hours, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then vacuum drying to obtain the aminated nano montmorillonite (NP-MMT-NH) 2 )；
2) 10 parts of NP-MMT-NH 2 Added to 1000 parts of tetrahydrofuranAdding 100 parts of hexachlorocyclotriphosphazene and 1, 6-hexamethylenediamine into the pyran solution according to a feeding ratio of 1:4; adding 1 part of triethylamine as an acid binding agent, introducing nitrogen, and reacting for 6 hours at the temperature of 75 ℃ at the rotation speed of 500r/min 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 polyethylene glycol, 2-dimethylolpropionic acid and toluene diisocyanate with the total amount of 100 parts in a ratio of 22:1:9, and reacting at 80 ℃ for 7 hours to prepare an isocyanate group-terminated prepolymer solution;
4) Adding 18 parts of 2-urea-4[H ] -pyrimidinone, 2' -dihydroxybutane diselenide and HBPC-MMT into the prepolymer solution obtained in the step 3) according to the ratio of 1:3:2, and reacting for 2 hours at 60 ℃ 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 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 aqueous polyurethane (WPU/HBPC-MMT) with the flame-retardant self-repairing function.
The Limiting 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, so that the coating has good flame retardant property; the tensile strength of the WPU/HBPC-MMT coating is 43.55MPa, the WPU/HBPC-MMT coating is completely cut off, the tensile strength of the WPU/HBPC-MMT coating is 41.16MPa after the WPU/HBPC-MMT coating is repaired for 8 hours at room temperature, the tensile strength is taken as an investigation index, and the repair efficiency of the coating is 94.51%.
Example 7
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano two-dimensional metal organic framework film (HBPC-MOF)
1) Dispersing 5 parts of 1000nm two-dimensional metal organic frame film (MOF) in 500 parts of water/ethanol mixed solution by ultrasonic, slowly adding 0.05 part of 3-aminopropyl triethoxysilane as a coupling agent, reacting at 60 ℃ for 6 hours at the rotating speed of 450r/min, centrifugally washing with deionized water and absolute ethanol after the reaction is finished, and then vacuum drying to obtain the aminated nano two-dimensional metal organic frameFrame film (NP-MOF-NH) 2 )；
2) 5 parts of NP-MOF-NH 2 Adding the mixture into 500 parts of tetrahydrofuran solution, and adding hexachlorocyclotriphosphazene and 1, 8-octanediamine with the total amount of 40 parts according to the feed ratio of 1:3; adding 1 part of triethylamine as an acid binding agent, introducing nitrogen, and reacting for 6 hours at the temperature of 65 ℃ at the rotating speed of 300r/min to obtain an amino-terminated hyperbranched polyphosphazene modified nano two-dimensional metal organic framework film (HBPC-MOF);
2. preparation of HBPC-MOF aqueous polyurethane (WPU/HBPC-MOF) with flame-retardant self-repairing function
3) Mixing 30 parts by weight 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 an isocyanate group-terminated prepolymer solution;
4) Adding 10 parts of total amount of 5, 6-diamino-1, 3-dimethyluracil, 3, 5-dimethoxy phenylboronic acid and HBPC-MOF into the prepolymer solution obtained in the step 3) according to the proportion of 1:2:2, and reacting for 1h at 60 ℃ to prepare 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 aqueous polyurethane (WPU/HBPC-MOF) with the flame-retardant self-repairing function.
The Limiting 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 tensile strength of the WPU/HBPC-MOF coating is 37.93MPa, the WPU/HBPC-MOF coating is completely cut off, the tensile strength of the WPU/HBPC-MOF coating is 33.55MPa after the WPU/HBPC-MOF coating is repaired for 6 hours at room temperature, the tensile strength is taken as an inspection index, and the repair efficiency of the coating is 88.45%.
Example 8
1. Preparation of amino-terminated hyperbranched polyphosphazene modified nano magnesium hydroxide (HBPC-MH)
1) 1 part of 1000nm Magnesium Hydroxide (MH) is dispersed in 100 parts of water/ethanol mixed solution by ultrasonic, 0.01 part of N-2-aminoethyl-3-aminopropyl triethoxysilane is slowly added as a coupling agent to react at 70 ℃ at a rotating speed of 500r/minAfter the reaction is finished, centrifugal washing is carried out by deionized water and absolute ethyl alcohol for 8 hours, and then vacuum drying is carried out, thus obtaining the aminated nano magnesium hydroxide (NP-MH-NH) 2 )；
2) 0.5 part of NP-MH-NH 2 Adding into 500 parts of tetrahydrofuran solution, and adding 5 parts of hexachlorocyclotriphosphazene and polyoxyethylene diamine according to a feeding ratio of 1:4; adding 0.5 part of triethylamine as an acid binding agent, introducing nitrogen, and reacting for 7 hours at the temperature of 75 ℃ at the rotation speed of 450r/min 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 by weight 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 group-terminated prepolymer solution;
4) Adding 3 parts of 2, 6-diaminopyridine, 2' -diaminodiphenyl disulfide and HBPC-MH into the prepolymer solution obtained in the step 3) according to the proportion of 1:2:3, and reacting for 2 hours at 60 ℃ to obtain a chain extension product solution;
5) And (3) dropwise adding 0.3 part of zinc trifluoromethane sulfonate 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 Limiting 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, so 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 of the WPU/HBPC-MH coating 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 repair efficiency of the coating is 84.11%.
The flame-retardant self-repairing type water-based polyurethane composite finishing 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 finishing agent with excellent comprehensive properties, does not need external stimulation, has high strength and good repairing effect, can protect materials at high temperature and realize high-efficiency self-healing, and can be applied to various fields of construction, aerospace, traffic, electronics and the like. The preparation method of the reversible self-repairing finishing 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 is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. The preparation method of the flame-retardant self-repairing type water-based polyurethane composite finishing agent is characterized by comprising the following steps of:
1) Dissolving the nano particles, adding a coupling agent for reaction, washing and drying to obtain the amination nano particles;
2) Dissolving the amination nano particles prepared in the step 1), and adding hexachlorocyclotriphosphazene and diamine; adding an acid binding agent, and introducing nitrogen to react to obtain HBPC;
3) Mixing polyester glycol, hydrophilic monomer and diisocyanate to react to prepare isocyanate group blocked prepolymer solution;
4) Adding a dynamic reversible covalent bond monomer, a dynamic reversible non-covalent bond monomer and HBPC into the prepolymer solution obtained in the step 3) to perform a chain extension reaction to obtain a chain extension product solution;
5) Adding a neutralizing agent into the chain extension product solution obtained in the step 4) for reaction; cooling, adding water, stirring and emulsifying to obtain the HBPC aqueous polyurethane with the flame-retardant self-repairing function.
2. The method for preparing the flame-retardant self-repairing type water-based polyurethane composite finishing agent according to claim 1, wherein in the step 1), the nano particles are one of nano silicon dioxide, 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-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-2-aminoethyl-3-aminopropyl triethoxysilane, isopropoxytri (ethylenediamine-N-ethoxy) titanate and neoalkoxy tri (p-aminophenoxy) zirconate.
3. The method for preparing the flame-retardant self-repairing aqueous polyurethane composite finishing agent according to claim 1, wherein in the step 1), the reaction condition is that the reaction is carried out at the temperature of 60-80 ℃ and the rotation speed of 300-500 r/min and the reaction temperature of 5-8 h; in the step 2), the reaction condition is that the reaction is carried out under the condition of the rotating speed of 300-500 r/min and the temperature of 60-80 ℃ of 4-8 h.
4. The method for preparing the flame-retardant self-repairing aqueous polyurethane composite finishing 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 feed ratio of the hexachlorocyclotriphosphazene to the diamine is (1-3) and (4-5).
5. The method for preparing the flame-retardant self-repairing type water-based polyurethane composite finishing agent according to claim 1, wherein in the step 3), 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 method for preparing the flame-retardant self-repairing aqueous polyurethane composite finishing agent according to claim 1, wherein in the step 3), the feeding ratio of the polyester glycol to the hydrophilic monomer to the diisocyanate is (20-25): 1 (8-10).
7. The method for preparing the flame-retardant self-repairing aqueous polyurethane composite finishing agent according to claim 1, wherein in the 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-dimethoxyphenylboric acid and cystine; the dynamic reversible non-covalent bond monomer comprises one or more of 2-urea-4[H ] -pyrimidinone, 5, 6-diamino-1, 3-dimethyluracil, 2, 6-diaminopyridine, 2, 6-dipicolinic acid and 4, 5-dihydroxymethyl-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); in the step 5), the neutralizer is one or more of triethylamine, zinc chloride, ferric chloride, terbium trifluoromethane sulfonate and zinc trifluoromethane sulfonate.
8. The method for preparing the flame-retardant self-repairing aqueous polyurethane composite finishing agent according to claim 1, wherein in the step 3), the reaction condition is that 5-7 h is reacted at the temperature of 70-90 ℃; in the step 4), the reaction condition is that 1-2 h is reacted 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 aqueous polyurethane composite finishing agent prepared by the preparation method of the flame-retardant self-repairing aqueous polyurethane composite finishing agent according to any one of claims 1-8.
10. The use of the flame retardant self-repairing aqueous polyurethane composite finishing agent of claim 9 in flame retardant self-repairing paint of wood lacquer.
CN202210158953.5A 2022-02-21 2022-02-21 Flame-retardant self-repairing type water-based polyurethane composite finishing agent and preparation method and application thereof Active CN114560983B (en)

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CN116042173B (en) * 2023-02-14 2023-08-25 安徽斯迈特新材料股份有限公司 Alkali-resistant self-leveling silicone sealant and production process thereof
CN116396536B (en) * 2023-03-22 2024-05-28 中国安全生产科学研究院 Preparation method and application of multi-component core-shell structure flame retardant
CN116694204A (en) * 2023-04-12 2023-09-05 北京理工大学 Flame-retardant impact-resistant polyurea coating based on modified ammonium polyphosphate/two-dimensional nano filler reinforcement and preparation method thereof
CN117304790B (en) * 2023-11-27 2024-02-09 石狮佳南热熔胶有限公司 Water-based environment-friendly paint and water-based leather
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