A surface repair agent, a method for preparing the same, and a method for repairing a surface of an inflatable

Abstract

The application belongs to the field of repairing agents, and particularly relates to a surface repairing agent, a preparation method thereof and a surface repairing method for inflatable objects. The surface repairing agent comprises, in mass parts, 5-10 parts of a yellowing-resistant fluorine-containing polyurethane, 0.5-2 parts of an antioxidant, 1-2 parts of an ultraviolet absorber, 0.5-1 part of a hydrolysis stabilizer, 2-3 parts of a mildew-proof agent, 0.5-1 part of a flame retardant and 79-90 parts of a volatile organic solvent. The yellowing-resistant fluorine-containing polyurethane has a chemical structure as shown in formula (I). The volatile organic solvent has a boiling point of less than or equal to 90 DEG C. The surface repairing agent is suitable for rapid repairing of surface defects of inflatable objects, and has the advantages of fast repairing speed, high repairing efficiency, long-lasting repairing effect, high adhesive strength, good rubbing resistance and good yellowing resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of repair agents, and particularly relates to a surface repair agent, a preparation method thereof and a surface repair method for an inflatable object. BACKGROUND

[0002] The inflatable object refers to a structure in which air, helium or the like is filled into a film product or a fabric / film laminated composite made of a high polymer material to form a closed space, and mainly includes airships, tethered balloons, inflatable decoys, inflatable membrane structures and the like. The inflatable object has the characteristics of light weight, high strength, fatigue resistance, distortion resistance, good load bearing effect, easy storage and retrieval, long service life and the like, and has been widely applied at present.

[0003] The airships and tethered balloons and the like floaters rely on the buoyancy generated by the gas (such as helium) lighter than air to realize hovering, carry various types of payloads, and cover the monitoring visual area by using the hovering height, and have wide applications in the fields of traffic transportation, environmental monitoring, communication broadcasting, comprehensive remote sensing, air early warning and the like. The floater is a multi-layer composite structure, and the outermost layer is a weather-resistant layer, and the constituent material thereof is usually PVF, PVDF, TPU and the like.

[0004] The inflatable decoy is an important weapon equipment in the modern army, and has multiple advantages such as light weight, convenient transportation, fast erection and withdrawal and the like, and is made according to the 1:1 ratio of the weapon equipment, can simulate the real weapon equipment, and can confuse the enemy under the monitoring of the modernized reconnaissance equipment such as infrared, thermal imaging and radar, so as to achieve the demand of performing deceptive tactics / strategy in the modern war. The inflatable decoy in the prior art is mostly made of the blended textile as the base fabric of the radar high-reflection coating cloth, and is made by direct coating or composite flexible gas-resistant PVC film.

[0005] The inflatable membrane structure is usually made of a fabric base material and a PVF or PVDF coating layer, and is mainly used in the fields of the building industry, mobile hangars, boat houses, tents and inflatable boats and the like. Due to the flexibility and light weight of the film material, the inflatable membrane structure meets the demand of large-span space, and is often used in large-area operation workshops, warehouses, sports venues, exhibition halls and the like.

[0006] At present, the inflatable object has been widely applied in daily life and military fields, but the inflatable object is inevitably subjected to friction, wear and tear and folding damage in the process of processing, storage, use and transfer, and these damages will cause cracks on the surface of the inflatable object, become the gas leakage channels, and further seriously affect the use and operation of the inflatable object. Among them, the airships and tethered balloons and the like floaters are particularly sensitive to surface defects, and the tiny cracks will also become helium leakage channels, and further seriously affect the hovering performance of the floater.

[0007] Therefore, it is necessary to develop an inflatables surface repairing agent with fast repairing speed, high repairing efficiency, long-lasting repairing effect, high bonding strength, good rubbing resistance and good yellowing resistance. SUMMARY

[0008] Therefore, the present application provides a surface repairing agent, a preparation method of the surface repairing agent and a surface repairing method of inflatables.

[0009] The surface repairing agent comprises, in mass fraction, the following components:

[0010]

[0011] The chemical structure of the yellowing-resistant fluorine-containing polyurethane is shown in formula (I):

[0012]

[0013] In formula (I), m and n represent polymers.

[0014] The boiling point of the volatile organic solvent is less than or equal to 90 DEG C.

[0015] Preferably, the number average molecular weight of the yellowing-resistant fluorine-containing polyurethane is 30,000-100,000; and the number average molecular weight corresponding to the structure of the compound in formula (I) is 1,000-2,000.

[0016] Preferably, the volatile organic solvent is one or more of diethyl ether, ethyl acetate and acetone.

[0017] Preferably, the antioxidant is one or more of 3,5-di-tert-butyl-4-hydroxyphenyl propionate octadecanol, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and tris(2,4-di-tert-butylphenyl) phosphite.

[0018] The ultraviolet absorber is one or more of phenyl o-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole and 2,4-dihydroxybenzophenone.

[0019] The hydrolysis stabilizer is carbodiimide and / or N-phenyl-β-naphthylamine.

[0020] The mildew-proof agent is n-dichloroethylene salicylamide and / or N-octyl-4-isothiazoline-3-ketone.

[0021] ​The flame retardant is one or more of tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate and dimethyl methylphosphonate.

[0022] Preferably, the components of the surface repair agent further include 0.5-2 parts by mass of a yellowing-resistant agent;

[0023] The yellowing-resistant agent is one or more of Fisorb L-9322, V-920 and UV-1260.

[0024] Preferably, the surface repair agent is a spray-type surface repair agent.

[0025] The present application also provides a preparation method of a surface repair agent, comprising the following steps:

[0026] Mixing 5-10 parts by mass of a yellowing-resistant fluorine-containing polyurethane, 0.5-2 parts by mass of an antioxidant, 1-2 parts by mass of an ultraviolet absorber, 0.5-1 part by mass of a hydrolysis stabilizer, 2-3 parts by mass of a mildew-proof agent, 0.5-1 part by mass of a flame retardant and 79-90 parts by mass of a volatile organic solvent to obtain a surface repair agent;

[0027] The chemical structure of the yellowing-resistant fluorine-containing polyurethane is shown in formula (I):

[0028]

[0029] In formula (I), m and n represent a polymer;

[0030] The boiling point of the volatile organic solvent is ≤90℃.

[0031] Preferably, the yellowing-resistant fluorine-containing polyurethane is prepared by the following steps:

[0032] a) Pre-polymerizing polytetrahydrofuran diol and hexamethylene diisocyanate to obtain a polyurethane prepolymer;

[0033] b) Polymerizing the polyurethane prepolymer with 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol to obtain a yellowing-resistant fluorine-containing polyurethane with the structure of formula (I).

[0034] Preferably, in step a), the molar ratio of the polytetrahydrofuran diol in terms of the number of hydroxyl groups to the hexamethylene diisocyanate in terms of the number of isocyanate groups is 1:2; the temperature of the pre-polymerization is 60-100℃, and the time of the pre-polymerization is 2-4h;

[0035] In step b), the molar ratio of the polyurethane prepolymer to the 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol, calculated based on the isocyanate group number, is 1:1; the temperature of the polymerization is 100-140℃, and the time of the polymerization is 2-8h.

[0036] The application further provides a surface repairing method of an inflatable object, comprising the following steps:

[0037] applying a repairing agent to the area to be repaired on the surface of the inflatable object and placing for a period of time until the applied repairing agent is solidified;

[0038] The repairing agent is the surface repairing agent prepared by the preparation method described in the above technical solution.

[0039] Preferably, the material of the surface of the inflatable object is one or more of polyvinyl fluoride, polyvinylidene fluoride, polyurethane and polyvinyl chloride.

[0040] Compared with the prior art, the application provides a surface repairing agent, a preparation method thereof and a surface repairing method of an inflatable object. The surface repairing agent provided by the application comprises, in mass parts, 5-10 parts of a yellowing-resistant fluorine-containing polyurethane, 0.5-2 parts of an antioxidant, 1-2 parts of an ultraviolet absorber, 0.5-1 part of a hydrolysis stabilizer, 2-3 parts of a mildew-proof agent, 0.5-1 part of a flame retardant and 79-90 parts of a volatile organic solvent. The chemical structure of the yellowing-resistant fluorine-containing polyurethane is shown in formula (I). The boiling point of the volatile organic solvent is ≤90℃. The application optimizes the composition of the surface repairing agent, and particularly adds the volatile organic solvent and the yellowing-resistant fluorine-containing polyurethane with the specific chemical structure, thereby significantly improving the comprehensive performance of the surface repairing agent. The surface repairing agent provided by the application can be applied to the rapid repairing of surface defects of an inflatable object with a surface material of PVF, PVDF, PU, PVC or the like. The repairing can be completed after spraying and placing for 2-5 minutes, and the surface repairing agent has the advantages of fast repairing speed, high repairing efficiency, long-lasting repairing effect, high adhesive strength, wide application range, excellent elasticity, good rubbing resistance, good yellowing resistance and low cost. BRIEF DESCRIPTION OF DRAWINGS

[0041] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description are only the embodiments of the application, and for those skilled in the art, other drawings can also be obtained without creative labor based on the provided drawings.

[0042] Figure 1A synthetic route of the yellowing-resistant fluorine-containing polyurethane of formula (I) provided in the embodiment of the present application is shown in the following chart:

[0043] Figure 2 A digital photograph of the capsule material with three puncture marks (0.6 mm in diameter) in Example 1 of the present application is shown in the following chart:

[0044] Figure 3 A digital photograph of the repaired capsule material in Example 1 of the present application is shown in the following chart:

[0045] Figure 4 A digital photograph of the capsule material with wallpaper knife scratch marks in Example 4 of the present application is shown in the following chart:

[0046] Figure 5 A digital photograph of the repaired capsule material in Example 4 of the present application is shown in the following chart:

[0047] Figure 6 A digital photograph of the capsule material with wear defects in Example 10 of the present application is shown in the following chart:

[0048] Figure 7 A digital photograph of the repaired capsule material in Example 10 of the present application is shown in the following chart:

[0049] Figure 8 A surface state chart of the repaired capsule material in Example 1 of the present application after xenon lamp aging is shown in the following chart:

[0050] Figure 9 A surface state chart of the repaired capsule material in Example 11 of the present application after xenon lamp aging is shown in the following chart:

[0051] Figure 10 A surface state chart of the repaired capsule material in Comparative Example 2 of the present application after xenon lamp aging is shown in the following chart. DETAILED DESCRIPTION

[0052] The technical solutions in the embodiments of the present application are described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts fall within the protection scope of the present application.

[0053] The present application provides a surface repair agent, the components of which include, in mass parts:

[0054]

[0055] In the surface repair agent provided in the present application, the chemical structure of the yellowing-resistant fluorine-containing polyurethane is shown in formula (I):

[0056]

[0057] In formula (I), m and n represent a polymer.

[0058] In the surface repair agent provided by the present application, the number average molecular weight of the yellowing-resistant fluorine-containing polyurethane is preferably 30000-100000, and can be specifically 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, 70000, 75000, 80000, 85000, 90000, 95000 or 100000.

[0059] In the surface repair agent provided by the present application, the number average molecular weight of the yellowing-resistant fluorine-containing polyurethane is preferably 30000-100000, and can be specifically 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, 70000, 75000, 80000, 85000, 90000, 95000 or 100000. The structure corresponds to a number average molecular weight of 1000-2000, and can be specifically 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000.

[0060] In the surface repair agent provided by the present application, the content of the yellowing-resistant fluorine-containing polyurethane in the surface repair agent can be specifically 5 parts by mass, 5.5 parts by mass, 6 parts by mass, 6.5 parts by mass, 7 parts by mass, 7.5 parts by mass, 8 parts by mass, 8.5 parts by mass, 9 parts by mass, 9.5 parts by mass or 10 parts by mass.

[0061] In the surface repair agent provided by the present application, the antioxidant is preferably one or more of octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate (1076), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010) and tris(2,4-di-tert-butylphenyl) phosphite (168).

[0062] In the surface repair agent provided by the present application, the content of the antioxidant in the surface repair agent can be specifically 0.5 parts by mass, 0.6 parts by mass, 0.7 parts by mass, 0.8 parts by mass, 0.9 parts by mass, 1 part by mass, 1.1 parts by mass, 1.2 parts by mass, 1.3 parts by mass, 1.4 parts by mass, 1.5 parts by mass, 1.6 parts by mass, 1.7 parts by mass, 1.8 parts by mass, 1.9 parts by mass or 2 parts by mass.

[0063] In the surface repair agent provided by the present application, the ultraviolet absorber is preferably one or more of phenyl o-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2,4-dihydroxybenzophenone.

[0064] In the surface repair agent provided in the present application, the content of the ultraviolet absorber in the surface repair agent can be specifically 1 part by mass, 1.1 parts by mass, 1.2 parts by mass, 1.3 parts by mass, 1.4 parts by mass, 1.5 parts by mass, 1.6 parts by mass, 1.7 parts by mass, 1.8 parts by mass, 1.9 parts by mass, or 2 parts by mass.

[0065] In the surface repair agent provided in the present application, the hydrolysis stabilizer is preferably a carbodiimide and / or N-phenyl-β-naphthylamine.

[0066] In the surface repair agent provided in the present application, the content of the hydrolysis stabilizer in the surface repair agent can be specifically 0.5 parts by mass, 0.55 parts by mass, 0.6 parts by mass, 0.65 parts by mass, 0.7 parts by mass, 0.75 parts by mass, 0.8 parts by mass, 0.85 parts by mass, 0.9 parts by mass, 0.95 parts by mass, or 1 part by mass.

[0067] In the surface repair agent provided in the present application, the antifungal agent is preferably n-dichloroethylene salicylamide and / or N-octyl-4-isothiazolin-3-one.

[0068] In the surface repair agent provided in the present application, the content of the antifungal agent in the surface repair agent can be specifically 2 parts by mass, 2.1 parts by mass, 2.2 parts by mass, 2.3 parts by mass, 2.4 parts by mass, 2.5 parts by mass, 2.6 parts by mass, 2.7 parts by mass, 2.8 parts by mass, 2.9 parts by mass, or 3 parts by mass.

[0069] In the surface repair agent provided in the present application, the flame retardant is preferably one or more of tris(2-chloroethyl) phosphate (TCEP), tris(2-chloropropyl) phosphate (TCPP), and dimethyl methylphosphonate (DMMP).

[0070] In the surface repair agent provided in the present application, the content of the flame retardant in the surface repair agent can be specifically 0.5 parts by mass, 0.55 parts by mass, 0.6 parts by mass, 0.65 parts by mass, 0.7 parts by mass, 0.75 parts by mass, 0.8 parts by mass, 0.85 parts by mass, 0.9 parts by mass, 0.95 parts by mass, or 1 part by mass.

[0071] In the surface repair agent provided in the present application, the boiling point of the boiling point solvent is ≤90°C, preferably 30-80°C; the volatile organic solvent is preferably one or more of diethyl ether (boiling point 34°C), ethyl acetate (boiling point 77°C), and acetone (boiling point 56°C). In an embodiment provided in the present application, the volatile organic solvent is a mixture of ethyl acetate and acetone, and the mass ratio of ethyl acetate to acetone is preferably 1:(0.5-2), more preferably 1:1.

[0072] In the surface repair agent provided in the present application, the content of the boiling point solvent in the surface repair agent is specifically 79 parts by mass, 79.5 parts by mass, 80 parts by mass, 80.5 parts by mass, 81 parts by mass, 81.5 parts by mass, 82 parts by mass, 82.5 parts by mass, 83 parts by mass, 83.5 parts by mass, 84 parts by mass, 84.5 parts by mass, 85 parts by mass, 85.5 parts by mass, 86 parts by mass, 86.5 parts by mass, 87 parts by mass, 87.5 parts by mass, 88 parts by mass, 88.5 parts by mass, 89 parts by mass, 89.5 parts by mass, or 90 parts by mass.

[0073] In the surface repair agent provided in the present application, the components of the surface repair agent preferably further include a yellowing-resistant agent, and the brand of the yellowing-resistant agent is preferably one or more of Fisorb L-9322, V-920, and UV-1260.

[0074] In the surface repair agent provided in the present application, the content of the yellowing-resistant agent in the surface repair agent is preferably 0.5-2 parts by mass, and specifically 0.5 parts by mass, 0.6 parts by mass, 0.7 parts by mass, 0.8 parts by mass, 0.9 parts by mass, 1 part by mass, 1.1 parts by mass, 1.2 parts by mass, 1.3 parts by mass, 1.4 parts by mass, 1.5 parts by mass, 1.6 parts by mass, 1.7 parts by mass, 1.8 parts by mass, 1.9 parts by mass, or 2 parts by mass.

[0075] In the surface repair agent provided in the present application, the total content of the yellowing-resistant type fluorine-containing polyurethane, the antioxidant, the ultraviolet absorber, the hydrolysis stabilizer, the mildew-proof agent, the yellowing-resistant agent, the flame retardant, and the volatile organic solvent in the surface repair agent is preferably 100 parts by mass.

[0076] In the present application, in order to facilitate the operation and use of the surface repair agent, the surface repair agent is preferably a spray-type surface repair agent.

[0077] The surface repair agent provided in the present application can be applied to the rapid repair of surface defects of inflatable objects with surface materials being PVF, PVDF, PU, PVC, etc., and the repair can be completed after spraying and placing for 2-5 minutes, and the surface repair agent has the advantages of fast repair speed, high repair efficiency, long-lasting repair effect, high adhesive strength, wide application range, excellent elasticity, good rubbing resistance, good yellowing resistance, and low cost.

[0078] The present application also provides a preparation method of the surface repair agent described in the above technical solution, which comprises the following steps:

[0079] The yellowing-resistant type fluorine-containing polyurethane, the antioxidant, the ultraviolet absorber, the hydrolysis stabilizer, the mildew-proof agent, the yellowing-resistant agent, the flame retardant, and the volatile organic solvent are mixed according to the mass ratio to obtain the surface repair agent.

[0080] In the preparation method provided by the present application, the yellowing-resistant fluorine-containing polyurethane is preferably prepared according to the following steps:

[0081] a) Pre-polymerization of polytetramethylene glycol (PTMG) and hexamethylene diisocyanate (HDI) to obtain a polyurethane prepolymer;

[0082] b) Polymerization of the polyurethane prepolymer with 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol to obtain a yellowing-resistant fluorine-containing polyurethane of formula (I).

[0083] In the above preparation steps of the yellowing-resistant fluorine-containing polyurethane provided by the present application, the synthesis route of the yellowing-resistant fluorine-containing polyurethane is specifically as follows: Figure 1 , Figure 1 is a synthesis route diagram of the yellowing-resistant fluorine-containing polyurethane of formula (I) provided by the present application.

[0084] In the above preparation steps of the yellowing-resistant fluorine-containing polyurethane provided by the present application, in step a), the molar ratio of the polytetramethylene glycol counted by the number of hydroxyl groups to the hexamethylene diisocyanate counted by the number of isocyanate groups is preferably 1:2; the pre-polymerization is carried out in a protective gas atmosphere, and the protective gas is preferably nitrogen; the temperature of the pre-polymerization is preferably 60-100℃, and specifically can be 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or 100℃; and the time of the pre-polymerization is preferably 2-4h, and specifically can be 2h, 2.3h, 2.5h, 2.7h, 3h, 3.2h, 3.5h, 3.7h or 4h.

[0085] In the above preparation steps of the yellowing-resistant fluorine-containing polyurethane provided by the present application, in step b), the molar ratio of the polyurethane prepolymer counted by the number of isocyanate groups to the 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol counted by the number of hydroxyl groups is preferably 1:1; the content of isocyanate groups in the polyurethane prepolymer is preferably obtained by titration with di-n-butylamine; the temperature of the polymerization is preferably 100-140℃, and specifically can be 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃ or 140℃; and the time of the polymerization is preferably 2-8h, and specifically can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h.

[0086] In the preparation method provided by the application, the yellowing-resistant fluorine-containing polyurethane is preferably subjected to a drying treatment before participating in the mixing; the temperature of the drying treatment is preferably 100-140 DEG C, and can be specifically 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C or 140 DEG C; and the time of the drying treatment is preferably 2-10 h, and can be specifically 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h.

[0087] In the preparation method provided by the application, the raw materials are preferably added with a certain amount of yellowing-resistant agent during the mixing.

[0088] In the preparation method provided by the application, the mixed product is preferably subjected to a filling; the capacity of the filling bottle is preferably 500 mL; the pressure of the filling is preferably set to 0.1-0.2 MPa; the time of single-bottle filling is preferably set to 15-20 s; and the filling amount of a single bottle is preferably 400-450 mL.

[0089] The preparation method provided by the application can prepare a surface repair agent with fast repair speed, high repair efficiency, long-lasting repair effect, high bonding strength, good rubbing resistance and good yellowing resistance, and is particularly suitable for the rapid repair of surface defects of an inflatable object.

[0090] The application further provides a surface repair method for an inflatable object, comprising the following steps:

[0091] Coating the repair agent on the surface of the inflatable object to be repaired and placing for a period of time until the coated repair agent is solidified;

[0092] The repair agent is the surface repair agent described in the above technical solution or prepared by the preparation method described in the above technical solution.

[0093] In the surface repair method provided by the application, the inflatable object includes but is not limited to a stratospheric airship, a tethered balloon or an inflatable membrane structure; and the material of the surface of the inflatable object is preferably one or more of polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polyurethane (PU) and polyvinyl chloride (PVC).

[0094] In the surface repair method provided by the application, the area of the surface of the inflatable object to be repaired refers to an area with defects, and the defects include but are not limited to needle puncture, knife scratch or wear; after the area to be repaired is determined, the surface of the target area is preferably subjected to a cleaning treatment to remove impurities and dirt such as dust and moisture, and keep the material surface clean.

[0095] In the surface repair method provided by the application, the coating method is preferably spraying, and the spraying distance is preferably controlled to be 20-30 cm.

[0096] In the surface repairing method provided by the application, the coating of the repairing agent should be thin and uniform to ensure that the repaired material surface is completely infiltrated and air bubbles are avoided.

[0097] In the surface repairing method provided by the application, the placement time is preferably 2-5 min, and can be 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min or 5 min.

[0098] The surface repairing method provided by the application can quickly repair the surface defects of the inflatable object, has high repairing efficiency and good repairing effect. Experimental results show that, after the inflatable object surface defects are repaired by the method provided by the application, the air permeability of the repaired inflatable object is (0.4-7) L / m 2 ·24h·atm; the peeling strength between the repairing agent and the repaired inflatable object surface can reach 1.0-2.5 kN / m; after the inflatable object is repaired and rubbed 100-200 times at room temperature, the air permeability is (0.5-8) L / m 2 ·24h·atm; after the inflatable object is repaired and subjected to high-low temperature cycles (high-low temperature cycles: -70℃-60℃, temperature change rate 5℃ / min, high and low temperatures are balanced for 60 min respectively, 20 cycles), the air permeability is (0.4-7) L / m 2 ·24h·atm.

[0099] For a clearer understanding, the following examples and comparative examples are described in detail.

[0100] Example 1

[0101] The example provides a spray type inflatable object surface repairing agent with a solute mass fraction of 10%, which is prepared by mixing the following raw materials in parts by mass: 5 parts of a yellowing-resistant fluorine-containing polyurethane, 0.5 parts of an antioxidant 1076, 1 part of an ultraviolet absorber phenyl salicylate, 0.5 parts of a hydrolysis stabilizer carbodiimide, 2 parts of a mildew-resistant agent n-dichloroethylene salicylamide, 0.5 parts of a yellowing-resistant agent Fisorb L-9322, 0.5 parts of a flame retardant TCEP, and 90 parts of a volatile organic solvent ethyl acetate.

[0102] The yellowing-resistant fluorine-containing polyurethane in the repairing agent is prepared as follows:

[0103] (1) Put the previously dehydrated PTMG (M n =1000) and HDI into a three-necked flask equipped with mechanical stirring, N2 protection and a constant-pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 60℃ for 4h under the protection of N2 atmosphere to obtain a polyurethane prepolymer;

[0104] (2) After the end of prepolymerization, NCO% titration is carried out by using di-n-butylamine method, then a metering ratio of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added, and the system temperature is gradually increased to 120°C, and the reaction is stopped after 2 hours, so that a yellowing-resistant fluorine-containing polyurethane FPU with M n = 30000.

[0105] The preparation method of the spray type inflatable surface repair agent is as follows:

[0106] (1) The prepared yellowing-resistant fluorine-containing polyurethane is placed in a 120°C oven for 6 hours for drying treatment;

[0107] (2) The dried yellowing-resistant fluorine-containing polyurethane particles are respectively mixed with antioxidants, ultraviolet absorbers, hydrolysis stabilizers, mildewproof agents, yellowing-resistant agents, flame retardants, and volatile organic solvents by stirring until all the ingredients are completely dissolved in the volatile organic solvent;

[0108] (3) The repair agent is filled by using a liquid filling machine, the filling bottle capacity is selected to be 500 mL, the filling pressure is set to be 0.1 MPa, the filling time is set to be 15 s, and the filling amount is 400 mL each time.

[0109] The repair method of the spray type inflatable surface repair agent is as follows:

[0110] (1) A floating body material with a PVF surface is selected in advance, and is cut into a size of 50 cm x 50 cm, and the surface of the material is cleaned to remove dust, moisture and other impurities and dirt, and the material surface is kept clean;

[0111] (2) A thumbtack is used to randomly pierce three holes with a diameter of 0.6 mm in the material, as shown in Figure 2 ;

[0112] (3) The repair agent spray tank body is straightened, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is pressed to continuously spray horizontally, and the surface of the repaired material is completely infiltrated and bubbles are avoided;

[0113] (4) The repaired material is placed for 2 min to complete the repair, as shown in Figure 3 .

[0114] Example 2

[0115] This example provides a spray type inflatable surface repair agent with a solute mass fraction of 15.5%, which is prepared by mixing the following raw materials by mass:

[0116] 8 parts of yellowing-resistant fluorine-containing polyurethane, 1 part of antioxidant 1010, 1 part of ultraviolet absorber 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 1 part of hydrolysis stabilizer N-phenyl-β-naphthylamine, 3 parts of mildewcide n-dichloroethylene salicylamide, 1 part of yellowing-resistant agent Fisorb L-9322, 0.5 part of flame retardant TCEP, 84.5 parts of volatile organic solvent diethyl ether.

[0117] The yellowing-resistant fluorine-containing polyurethane in the repair agent is prepared as follows:

[0118] (1) Put the PTMG (M n = 2000) and HDI that have been subjected to dehydration treatment in advance into a three-necked flask equipped with mechanical stirring, N2 protection, and a constant-pressure dropping funnel, control n(OH):n(NCO) = 1:2, and react at 80°C for 3h under the protection of N2 atmosphere to obtain a polyurethane prepolymer;

[0119] (2) After the pre-reaction, titrate the NCO% by using di-n-butylamine method, then add a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol, and gradually increase the temperature of the system to 120°C, and stop the reaction after 4h to obtain the yellowing-resistant fluorine-containing polyurethane FPU, M n = 50000.

[0120] The preparation method of the spray-type inflatable surface repair agent is as follows:

[0121] (1) Dry the yellowing-resistant fluorine-containing polyurethane prepared by placing it in an oven at 120°C for 6h;

[0122] (2) Mix the dried yellowing-resistant fluorine-containing polyurethane particles with the antioxidant, ultraviolet absorber, hydrolysis stabilizer, mildewcide, yellowing-resistant agent, flame retardant, and volatile organic solvent by stirring until all the ingredients are completely dissolved in the volatile organic solvent;

[0123] (3) Fill the repair agent by using a liquid filling machine, select a filling bottle with a capacity of 500mL, set the filling pressure to 0.1MPa, set the filling time to 20s, and the filling amount of each time is 450mL.

[0124] The method for repairing the inflatable object by using the spray-type inflatable surface repair agent is as follows:

[0125] (1) Select a PVF surface inflatable object capsule material in advance, cut it into a size of 50cm x 50cm, clean the surface of the capsule material to remove dust, moisture, and other impurities and dirt, and keep the surface of the material clean;

[0126] (2) Using a thumbtack to randomly puncture three holes with a diameter of 0.6 mm in the capsule material;

[0127] (3) The repair agent spray tank is straightened, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is pressed to spray continuously laterally, the surface of the repaired material is completely infiltrated, and air bubbles are avoided;

[0128] (4) The repaired material is placed for 4 minutes to complete the repair.

[0129] Example 3

[0130] The present example provides a spray type aerated material surface repair agent with a solute mass fraction of 16.5%, which is prepared by mixing the following raw materials by mass:

[0131] 10 parts of yellowing-resistant fluorine-containing polyurethane, 0.5 parts of antioxidant 168, 1 part of ultraviolet absorber 2,4-dihydroxybenzophenone, 1 part of hydrolysis stabilizer carbodiimide, 3 parts of mildewcide n-dichloroethylene salicylamide, 0.5 parts of yellowing-resistant agent UV-1260, 0.5 parts of flame retardant DMMP, and 83.5 parts of volatile organic solvent acetone.

[0132] The specific preparation process of the yellowing-resistant fluorine-containing polyurethane in the repair agent is as follows:

[0133] (1) Put the previously dehydrated PTMG (M n = 1000), HDI into a three-necked flask equipped with mechanical stirring, N2 protection, and a constant pressure dropping funnel, control n(OH):n(NCO)=1:2, react at 100°C for 2h under the protection of N2 atmosphere to obtain polyurethane prepolymer;

[0134] (2) After the pre-polymerization is completed, NCO% titration is carried out by using di-n-butylamine method, then a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added, and the system temperature is gradually increased to 120°C, and the reaction is stopped after 6 hours to obtain yellowing-resistant fluorine-containing polyurethane FPU, M n = 70000.

[0135] The preparation method of the spray type aerated material surface repair agent is as follows:

[0136] (1) Dry the yellowing-resistant fluorine-containing polyurethane prepared by placing it in a 120°C oven for 6 hours;

[0137] (2) Mix the dried yellowing-resistant fluorine-containing polyurethane particles with antioxidants, ultraviolet absorbers, hydrolysis stabilizers, mildewcides, yellowing-resistant agents, flame retardants, and volatile organic solvents, respectively, until all the ingredients are completely dissolved in the volatile organic solvent;

[0138] (3) The liquid filling machine is used for repairing agent filling, the filling bottle capacity is 500 mL, the filling pressure is set to 0.1 MPa, the filling time is set to 20 s, and the filling amount is 450 mL each time.

[0139] The spray type aerostat surface repairing agent repairing aerostat method is as follows:

[0140] (1) A PVF surface aerostat capsule material is selected in advance, and is cut into a size of 50 cm x 50 cm. The surface of the capsule material is cleaned to remove dust, moisture and other impurities and dirt, and the material surface is kept clean;

[0141] (2) Use a drawing pin to randomly puncture three holes with a diameter of 0.4 mm on the capsule material;

[0142] (3) The repairing agent spray tank body is straightened, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is pressed and continuously sprayed transversely, the surface of the repaired material is completely infiltrated and the generation of bubbles is avoided;

[0143] (4) The repaired material is placed for 2 min, and the repair is completed.

[0144] Example 4

[0145] The present embodiment provides a spray type aerostat surface repairing agent with a solute mass fraction of 13%, which is prepared by mixing the following raw materials by mass:

[0146] 5 parts of yellowing-resistant fluorine-containing polyurethane, 1 part of antioxidant 1076, 1 part of ultraviolet absorber phenyl o-hydroxybenzoate, 1 part of hydrolysis stabilizer carbodiimide, 3 parts of mildewcide N-octyl-4-isothiazolin-3-ketone, 1 part of yellowing-resistant agent V-920, 1 part of flame retardant TCEP, 87 parts of volatile organic solvent ethyl acetate / acetone mixed solvent (prepared according to a mass ratio of 1:1).

[0147] The yellowing-resistant fluorine-containing polyurethane in the repairing agent is prepared as follows:

[0148] (1) The previously dehydrated PTMG (M n =1000) and HDI are placed in a three-necked flask equipped with mechanical stirring, N2 protection and constant pressure dropping funnel, n(OH):n(NCO) is controlled to be 1:2, and the polyurethane prepolymer is obtained by reacting at 60°C for 4 h under the protection of N2 atmosphere;

[0149] (2) After the end of prepolymerization, NCO% titration is carried out by using di-n-butylamine method, then a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added, and the system temperature is gradually increased to 120°C, and the reaction is stopped after 8 hours, so that a yellowing-resistant fluorine-containing polyurethane FPU with M n = 100000.

[0150] The preparation method of the spray type inflatable surface repair agent is as follows:

[0151] (1) The prepared yellowing-resistant fluorine-containing polyurethane is placed in a 120°C oven for 6 hours for drying treatment;

[0152] (2) The dried yellowing-resistant fluorine-containing polyurethane particles are respectively mixed with antioxidants, ultraviolet absorbers, hydrolysis stabilizers, mildewproof agents, yellowing-resistant agents, flame retardants, and solvents by stirring until all the ingredients are completely dissolved in the solvent;

[0153] (3) The repair agent is filled by using a liquid filling machine, the filling bottle capacity is selected to be 500 mL, the filling pressure is set to be 0.1 MPa, the filling time is set to be 15 s, and the filling amount is 400 mL each time.

[0154] The repair method of the spray type inflatable surface repair agent is as follows:

[0155] (1) A floating body material with a PVDF surface is selected in advance, and is cut into a size of 50 cm x 50 cm, and the surface of the material is cleaned to remove dust, moisture, and other impurities and dirt, so as to keep the surface clean;

[0156] (2) A wallpaper knife is used to scratch the surface of the material, as shown in Figure 4 ;

[0157] (3) The repair agent spray tank body is straightened, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is pressed to continuously spray horizontally, so as to ensure that the surface of the repaired material is completely infiltrated and bubbles are avoided;

[0158] (4) The repaired material is placed for 3 min, and the repair is completed, as shown in Figure 5 .

[0159] Example 5

[0160] The present embodiment provides a spray type inflatable surface repair agent with a solute mass fraction of 12%, which is prepared by mixing the following raw materials by mass:

[0161] 6 parts of the yellowing-resistant fluorine-containing polyurethane, 0.5 parts of antioxidant 1076, 1 part of ultraviolet absorber 2,4-dihydroxybenzophenone, 0.5 parts of hydrolysis stabilizer carbodiimide, 2 parts of mildewcide n-dichloroethylene salicylamide, 1 part of yellowing-resistant agent Fisorb L-9322, 1 part of flame retardant TCEP, 88 parts of volatile organic solvent ethyl acetate.

[0162] The yellowing-resistant fluorine-containing polyurethane in the repair agent is prepared as follows:

[0163] (1) Put the PTMG (M n = 1000) and HDI that have been dehydrated in advance into a three-necked flask equipped with mechanical stirring, N2 protection, and a constant-pressure dropping funnel, control n(OH):n(NCO) = 1:2, and react at 80°C for 3h under the protection of N2 atmosphere to obtain a polyurethane prepolymer;

[0164] (2) After the pre-reaction, titrate the NCO% by using di-n-butylamine method, then add a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol, and gradually increase the temperature of the system to 120°C, and stop the reaction after 2h to obtain the yellowing-resistant fluorine-containing polyurethane FPU, M n = 30000.

[0165] The preparation method of the spray-type inflatable surface repair agent is as follows:

[0166] (1) Dry the yellowing-resistant fluorine-containing polyurethane prepared by placing it in a 120°C oven for 6h;

[0167] (2) Mix the dried yellowing-resistant fluorine-containing polyurethane particles with the antioxidant, ultraviolet absorber, hydrolysis stabilizer, mildewcide, yellowing-resistant agent, flame retardant, and volatile organic solvent by stirring until all the ingredients are completely dissolved in the volatile organic solvent;

[0168] (3) Use a liquid filling machine to fill the repair agent, select a filling bottle capacity of 500mL, set the filling pressure to 0.1MPa, set the filling time to 20s, and the filling amount for each time is 400mL.

[0169] The repair method of the spray-type inflatable surface repair agent is as follows:

[0170] (1) Select a PVDF surface airship envelope material in advance, cut it into a size of 50cm×50cm, clean the surface of the envelope material to remove dust, moisture, and other impurities and dirt, and keep the surface clean;

[0171] (2) Use a drawing pin to randomly pierce three holes with a diameter of 0.6mm in the envelope material;

[0172] (3) The repair agent spray tank is straightened up, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is pressed to spray transversely continuously, the surface of the repaired material is ensured to be completely immersed and air bubbles are avoided;

[0173] (4) The repaired material is placed for 2 min to complete the repair.

[0174] Example 6

[0175] The present example provides a spray type aerated material surface repair agent with a solute mass fraction of 16%, which is prepared by mixing the following raw materials in parts by mass:

[0176] 8 parts of yellowing-resistant fluorine-containing polyurethane, 2 parts of antioxidant 1076, 2 parts of ultraviolet absorber phenyl o-hydroxybenzoate, 0.5 parts of hydrolysis stabilizer carbodiimide, 2 parts of mildewcide n-dichloroethylene salicylamide, 0.5 parts of yellowing-resistant agent V-920, 1 part of flame retardant DMMP, and 84 parts of volatile organic solvent diethyl ether.

[0177] The specific preparation process of the yellowing-resistant fluorine-containing polyurethane in the repair agent is as follows:

[0178] (1) The previously dehydrated PTMG (M n = 2000), HDI is placed in a three-necked flask equipped with mechanical stirring, N2 protection, and a constant pressure dropping funnel, n(OH):n(NCO) is controlled to be 1:2, and the polyurethane prepolymer can be obtained by reacting at 60°C for 4 h under the protection of N2 atmosphere;

[0179] (2) After the pre-polymerization is completed, NCO% titration is performed by using di-n-butylamine method, then a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added, and the temperature of the system is gradually increased to 120°C, and the reaction is stopped after 4 h, so that the yellowing-resistant fluorine-containing polyurethane FPU with M n = 50000 can be obtained.

[0180] The preparation method of the spray type aerated material surface repair agent is as follows:

[0181] (1) The yellowing-resistant fluorine-containing polyurethane prepared is dried by being placed in a 120°C oven for 6 h;

[0182] (2) The yellowing-resistant fluorine-containing polyurethane particles after drying are respectively mixed with the antioxidant, the ultraviolet absorber, the hydrolysis stabilizer, the mildewcide, the yellowing-resistant agent, the flame retardant, and the volatile organic solvent by stirring until all the ingredients are completely dissolved in the volatile organic solvent;

[0183] (3) The liquid filling machine is used for repairing agent filling, the filling bottle capacity is selected as 500 mL, the filling pressure is set as 0.2 MPa, the filling time is set as 15 s, and the filling amount is 450 mL each time.

[0184] The spray type inflatable surface repairing agent repairing inflatable method is as follows:

[0185] (1) A piece of inflatable material with a PVC surface is selected in advance, and is cut into a size of 50 cm*50 cm. The material surface is cleaned to remove dust, moisture and other impurities and dirt, and the material surface is kept clean;

[0186] (2) A thumbtack is used to randomly pierce three holes with a diameter of 0.6 mm in the material;

[0187] (3) The repairing agent spray tank body is straightened, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is pressed to continuously spray transversely, the surface of the repaired material is completely infiltrated, and air bubbles are avoided;

[0188] (4) The repaired material is placed for 4 min to complete the repair.

[0189] Example 7

[0190] The embodiment provides a spray type inflatable surface repairing agent with a solute mass fraction of 19%, which is prepared by mixing the following raw materials in parts by mass:

[0191] 10 parts of yellowing-resistant fluorine-containing polyurethane, 1 part of antioxidant 1010, 2 parts of ultraviolet absorber phenyl o-hydroxybenzoate, 1 part of hydrolysis stabilizer N-phenyl-β-naphthylamine, 3 parts of mildewcide N-octyl-4-isothiazolin-3-ketone, 1 part of yellowing-resistant agent Fisorb L-9322, 1 part of flame retardant DMMP, and 81 parts of volatile organic solvent ethyl acetate.

[0192] The yellowing-resistant fluorine-containing polyurethane in the repairing agent is prepared according to the following process:

[0193] (1) PTMG (M n =1000) and HDI that have been dehydrated in advance are placed in a three-necked flask provided with mechanical stirring, N2 protection and a constant-pressure dropping funnel, n(OH):n(NCO) is controlled to be 1:2, and the polyurethane prepolymer can be obtained by reacting at 60°C for 4 h under the protection of N2 atmosphere;

[0194] (2) After the pre-polymerization is completed, NCO% titration is performed by using di-n-butylamine, then a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added, the temperature of the system is gradually increased to 120°C, and the reaction is stopped after 8 h, so that the yellowing-resistant fluorine-containing polyurethane FPU can be obtained.n = 100000.

[0195] The preparation method of the spray type inflatable surface repair agent is as follows:

[0196] (1) The prepared yellowing-resistant fluorine-containing polyurethane is placed in a 120°C oven for 6 hours for drying treatment;

[0197] (2) The dried yellowing-resistant fluorine-containing polyurethane particles are respectively mixed with antioxidants, ultraviolet absorbers, hydrolysis stabilizers, mildewproof agents, yellowing-resistant agents, flame retardants, and volatile organic solvents by stirring until all the ingredients are completely dissolved in the volatile organic solvents;

[0198] (3) The repair agent is filled by using a liquid filling machine, the filling bottle capacity is selected to be 500 mL, the filling pressure is set to be 0.2 MPa, the filling time is set to be 15 s, and the filling amount is 450 mL each time.

[0199] The repair method of the spray type inflatable surface repair agent is as follows:

[0200] (1) A TPU surface airship capsule material is selected in advance, and is cut into a size of 50 cm x 50 cm. The surface of the capsule material is cleaned to remove dust, moisture, and other impurities and dirt, and the material surface is kept clean;

[0201] (2) Three holes with a diameter of 0.6 mm are randomly needled on the capsule material using a drawing pin;

[0202] (3) The repair agent spray tank body is straightened, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is continuously sprayed transversely, the surface of the repaired material is completely infiltrated, and the generation of air bubbles is avoided;

[0203] (4) The repaired material is placed for 5 min to complete the repair.

[0204] Example 8

[0205] The present embodiment provides a spray type inflatable surface repair agent with a solute mass fraction of 17%, which is prepared by mixing the following raw materials by mass:

[0206] 9 parts of yellowing-resistant fluorine-containing polyurethane, 1 part of antioxidant 1076, 1 part of ultraviolet absorber phenyl o-hydroxybenzoate, 1 part of hydrolysis stabilizer carbodiimide, 3 parts of mildewproof agent N-octyl-4-isothiazolin-3-one, 1 part of yellowing-resistant agent Fisorb L-9322, 1 part of flame retardant TCEP, and 83 parts of volatile organic solvent diethyl ether.

[0207] The specific preparation process of the yellowing-resistant fluorine-containing polyurethane in the repair agent is as follows:

[0208] (1) The PTMG (M n = 2000), HDI were placed in a three-necked flask equipped with mechanical stirring, N2 protection, constant pressure dropping funnel, and the n(OH):n(NCO) was controlled to be 1:2. The polyurethane prepolymer was obtained by reacting at 60°C for 4h under N2 atmosphere protection.

[0209] (2) After the pre-polymerization, the NCO% titration was carried out by using di-n-butylamine method, then the measured amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol was added, and the temperature of the system was gradually increased to 120°C. The reaction was stopped after 6h, and the yellowing-resistant fluorine-containing polyurethane FPU with M n = 80000 was obtained.

[0210] The preparation method of the spray type inflatable surface repair agent is as follows:

[0211] (1) The prepared yellowing-resistant fluorine-containing polyurethane was dried by placing it in an oven at 120°C for 6h;

[0212] (2) The dried yellowing-resistant fluorine-containing polyurethane particles were mixed with antioxidants, ultraviolet absorbers, hydrolysis stabilizers, mildewproof agents, yellowing-resistant agents, flame retardants, and volatile organic solvents by stirring until all the ingredients were completely dissolved in the volatile organic solvent;

[0213] (3) The repair agent was filled by using a liquid filling machine, the filling bottle capacity was selected to be 500mL, the filling pressure was set to be 0.1MPa, the filling time was set to be 20s, and the filling amount was 400mL each time.

[0214] The repair method of the spray type inflatable surface repair agent is as follows:

[0215] (1) A floating body material with a PVF surface was selected in advance, and was cut into a size of 50cm×50cm. The surface of the material was cleaned to remove dust, moisture, and other impurities and dirt, and the material surface was kept clean;

[0216] (2) Three holes with a diameter of 0.6mm were randomly needled on the material surface by using a drawing pin;

[0217] (3) The repair agent spray tank body was straightened, the nozzle was aimed at the place to be repaired, the distance was 20cm, and the nozzle was continuously sprayed horizontally to ensure that the repaired material surface was completely infiltrated and bubbles were avoided;

[0218] (4) The repaired material was placed for 5min to complete the repair.

[0219] Example 9

[0220] The embodiment provides a spraying type aeriform surface repairing agent with a solute mass fraction of 18%, which is prepared by mixing raw materials in the following mass fractions:

[0221] 10 parts of the yellowing-resistant fluorine-containing polyurethane, 2 parts of the antioxidant 168, 1 part of the ultraviolet absorber 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 1 part of the hydrolysis stabilizer N-phenyl-beta-naphthylamine, 2 parts of the mildewproof agent n-dichloroethylene salicylamide, 1 part of the yellowing-resistant agent V-920, 1 part of the flame retardant DMMP, and 82 parts of the volatile organic solvent acetone.

[0222] The yellowing-resistant fluorine-containing polyurethane in the repairing agent is prepared according to the following process:

[0223] (1) the PTMG (M n =2000) and HDI that have been subjected to dehydration treatment in advance are placed in a three-neck flask provided with mechanical stirring, N2 protection and a constant-pressure dropping funnel, n(OH):n(NCO) is controlled to be 1:2, and the polyurethane prepolymer can be obtained by reacting at 60 DEG C for 4h under the protection of N2 atmosphere;

[0224] (2) after the prepolymersation is completed, the NCO% titration is carried out by using the di-n-butylamine method, then the 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added in a metering ratio, the temperature of the system is gradually increased to 120 DEG C, and the reaction is stopped after 4h, so that the yellowing-resistant fluorine-containing polyurethane FPU, M n =50000 can be obtained.

[0225] The preparation method of the spraying type aeriform surface repairing agent is as follows:

[0226] (1) the yellowing-resistant fluorine-containing polyurethane prepared is placed in a 120 DEG C oven for drying treatment for 6h;

[0227] (2) the yellowing-resistant fluorine-containing polyurethane particles after drying are respectively mixed with the antioxidant, the ultraviolet absorber, the hydrolysis stabilizer, the mildewproof agent, the yellowing-resistant agent, the flame retardant and the volatile organic solvent by stirring until all the components are completely dissolved in the volatile organic solvent;

[0228] (3) the liquid filling machine is used for filling the repairing agent, the filling bottle capacity is selected to be 500mL, the filling pressure is set to be 0.1MPa, the filling time is set to be 20s, and the filling amount is 400mL each time.

[0229] The repairing method of the spraying type aeriform surface repairing agent is as follows:

[0230] (1) Pre-select a piece of surface as TPU airship capsule material, and cut into 50 cm x 50 cm size, clean the surface of the capsule material, remove dust, moisture and other impurities and dirt, keep the material surface clean;

[0231] (2) Use a pin to randomly puncture three holes with a diameter of 0.6 mm on the capsule material;

[0232] (3) The repair agent spray tank is straight, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is pressed continuously horizontally, the surface of the repaired material is completely infiltrated and the generation of bubbles is avoided;

[0233] (4) The repaired material is placed for 4 minutes to complete the repair.

[0234] Example 10

[0235] The present embodiment provides a solute mass fraction of 12.5% of a spray type aerostat surface repair agent, which is prepared by mixing the following mass parts of raw materials:

[0236] 6 parts of yellowing-resistant fluorine-containing polyurethane, 2 parts of antioxidant 1076, 1 part of ultraviolet absorber 2,4-dihydroxybenzophenone, 0.5 part of hydrolysis stabilizer carbodiimide, 2 parts of mildewcide n-dichloroethylene salicylamide, 0.5 part of yellowing-resistant agent V-920, 0.5 part of flame retardant TCEP, 87.5 parts of volatile organic solvent diethyl ether.

[0237] The specific preparation process of the yellowing-resistant fluorine-containing polyurethane in the repair agent is as follows:

[0238] (1) Put the PTMG (M n =2000) and HDI which have been dehydrated in advance into a three-necked flask equipped with mechanical stirring, N2 protection and constant pressure dropping funnel, control n(OH):n(NCO)=1:2, react at 60℃ for 4h under N2 atmosphere to obtain polyurethane prepolymer;

[0239] (2) After the pre-polymerization is completed, NCO% titration is carried out by using di-n-butylamine method, then a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added, and the temperature of the system is gradually increased to 120℃, and the reaction is stopped after 8 hours, thus obtaining yellowing-resistant fluorine-containing polyurethane FPU, M n =100000.

[0240] The preparation method of the spray type aerostat surface repair agent is as follows:

[0241] (1) Dry the prepared yellowing-resistant fluorine-containing polyurethane in an oven at 120℃ for 6 hours;

[0242] (2) The dried yellowing-resistant fluorinated polyurethane particles are stirred and mixed with antioxidants, ultraviolet absorbers, hydrolytic stabilizers, mildew inhibitors, yellowing-resistant agents, flame retardants and volatile organic solvents until all components are completely dissolved in the volatile organic solvents.

[0243] (3) Use a liquid filling machine to fill the repair agent. Select a filling bottle with a capacity of 500mL, set the filling pressure to 0.2MPa, set the filling time to 15s, and fill 400mL each time.

[0244] The method for repairing and replenishing inflatable structures using this spray-applied surface repair agent is as follows:

[0245] (1) Select a piece of airship capsule material with TPU surface in advance and cut it into 50cm×50cm size. Clean the surface of the capsule material to remove dust, moisture and other impurities and dirt, and keep the material surface clean.

[0246] (2) Use sandpaper to create wear defects on the bag material, such as Figure 6 As shown;

[0247] (3) Stand the repair agent spray can upright, aim the nozzle at the area to be repaired at a distance of 20cm, press the nozzle to spray horizontally and continuously to ensure that the surface of the material to be repaired is completely wetted and to avoid the generation of bubbles.

[0248] (4) The repair is complete after leaving the repaired material for 3 minutes. Figure 7 As shown.

[0249] Example 11

[0250] This embodiment provides a sprayable inflatable surface repair agent with a solute mass fraction of 12%, which is prepared by mixing the following raw materials in parts by mass:

[0251] 6 parts yellowing-resistant fluorinated polyurethane, 2 parts antioxidant 1076, 1 part ultraviolet absorber 2,4-dihydroxybenzophenone, 0.5 parts hydrolytic stabilizer carbodiimide, 2 parts mildew inhibitor n-dichloroethylene salicylate, 0.5 parts flame retardant TCEP, and 88 parts volatile organic solvent diethyl ether.

[0252] The specific preparation process of the yellowing-resistant fluorinated polyurethane in this repair agent is as follows:

[0253] (1) The PTMG (M) that has been dehydrated beforehand n =2000), HDI is placed in a three-necked flask equipped with mechanical stirring, N2 protection, and constant pressure dropping funnel, and the ratio of n(OH):n(NCO) is controlled to be 1:2. The polyurethane prepolymer can be obtained by reacting at 60°C for 4 hours under N2 atmosphere protection.

[0254] (2) After the end of prepolymerization, NCO% titration is carried out by using di-n-butylamine method, then a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added, and the system temperature is gradually increased to 120°C, and the reaction is stopped after 8 hours, so that a yellowing-resistant fluorine-containing polyurethane FPU with M n = 100000.

[0255] The preparation method of the spray type inflatable surface repair agent is as follows:

[0256] (1) The prepared yellowing-resistant fluorine-containing polyurethane is placed in a 120°C oven for 6 hours for drying treatment;

[0257] (2) The dried yellowing-resistant fluorine-containing polyurethane particles are respectively mixed with antioxidants, ultraviolet absorbers, hydrolysis stabilizers, mildewproof agents, flame retardants, and volatile organic solvents by stirring until all the ingredients are completely dissolved in the volatile organic solvent;

[0258] (3) The repair agent is filled by using a liquid filling machine, the filling bottle capacity is selected to be 500 mL, the filling pressure is set to be 0.2 MPa, the filling time is set to be 15 s, and the filling amount is 400 mL each time.

[0259] The repair method of the spray type inflatable surface repair agent is as follows:

[0260] (1) A TPU surface floating body material is selected in advance, and is cut into a size of 50 cm x 50 cm, and the surface of the material is cleaned to remove dust, moisture, and other impurities and dirt, so as to keep the material surface clean;

[0261] (2) Three holes with a diameter of 0.6 mm are randomly needled on the material surface by using a drawing pin;

[0262] (3) The repair agent spray tank body is straightened, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is continuously sprayed horizontally, the repaired material surface is completely infiltrated, and air bubbles are avoided;

[0263] (4) The repaired material is placed for 4 min, and the repair is completed.

[0264] Comparative Example 1

[0265] The comparative example provides a spray type aerostat surface repair agent with a solute mass fraction of 10%, which is prepared by mixing the following raw materials in parts by mass: 5 parts of a yellowing-resistant fluorine-containing polyurethane, 0.5 parts of an antioxidant 1076, 1 part of a UV absorber phenyl salicylate, 0.5 parts of a hydrolysis stabilizer carbodiimide, 2 parts of a mildew inhibitor n-dichloroethylene salicylamide, 0.5 parts of a yellowing-resistant agent Fisorb L-9322, 0.5 parts of a flame retardant TCEP, and 90 parts of a high-boiling-point solvent N,N-dimethylformamide (DMF).

[0266] The yellowing-resistant fluorine-containing polyurethane in the repair agent is prepared as follows:

[0267] (1) Put the PTMG (M n = 1000) and HDI that have been subjected to dehydration treatment in advance into a three-necked flask equipped with mechanical stirring, N2 protection, and a constant-pressure dropping funnel, control n(OH):n(NCO) = 1:2, and react at 60°C for 4 h under the protection of N2 atmosphere to obtain a polyurethane prepolymer;

[0268] (2) After the pre-reaction is completed, perform NCO% titration by using the di-n-butylamine method, then add a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol, and gradually increase the temperature of the system to 120°C, and stop the reaction after 2 h to obtain the yellowing-resistant fluorine-containing polyurethane FPU, M n = 30000.

[0269] The preparation method of the spray type aerostat surface repair agent is as follows:

[0270] (1) Dry the yellowing-resistant fluorine-containing polyurethane prepared by placing it in a 120°C oven for 6 h;

[0271] (2) Mix the dried yellowing-resistant fluorine-containing polyurethane particles with the antioxidant, the UV absorber, the hydrolysis stabilizer, the mildew inhibitor, the yellowing-resistant agent, the flame retardant, and the high-boiling-point solvent by stirring until all the ingredients are completely dissolved in DMF;

[0272] (3) Perform repair agent filling by using a liquid filling machine, select a filling bottle capacity of 500 mL, set the filling pressure to 0.1 MPa, set the filling time to 15 s, and fill 400 mL each time.

[0273] The repair method of the spray type aerostat surface repair agent is as follows:

[0274] (1) Select a PVF surface aerostat capsule material in advance, cut it into a size of 50 cm x 50 cm, clean the surface of the capsule material to remove dust, moisture, and other impurities and dirt, and keep the surface of the material clean;

[0275] (2) Using a thumbtack to randomly puncture three holes with a diameter of 0.6 mm in the capsule material;

[0276] (3) The repair agent spray tank is placed vertically, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is pressed to spray continuously laterally, and the surface of the repaired material is completely infiltrated and bubbles are avoided;

[0277] (4) The repaired material is placed for 5 min, and since the boiling point of DMF is high, it cannot be completely volatilized at room temperature for 5 min.

[0278] Comparative Example 2

[0279] The present example provides a spray type aerated surface repair agent with a solute mass fraction of 10%, which is prepared by mixing the following mass parts of raw materials: 5 parts of ordinary fluorine-containing polyurethane, 0.5 parts of antioxidant 1076, 1 part of ultraviolet absorber phenyl o-hydroxybenzoate, 0.5 parts of hydrolysis stabilizer carbodiimide, 2 parts of mildewcide n-dichloroethylene salicylamide, 0.5 parts of yellowing-resistant agent Fisorb L-9322, 0.5 parts of flame retardant TCEP, and 90 parts of volatile organic solvent ethyl acetate.

[0280] The specific preparation process of the ordinary fluorine-containing polyurethane in the repair agent is as follows:

[0281] (1) Put the previously dehydrated PTMG (M n = 1000), 4,4'-diphenyl methane diisocyanate (MDI) into a three-necked flask equipped with mechanical stirring, N2 protection, and a constant pressure dropping funnel, control n(OH):n(NCO)=1:2, and react at 60°C for 4h under the protection of N2 atmosphere to obtain a polyurethane prepolymer;

[0282] (2) After the pre-polymerization is completed, NCO% titration is performed by using di-n-butylamine method, then a metered amount of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol is added, and the system temperature is gradually increased to 120°C, and the reaction is stopped after 2h to obtain ordinary fluorine-containing polyurethane FPU, M n = 30000.

[0283] The preparation method of the spray type aerated surface repair agent is as follows:

[0284] (1) The prepared ordinary fluorine-containing polyurethane is placed in a 120°C oven for 6h for drying treatment;

[0285] (2) After drying, the common type fluorine-containing polyurethane particles are mixed with an antioxidant, an ultraviolet absorber, a hydrolysis stabilizer, a mildew-proof agent, a yellowing-resistant agent, a flame retardant, and a volatile organic solvent by stirring until all the components are completely dissolved in the volatile organic solvent;

[0286] (3) The liquid filling machine is used for filling the repair agent, the filling bottle capacity is selected as 500 mL, the filling pressure is set as 0.1 MPa, the filling time is set as 15 s, and the filling amount is 400 mL each time.

[0287] The spray type aeriform surface repair agent repair aeriform method is as follows:

[0288] (1) A PVF surface aerostat capsule material is selected in advance, and is cut into a size of 50 cm*50 cm, the capsule material surface is cleaned to remove dust, moisture and other impurities and dirt, and the material surface is kept clean;

[0289] (2) The drawing pin is used to randomly puncture three holes with a diameter of 0.6 mm on the capsule material;

[0290] (3) The repair agent spray tank body is vertically erected, the nozzle is aimed at the place to be repaired, the distance is 20 cm, the nozzle is continuously sprayed transversely, the repaired material surface is completely infiltrated, and the generation of bubbles is avoided;

[0291] (4) The repaired material is placed for 2 min.

[0292] Effect evaluation

[0293] In order to verify the technical effects obtained by the application, the repaired materials obtained by Examples 1-11 and Comparative Example 1 are respectively tested in terms of weight gain, helium permeation rate, peeling strength, helium permeation rate after high-low temperature cycle, and the results are shown in Table 1; for the convenience of writing, Examples 1-11 are coded as No. 1-11, and Comparative Example 1 is coded as No. 12.

[0294] Table 1 Test results of the repaired materials obtained by Examples 1-11 and Comparative Example 1

[0295]

[0296]

[0297] From Table 1, 1-11, it can be seen that the present application realizes the repairing of the damaged aeriform material by a simple method, the air permeability of the repaired material is basically the same as that before the damage, the weight gain is less, the effect on the hovering performance of the aerostat is very small, the peeling strength between the repairing agent and the surface of the adherend is high, the air permeability does not increase after 100 and 200 times of rubbing at room temperature, and the repairing agent also has good high and low temperature resistance, and the air permeability of the repaired surface does not change after high and low temperature cycles. It can be found from Comparative Example 1 that the repairing agent does not completely dry in 5 minutes after using a high-boiling-point DMF solvent, resulting in a very poor repair effect, and the He air permeability test result shows that it leaks.

[0298] Xenon lamp aging experiments were respectively conducted on the repaired materials obtained from Example 1, Example 11 and Comparative Example 2, and the yellowing resistance and helium permeability of the repaired materials after aging were tested. The surface states of the repaired materials after xenon lamp aging are shown in Figure 8 (the repaired material obtained from Example 1), Figure 9 (the repaired material obtained from Example 11), and Figure 10 (the repaired material obtained from Comparative Example 2), and the helium permeability test results are shown in Table 2. In Table 2, for the convenience of writing, the sample of Example 1 before xenon lamp aging is coded as No. 1, the sample of Example 11 before xenon lamp aging is coded as No. 2, the sample of Comparative Example 2 before xenon lamp aging is coded as No. 3, the sample of Example 1 after xenon lamp aging is coded as No. 4, the sample of Example 11 after xenon lamp aging is coded as No. 5, and the sample of Comparative Example 2 after xenon lamp aging is coded as No. 6.

[0299] Table 2 Test results of the repaired materials obtained from Example 1, Example 11 and Comparative Example 2 after xenon lamp aging

[0300]

[0301] It can be found from Figure 8 that the surface of the material layer repaired by the repairing agent made of the yellowing-resistant fluorine-containing polyurethane and the yellowing-resistant agent does not change after xenon lamp accelerated aging, which is because the yellowing-resistant fluorine-containing polyurethane does not contain benzene ring structure and does not produce yellowing phenomenon under ultraviolet light irradiation; it can be found from Figure 9 that the surface of the material layer repaired by the repairing agent made of the yellowing-resistant fluorine-containing polyurethane alone without the yellowing-resistant agent slightly changes yellow after xenon lamp accelerated aging; and Figure 10 the repairing agent uses ordinary polyurethane, and the ordinary fluorine-containing polyurethane contains benzene ring structure, which is oxidized into quinone structure under ultraviolet light irradiation, thereby producing yellowing phenomenon.

[0302] It can be found from Table 2 that the helium permeation rate of the repaired capsule material prepared by using the yellowing-resistant fluorine-containing polyurethane and the yellowing-resistant agent is almost unchanged after xenon lamp accelerated aging, and still has good rubbing resistance and high-low temperature resistance; the helium permeation rate of the repaired capsule material prepared by using the yellowing-resistant fluorine-containing polyurethane alone is slightly increased after xenon lamp accelerated aging; and the ordinary fluorine-containing polyurethane is oxidized under ultraviolet light, the structure is changed, which leads to the loss of the repairing function of the fluorine-containing polyurethane, and further leads to the air leakage of the repaired capsule material.

[0303] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method of repairing a surface of an inflatable article, characterized by, The method comprises the following steps: applying a surface repair agent to a region to be repaired on the surface of the inflatable object, and leaving for a period of time until the applied surface repair agent solidifies; the components of the surface repair agent include, in terms of mass fraction: a yellowing-resistant fluorine-containing polyurethane 5-10 parts; an antioxidant 0.5-2 parts; a UV absorber 1-2 parts; a hydrolysis stabilizer 0.5-1 part; a mildew-proof agent 2-3 parts; a flame retardant 0.5-1 part; a yellowing-resistant agent 0.5-2 parts; a volatile organic solvent 79-90 parts; the yellowing-resistant fluorine-containing polyurethane has a number average molecular weight of 30000-100000, and is prepared according to the following steps: a) pre-polymerizing polytetrahydrofuran diol with a number average molecular weight of 1000-2000 and hexamethylene diisocyanate to obtain a polyurethane prepolymer; b) polymerizing the polyurethane prepolymer with 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol to obtain a yellowing-resistant fluorine-containing polyurethane with a number average molecular weight of 30000-100000; the yellowing-resistant agent is one or more of Fisorb L-9322, V-920 and UV-1260; the volatile organic solvent has a boiling point of ≤90℃; the application method is spraying.

2. The surface repair method according to claim 1, wherein, the volatile organic solvent is one or more of diethyl ether, ethyl acetate and acetone.

3. The surface repair method according to claim 1, wherein the antioxidant is one or more of 3,5-di-tert-butyl-4-hydroxyphenyl octadecyl propionate, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and tris(2,4-di-tert-butylphenyl) phosphite; the UV absorber is one or more of phenyl o-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole and 2,4-dihydroxybenzophenone; the hydrolysis stabilizer is carbodiimide and / or N-phenyl-β-naphthylamine; the mildew-proof agent is n-dichloroethylene salicylamide and / or N-octyl-4-isothiazolin-3-one; the flame retardant is one or more of tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate and dimethyl methylphosphonate.

4. The surface repair method according to claim 1, wherein the surface repair agent is prepared according to the following steps: 5-10 parts by mass of the yellowing-resistant fluorine-containing polyurethane, 0.5-2 parts by mass of the antioxidant, 1-2 parts by mass of the UV absorber, 0.5-1 part by mass of the hydrolysis stabilizer, 2-3 parts by mass of the mildew-proof agent, 0.5-1 part by mass of the flame retardant, 0.5-2 parts by mass of the yellowing-resistant agent and 79-90 parts by mass of the volatile organic solvent are mixed to obtain the surface repair agent.

5. The surface repair method according to claim 1, wherein the material of the surface of the inflatable object is one or more of polyvinyl fluoride, polyvinylidene fluoride, polyurethane and polyvinyl chloride.

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