Acrylates containing phosphazene and hydroxyl functional groups, isocyanates containing quaternary ammonium salt structures, and methods of making, coatings, and applications thereof

Abstract

The application provides an acrylic ester containing phosphazene and a hydroxyl functional group, an isocyanate containing a quaternary ammonium salt structure and a preparation method, a paint and an application, and belongs to the technical field of paints.The application provides an acrylic ester containing phosphazene and a hydroxyl functional group, combines an acrylic structure with phosphazene, designs and synthesizes a novel acrylic resin containing a phosphazene structural unit, and the structure further contains a hydroxyl functional group (-OH); the hydroxyl group acts as an active reaction group and can continue to react with an epoxy group and a functional group such as an isocyanate.The application provides an isocyanate containing a quaternary ammonium salt structure; the isocyanate is an important component of a thermosetting resin; the application introduces a quaternary ammonium salt structure into an isocyanate structure system; the quaternary ammonium salt has antibacterial and disinfecting effects; and the isocyanate structure can be chemically crosslinked with the aforementioned acrylic ester structural unit containing phosphazene and a hydroxyl functional group.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to an acrylate containing phosphazene and hydroxyl functional groups, an isocyanate containing a quaternary ammonium salt structure, a preparation method thereof, coatings thereof, and applications thereof. Background Technology

[0002] Coatings, as a highly dynamic industry within the field of polymer materials, have enjoyed enduring prosperity. With rapid economic development, safety has become paramount, and coatings with flame-retardant properties play a crucial role.

[0003] Photopolymerization (photocuring) technology, as a novel surface treatment technique for materials, refers to the process by which monomers or oligomers undergo polymerization and cross-linking reactions under visible / ultraviolet light irradiation, ultimately achieving curing. Photopolymerization technology boasts the "5Es" of high efficiency, high quality, environmental friendliness, energy saving, and controllability. However, for some components, certain areas may not receive sufficient light, and photopolymerization alone cannot achieve perfect results. Thermal curing technology, as a traditional curing technique, offers excellent curing effects. Combining thermal curing and photopolymerization technologies yields the desired results.

[0004] However, existing photothermal dual-curing resins have problems with poor flame retardant effect and poor antibacterial effect. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide an acrylate containing phosphazene and hydroxyl functional groups, an isocyanate containing a quaternary ammonium salt structure, a preparation method thereof, a coating, and an application thereof. The acrylate provided by this invention has good flame retardant properties, and the isocyanate has excellent antibacterial properties. The resulting photothermal dual-curing coating combines both flame retardant and antibacterial effects.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides an acrylate containing phosphazene and hydroxyl functional groups, having the structure shown in Formula A:

[0008]

[0009] In formula A, R1~R 12 Independently alkyl chain C y H 2y+1 , where y is an integer from 0 to 20.

[0010] Preferably, the acrylate containing phosphazene and hydroxyl functional groups has the structures shown in A1 to A6:

[0011]

[0012]

[0013] The present invention also provides a method for preparing the acrylate described in the above technical solution, comprising the following steps:

[0014] Pentaerythritol di(substituted acrylate), hexachlorophosphine, sodium hydride, and an organic solvent are mixed and subjected to a substitution reaction to obtain the acrylic resin containing phosphazene and hydroxyl functional groups.

[0015] Preferably, the equivalent ratio of pentaerythritol di(substituted acrylate) to hexachlorophosphine is 1:0.05 to 0.5.

[0016] Preferably, the equivalent ratio of pentaerythritol di(substituted acrylate) to sodium hydride is 1:1 to 2.

[0017] The present invention also provides an isocyanate containing a quaternary ammonium salt structure, having the structure shown in Formula B:

[0018]

[0019] In formula B, R1, R2 and R3 are independently benzyl, substituted benzyl, alkyl, halogen-substituted alkyl or halogen-substituted aryl;

[0020] X - It consists of fluoride ions, chloride ions, bromide ions, iodide ions, hexafluorophosphate ions, or nitrate ions;

[0021] n is an integer from 0 to 20, and m is an integer from 1 to 100.

[0022] Preferably, the isocyanate has a structure shown in any one of formulas B1 to B4:

[0023]

[0024] This invention also provides a method for preparing isocyanates containing quaternary ammonium salt structures as described in the above technical solution, comprising the following steps:

[0025] 3,6-dihydroxy-1,4-dibenzyl alcohol was mixed with terminal dibromo-substituted alkanes and organic solvents to carry out a substitution reaction, yielding an intermediate compound.

[0026] The intermediate compound, the trisubstituted amine, and the solvent were mixed and subjected to an amination reaction to obtain the monomer compound;

[0027] The monomeric compound, cyclohexane-1,4-diisocyanate, catalyst and organic solvent were mixed and subjected to a nucleophilic addition reaction to obtain the precursor compound;

[0028] The precursor compound was mixed with a sodium salt and subjected to ion exchange to obtain the isocyanate containing a quaternary ammonium salt structure.

[0029] The present invention also provides a photothermal dual-curing coating, comprising the following components in weight percentage:

[0030] The above technical solution comprises 5%–30% acrylate containing phosphazene and hydroxyl functional groups, 5%–40% isocyanate containing quaternary ammonium salt structure, 3%–50% filler, 0.1%–5% defoamer, 0.5%–10% thickener, 20%–70% solvent, 0.1%–5% tin reagent, and 0.1%–5% photoinitiator, with the sum of the mass percentages of all components being 100%.

[0031] The present invention also provides the application of the photothermal dual-curing coating described in the above technical solution in metal coating.

[0032] This invention provides an acrylate containing phosphazene and hydroxyl functional groups. By combining the acrylic acid structure with phosphazene, a novel acrylic resin containing phosphazene structural units is designed and synthesized. The structure also contains hydroxyl functional groups (-OH). The hydroxyl group, as an active reactive group, can continue to undergo epoxidation and react with functional groups such as isocyanates.

[0033] This invention provides an isocyanate containing a quaternary ammonium salt structure. Isocyanate is an important component of thermosetting resins. This invention introduces the quaternary ammonium salt structure into the isocyanate structure system. The quaternary ammonium salt has antibacterial and disinfecting effects. The isocyanate structure can undergo a chemical crosslinking reaction with the aforementioned acrylate structural units containing phosphazene and hydroxyl functional groups.

[0034] This invention provides a photothermal dual-curing coating, wherein the hydroxyl groups in the acrylic resin containing phosphazene structural units can undergo a thermal crosslinking reaction with the isocyanate groups in the isocyanate containing quaternary ammonium salt structures, and further enables the acrylate structural units in the acrylic resin component containing phosphazene structural units to undergo photocuring crosslinking under photoinitiator conditions. Detailed Implementation

[0035] This invention provides an acrylate containing phosphazene and hydroxyl functional groups, having the structure shown in Formula A:

[0036]

[0037] In formula A, R1~R 12 Independently alkyl chain C y H 2y+1 , where y is an integer from 0 to 20.

[0038] In this invention, the acrylate containing phosphazene and hydroxyl functional groups preferably has any one of the structures shown in A1 to A6:

[0039]

[0040]

[0041] The present invention also provides a method for preparing the acrylate described in the above technical solution, comprising the following steps:

[0042] Pentaerythritol di(substituted acrylate), hexachlorophosphine, sodium hydride, and an organic solvent are mixed and subjected to a substitution reaction to obtain the acrylic resin containing phosphazene and hydroxyl functional groups.

[0043] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0044] In this invention, the principle of the preparation method is shown in the following formula:

[0045] .

[0046] In this invention, the equivalent ratio of pentaerythritol di(substituted acrylate) to hexachlorophosphine is preferably 1:0.05 to 0.5.

[0047] In this invention, the equivalent ratio of pentaerythritol di(substituted acrylate) to sodium hydride is preferably 1:1 to 2.

[0048] In this invention, the organic solvent is preferably dichloromethane.

[0049] In this invention, the temperature of the substitution reaction is preferably 0 to 50°C, and the time is preferably 2 to 24 hours.

[0050] In a specific embodiment of the present invention, the pentaerythritol di(substituted acrylate) is preferably dissolved in dichloromethane, sodium hydride is added, the mixture is stirred at room temperature for 0.5 to 10 hours, the hexachlorophosphine is added to the reaction system, the reaction is heated for 2 to 24 hours, cooled, washed with water, dried and concentrated to obtain the acrylic resin containing phosphazene and hydroxyl functional groups.

[0051] The present invention also provides an isocyanate containing a quaternary ammonium salt structure, having the structure shown in Formula B:

[0052]

[0053] In formula B, R1, R2 and R3 are independently benzyl, substituted benzyl, alkyl, halogen-substituted alkyl or halogen-substituted aryl;

[0054] X - It consists of fluoride ions, chloride ions, bromide ions, iodide ions, hexafluorophosphate ions, or nitrate ions;

[0055] n is an integer from 0 to 20, and m is an integer from 1 to 100.

[0056] In this invention, the isocyanate preferably has a structure shown in any of formulas B1 to B4:

[0057]

[0058] This invention also provides a method for preparing isocyanates containing quaternary ammonium salt structures as described in the above technical solution, comprising the following steps:

[0059] 3,6-dihydroxy-1,4-dibenzyl alcohol was mixed with terminal dibromo-substituted alkanes and organic solvents to carry out a substitution reaction, yielding an intermediate compound.

[0060] The intermediate compound, the trisubstituted amine, and the solvent were mixed and subjected to an amination reaction to obtain the monomer compound;

[0061] The monomeric compound, cyclohexane-1,4-diisocyanate, catalyst and organic solvent were mixed and subjected to a nucleophilic addition reaction to obtain the precursor compound;

[0062] The precursor compound was mixed with a sodium salt and subjected to ion exchange to obtain the isocyanate containing a quaternary ammonium salt structure.

[0063] In this invention, the principle of the preparation method is shown in the following formula:

[0064]

[0065] In this invention, 3,6-dihydroxy-1,4-dibenzyl alcohol is mixed with a terminal dibromo-substituted alkane and an organic solvent to carry out a substitution reaction to obtain an intermediate compound.

[0066] In this invention, the equivalence ratio of the 3,6-dihydroxy-1,4-dibenzyl alcohol to the terminal dibromo-substituted alkane is preferably 1:1 to 4.

[0067] In this invention, the organic solvent is preferably dichloromethane.

[0068] In this invention, the temperature of the substitution reaction is preferably room temperature, and the time is preferably 5 to 36 hours.

[0069] In this invention, the substitution reaction is preferably carried out in an alkaline environment, which is preferably provided by potassium carbonate, and the equivalence ratio of 3,6-dihydroxy-1,4-dibenzyl alcohol to potassium carbonate is preferably 1:1 to 4.

[0070] In a specific embodiment of the present invention, preferably, the 3,6-dihydroxy-1,4-dibenzyl alcohol, potassium carbonate, and terminal dibromo-substituted alkane are dissolved in dichloromethane, stirred at room temperature for 5 to 36 hours, and the reaction is detected to be complete by thin-layer chromatography. After filtration, the filter residue is removed, the organic phase is washed three times with pure water, dried and concentrated to obtain the intermediate compound BO-3.

[0071] After obtaining the intermediate compound, the present invention mixes the intermediate compound, the trisubstituted amine, and the solvent to carry out an amination reaction to obtain the monomer compound.

[0072] In this invention, the equivalent ratio of the intermediate compound to the trisubstituted amine is preferably 1:1.

[0073] In this invention, the solvent is preferably ethanol-water, and the volume ratio of ethanol to water in the ethanol-water is preferably 1:1.

[0074] In this invention, the temperature of the amination reaction is preferably 90°C.

[0075] In a specific embodiment of the present invention, the intermediate compound BO-3 and the trisubstituted amine (BO-4) are preferably dissolved in an ethanol-water mixture (volume ratio 1:1), reacted overnight at 90°C, and concentrated under reduced pressure to obtain the monomer compound BO-5.

[0076] After obtaining the monomer compound, the present invention mixes the monomer compound, cyclohexane-1,4-diisocyanate, catalyst and organic solvent to carry out a nucleophilic addition reaction to obtain the precursor compound.

[0077] In this invention, the equivalence ratio of the monomer compound and cyclohexane-1,4-diisocyanate is preferably 1:1.2.

[0078] In this invention, the equivalence ratio of the monomer compound to the catalyst is preferably 1:0.01 to 0.5.

[0079] In this invention, the catalyst is preferably tin lauryl laurate.

[0080] In this invention, the organic solvent is preferably acetonitrile.

[0081] In a specific embodiment of the present invention, preferably, the monomer compound BO-5 and cyclohexane-1,4-diisocyanate BO-7 are dissolved in acetonitrile, tin laurylate is added, the mixture is refluxed overnight, cooled, poured into methanol to precipitate a solid, and dried to obtain the prepolymer compound BO-8.

[0082] After obtaining the precursor compound, the present invention mixes the precursor compound with a sodium salt and performs ion exchange to obtain the isocyanate containing the quaternary ammonium salt structure.

[0083] In this invention, the ion exchange is preferably carried out in an aqueous solution.

[0084] In this invention, the ion exchange time is preferably 1 to 5 hours.

[0085] In this invention, the equivalence ratio of the precursor compound to the sodium salt is preferably 1:2 to 5.

[0086] In this invention, X in the sodium salt NaX is preferably a fluoride ion, chloride ion, bromide ion, iodide ion, hexafluorophosphate ion, or nitrate ion.

[0087] In a specific embodiment of the present invention, the precursor compound BO-8 and its sodium salt are preferably dissolved in deionized water and heated for 1 to 5 hours, then filtered to obtain the isocyanate containing the quaternary ammonium salt structure.

[0088] The present invention also provides a photothermal dual-curing coating, comprising the following components in weight percentage:

[0089] The above technical solution comprises 5%–30% acrylate containing phosphazene and hydroxyl functional groups, 5%–40% isocyanate containing quaternary ammonium salt structure, 3%–50% filler, 0.1%–5% defoamer, 0.5%–10% thickener, 20%–70% solvent, 0.1%–5% tin reagent, and 0.1%–5% photoinitiator, with the sum of the mass percentages of all components being 100%.

[0090] In this invention, the mass percentage of acrylate in the coating is preferably 20% to 30%.

[0091] In this invention, the mass percentage of isocyanate in the coating is preferably 20% to 30%.

[0092] In this invention, the filler content in the coating is preferably 3% to 30% by mass.

[0093] In this invention, the filler is preferably barium sulfate.

[0094] In this invention, the mass percentage of thickener in the water-based coating is preferably 2.0% to 5%.

[0095] In this invention, the thickener is preferably ViscoPlus 300.

[0096] In this invention, the defoamer content in the water-based coating is preferably 0.2% to 5% by mass.

[0097] In this invention, the defoamer is preferably TEGO-81.

[0098] In this invention, the solvent content in the water-based coating is preferably 33.5% to 40% by mass.

[0099] In this invention, the solvent is preferably dipropylene glycol methyl ether and / or ethanol.

[0100] In this invention, the photoinitiator in the water-based coating is preferably 1% to 3% by mass.

[0101] In this invention, the photoinitiator is preferably 1-hydroxycyclohexylphenyl ketone (Irgacure-184), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Lucirin TPO), or 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocur1173).

[0102] The present invention does not impose any special limitation on the preparation method of the photothermal dual-curing coating; any preparation method of the composition known to those skilled in the art can be used.

[0103] The present invention also provides the application of the photothermal dual-curing coating described in the above technical solution in metal coating.

[0104] The present invention does not impose any special limitation on the specific method of application, and any method known to those skilled in the art can be used.

[0105] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0106] Example 1: Synthesis of acrylate A-1 containing phosphazene and hydroxyl functional groups, the principle of which is shown in the following formula:

[0107]

[0108] 146.4 g (0.6 mol) of pentaerythritol diacrylate was dissolved in 1 L of dichloromethane, and 28.8 g (0.76 mol, 60%) of sodium hydride was added. The mixture was stirred at room temperature for 2 h, and then 34.4 g (0.1 mol) of hexachlorophosphine was added to the reaction system. The reaction was heated for 12 h. After cooling, the mixture was washed with water and dried to obtain 142.7 g of concentrated compound A-1. 1 H NMR (500MHz, CDCl3) δ6.41 (dd, J=19.8, 4.4Hz, 12H), 6.12 (dd, J=33.5, 20.0Hz, 12H), 6.01 (s, 6H),5.83(dd,J=33.5,4.6Hz,12H),4.27(s,12H),3.92(s,12H),3.79(s,12H),3.20(s,12H).

[0109] Example 2: Synthesis of acrylate A-2 containing phosphazene and hydroxyl functional groups, the principle of which is shown in the following formula:

[0110]

[0111] 163.2 g (0.6 mol) of pentaerythritol diacrylate was dissolved in 1 L of dichloromethane, and 28.8 g (0.76 mol, 60%) of sodium hydride was added. The mixture was stirred at room temperature for 2 h, and then 34.4 g (0.1 mol) of hexachlorophosphine was added to the reaction system. The reaction was heated for 12 h. After cooling, the mixture was washed with water and dried to obtain 153.2 g of concentrated compound A-2. 1 H NMR (500MHz, CDCl3) δ6.43 (dt, J=4.0, 2.0Hz, 12H), 6.36 (dt, J=4.2, 2.0Hz, 12H), 5.04 (s,6H),4.49(s,12H),3.78(d,J=11.4Hz,24H),3.27(s,12H),2.00(t,J=2.0Hz,36H).

[0112] Example 3: Synthesis of acrylate A-3 containing phosphazene and hydroxyl functional groups, the principle of which is shown in the following formula:

[0113]

[0114] 180.0 g (0.6 mol) of pentaerythritol diacrylate was dissolved in 1 L of dichloromethane, and 28.8 g (0.76 mol, 60%) of sodium hydride was added. The mixture was stirred at room temperature for 2 h, and then 34.4 g (0.1 mol) of hexachlorophosphine was added to the reaction system. The reaction was heated for 12 h. After cooling, the mixture was washed with water and dried to obtain 176.8 g of concentrated compound A-3. 1 H NMR(500MHz, CDCl3) δ6.29(dt,J=4.1,2.0Hz,12H),5.46(dt,J=4.1,2.0Hz,12H),4.29(s,12H),3.90(s, 12H),3.79(s,12H),3.52(s,12H),2.44(qt,J=13.3,1.9Hz,24H),1.34(s,6H),1.07(t,J=13.3Hz,36H)..

[0115] Example 4: Synthesis of acrylate A-4 containing phosphazene and hydroxyl functional groups, the principle of which is shown in the following formula:

[0116]

[0117] 196.9 g (0.6 mol) of pentaerythritol diacrylate was dissolved in 1 L of dichloromethane, and 28.8 g (0.76 mol, 60%) of sodium hydride was added. The mixture was stirred at room temperature for 2 h, and then 34.4 g (0.1 mol) of hexachlorophosphine was added to the reaction system. The reaction was heated for 12 h. After cooling, the mixture was washed with water and dried to obtain 187.5 g of concentrated compound A-4. 1 H NMR(500MHz, CDCl3) δ6.29(dt,J=4.1,2.0Hz,12H),5.46(dt,J=4.1,2.0Hz,12H),4.22(s,12H),3.94(s,12H) ,3.79(s,12H),3.68(s,12H),2.51-2.24(m,24H),1.57(s,6H),1.50-1.28(m,24H),0.94(t,J=13.1Hz,36H).

[0118] Example 5: Synthesis of acrylates containing phosphazene and hydroxyl functional groups (A-5), the principle of which is shown in the following formula:

[0119]

[0120] 213.7 g (0.6 mol) of pentaerythritol diacrylate was dissolved in 1 L of dichloromethane, and 28.8 g (0.76 mol, 60%) of sodium hydride was added. The mixture was stirred at room temperature for 2 h, and then 34.4 g (0.1 mol) of hexachlorophosphine was added to the reaction system. The reaction was heated for 12 h. After cooling, the mixture was washed with water and dried to obtain 196.8 g of concentrated compound A-5. 1 H NMR (500MHz, CDCl3) δ6.29(s,12H),5.46(s,12H),4.31(s,12H),3.94(s,12H),3.79(s, 12H),3.58(s,12H),2.78(s,6H),2.41(s,24H),1.33(d,J=45.0Hz,49H),0.93(s,36H).

[0121] Example 6: Synthesis of A-6 acrylate containing phosphazene and hydroxyl functional groups, based on the following formula.

[0122]

[0123] 247.4 g (0.6 mol) of pentaerythritol diacrylate was dissolved in 1 L of dichloromethane, and 28.8 g (0.76 mol, 60%) of sodium hydride was added. The mixture was stirred at room temperature for 2 h, and then 34.4 g (0.1 mol) of hexachlorophosphine was added to the reaction system. The reaction was heated for 12 h. After cooling, the mixture was washed with water and dried to obtain 218.1 g of concentrated compound A-6. 1H NMR (500MHz, CDCl3) δ6.27(s,12H),5.44(s,12H),4.34(s,12H),3.91(s,12H),3.78(s, 12H),3.47(s,12H),2.60(s,6H),2.40(s,24H),1.31(t,J=10.0Hz,92H),0.89(s,36H).

[0124] Example 7: Synthesis of B-1 isocyanate containing a quaternary ammonium salt structure, the principle of which is shown in the following formula:

[0125]

[0126] 170g (1mol) of 3,6-dihydroxy-1,4-dibenzyl alcohol (7), 276g (2mol) of potassium carbonate, 370g (2mol) of 1,2-dibromoethane, and 2L of dichloromethane were mixed and stirred at room temperature for 24h. The reaction was detected to be complete by thin-layer chromatography. The mixture was filtered to remove the residue. The organic phase was washed three times with pure water and dried to obtain 312g of concentrated intermediate compound (9). 1 H NMR (500MHz, CDCl3) δ7.00(s,2H),4.61(s,4H),4.41-4.20(m,4H),3.88-3.66(m,4H),1.52(s,2H).

[0127] 76 g (0.2 mol) of compound (9) and 35.4 g (0.2 mol) of methyl butyl benzylamine (10) were dissolved in 1000 mL of ethanol-water (volume ratio 1:1) mixture and reacted overnight at 90 °C. The mixture was then concentrated under reduced pressure to obtain 98.3 g of monomer compound 11. 1 HNMR (500MHz, CDCl3) δ7.32-7.09(m,10H),6.99(s,2H),4.60(d,J=7.1Hz,8H),4.39(t,J=7.8Hz,4H),3.84(t,J= 7.9Hz,4H),3.56-3.24(m,10H),1.81(p,J=15.4Hz,4H),1.51(s,2H),1.37-1.08(m,4H),0.89(t,J=13.1Hz,6H).

[0128] 73.6 g (0.1 mol) of compound 11 and 19.9 g (0.12 mol) of isocyanate compound 12 were dissolved in 1 L of acetonitrile. 2 g of tin laurylate was added, and the mixture was refluxed overnight. After cooling, the mixture was poured into methanol to precipitate a solid, which was then dried to obtain 85.7 g of the target prepolymer compound B-1. 1HNMR (500MHz, CDCl3) δ7.31-7.11(m,10H),7.00(s,2H),5.65(s,1H),5.28-5.08(m,2H),5.05(s,2H),4.68(s,2H),4.61(s,4H),4.39(dtd,J=23 .8,19.2,1.2Hz,4H),4.26(s,1H),3.84(td,J=19.2,1.3Hz,4H),3.51-3 .25(m,10H),2.12-1.60(m,12H),1.45-1.00(m,4H),0.97-0.70(m,6H).

[0129] Example 8: Synthesis of B-2 isocyanate containing a quaternary ammonium salt structure, the principle of which is shown in the following formula:

[0130]

[0131] 76 g (0.2 mol) of compound (9) and 43.8 g (0.2 mol) of dibutylbenzylamine (13) were dissolved in 1000 mL of ethanol-water (volume ratio 1:1) mixture and reacted overnight at 90 °C. The mixture was then concentrated under reduced pressure to obtain 115.6 g of monomer compound 14. 1 H NMR (500MHz, CDCl3) δ7.35-7.09(m,10H),7.00(s,2H),4.72(s,4H),4.61(s,4H),4.39(t,J=7.5Hz,4H),3.85(dd,J=11.3,4 .0Hz,4H),3.40(t,J=15.3Hz,8H),1.83(p,J=15.4Hz,8H),1.38(s,2H),1.33-1.16(m,8H),0.89(dd,J=13.4,12.8Hz,12H).

[0132] 82 g (0.1 mol) of compound 11 and 19.9 g (0.12 mol) of isocyanate compound 12 were dissolved in 1 L of acetonitrile, 2 g of tin laurylate was added, the mixture was refluxed overnight, cooled, poured into methanol to precipitate a solid, dried, and 90.2 g of the target prepolymer compound B-2 was obtained. 1HNMR(500MHz, CDCl3)δ7.41-7.09(m,10H),7.00(s,2H),5.53(s,1H),5.2 2-5.06(m,2H),5.05(s,2H),4.99(s,4H),4.68(s,2H),4.41(dtd,J=24.4 ,19.2,1.2Hz,4H),4.28(s,1H),3.84(td,J=19.2,1.2Hz,4H),3.40(t,J= 21.7Hz,8H),2.12-1.61(m,16H),1.45-1.02(m,8H),1.01-0.72(m,12H).

[0133] Example 9: Synthesis of B-3 isocyanate containing a quaternary ammonium salt structure. The principle is shown in the following formula:

[0134]

[0135] 76 g (0.2 mol) of compound (9) and 28.6 g (0.2 mol) of methyl dibutylamine (15) were dissolved in 1000 mL of ethanol-water (volume ratio 1:1) mixture and reacted overnight at 90 °C. The mixture was then concentrated under reduced pressure to obtain 88.7 g of monomer compound 16. 1 HNMR (500MHz, CDCl3) δ6.99(s,2H),4.60(s,4H),4.38(t,J=7.9Hz,4H),3.84(t,J=7.9Hz,4H),3.40(t,J =15.5Hz,8H),3.28(s,6H),1.97-1.64(m,8H),1.47(s,2H),1.36-1.08(m,8H),0.89(t,J=13.1Hz,12H).

[0136] 66.8 g (0.1 mol) of compound 11 and 19.9 g (0.12 mol) of isocyanate compound 12 were dissolved in 1 L of acetonitrile, 2 g of tin laurylate was added, the mixture was refluxed overnight, cooled, poured into methanol to precipitate a solid, dried, and 72.9 g of the target prepolymer compound B-3 was obtained. 1HNMR (500MHz, CDCl3) δ7.00 (s, 2H), 5.52 (s, 1H), 5.14 (ddtd, J = 9.4, 7.5, 3. 6,2.0Hz,2H),5.05(s,2H),4.74(s,2H),4.40(td,J=9.6,8.1Hz,4H),4.30(s ,1H),3.84(t,J=9.6Hz,4H),3.40(t,J=10.9Hz,8H),3.27(s,6H),2.00-1.88 (m,8H),1.80(p,J=11.2Hz,8H),1.35-1.14(m,8H),0.89(t,J=12.1Hz,12H).

[0137] Example 10: Synthesis of B-4 isocyanate containing a quaternary ammonium salt structure, the principle of which is shown in the following formula:

[0138]

[0139] 76 g (0.2 mol) of compound (9) and 50.6 g (0.2 mol) of butyldibenzylamine (17) were dissolved in 1000 mL of ethanol-water (volume ratio 1:1) mixture and reacted overnight at 90 °C. The mixture was then concentrated under reduced pressure to obtain 112.5 g of monomer compound 18. 1 H NMR (500MHz, CDCl3) δ7.35-7.11(m,20H),6.99(s,2H),4.92(s,8H),4.60(s,4H),4.51-4.30(m,4H),3.98-3.70(m, 4H), 3.40 (t, J = 15.2Hz, 4H), 1.81 (p, J = 15.1Hz, 4H), 1.48 (s, 2H), 1.37-1.08 (m, 4H), 0.89 (dd, J = 13.3, 12.8Hz, 6H).

[0140] 89 g (0.1 mol) of compound 11 and 19.9 g (0.12 mol) of isocyanate compound 12 were dissolved in 1 L of acetonitrile, 2 g of tin laurylate was added, the mixture was refluxed overnight, cooled, poured into methanol to precipitate a solid, dried, and 90.2 g of the target prepolymer compound B-4 was obtained. 1H NMR (500MHz, CDCl3) δ7.34-7.12(m,20H),7.00(s,2H),5.60(s,1H),5.14(dtdd,J=15.0,10.8,4.2,2.3Hz,2H),5.05(s,2H),4.91(s,8H),4.8 2(s,2H),4.39-4.22(m,5H),3.84(td,J=19.2,1.5Hz,4H),3.40(t,J=2 1.7Hz,4H),2.07-1.65(m,12H),1.41-1.10(m,4H),1.01-0.69(m,6H).

[0141] Example 11

[0142] The coating formulation is shown in Table 1. The contents in Table 1 are mass contents.

[0143] Table 1. Water-based coating formulation for Formula 1

[0144]

[0145] Coating formulations two through six are the same as formulation one, except that the acrylic resin A-1 in formulation one is replaced with A-2, A-3, A-4, A-5, and A-6 respectively in formulations two through six.

[0146] Coating Formulation 7 is the same as Formulation 1, except that Formulation 7 replaces isocyanate B-1 in Formulation 1 with B-2.

[0147] Coating formulations 8-12 are the same as formulation 7, except that: in formulations 8-12, acrylic resin A-1 in formulation 7 is replaced with A-2, A-3, A-4, A-5, and A-6 respectively.

[0148] Coating formulation thirteen is the same as formulation one, except that in formulation thirteen, isocyanate B-1 in formulation one is replaced with B-3.

[0149] Coating formulations 14 to 18 are the same as formulation 13, except that: in formulations 14 to 18, acrylic resin A-1 in formulation 13 is replaced with A-2, A-3, A-4, A-5, and A-6 respectively.

[0150] Coating formulation nineteen is the same as formulation one, except that isocyanate B-1 in formulation one is replaced with B-4.

[0151] Coating formulations 20-24 are the same as formulation 19, except that: in formulations 20-24, acrylic resin A-1 in formulation 19 is replaced with A-2, A-3, A-4, A-5, and A-6 respectively.

[0152] Antibacterial activity test of isocyanates containing quaternary ammonium salt structure

[0153] Quantitative antibacterial tests were conducted using B-1, B-2, B-3, and B-4, with selected bacterial species including Escherichia coli, Staphylococcus aureus, Candida albicans, Salmonella, Klebsiella pneumoniae, and Pseudomonas aeruginosa. Using standard methods, the antibacterial rates of B-1, B-2, B-3, and B-4 all reached 100%.

[0154] Waterborne Coating Performance Testing

[0155] Painting

[0156] Clean the surface of the metal substrate with zirconium salt and deionized water to remove contaminants, and then dry. Spray the substrate surface with coatings of formulations one through twenty-four, heat in a tunnel oven at 200°C for 10 minutes, and then irradiate with UV-LED for 10 minutes to allow it to crosslink and cure.

[0157] The hardness, adhesion, solvent resistance (number of alcohol washes), and limiting oxygen index of the coatings obtained from formulations one through twenty-four were tested, and the results are shown in Table 2. The hardness of the cured film was tested according to GB / T 6739—1996 "Determination of Hardness of Coatings by Pencil Method", with a test range of 4B to 6H; the adhesion test was conducted according to GB / T 9286—1998; the yellowing resistance test was conducted according to GB-T 9761-2008 "Visual Colorimetry of Paints and Varnishes"; and the solvent resistance test was conducted according to Method A (immersion method) of GB 9274—1988 "Determination of Resistance to Liquid Media in Paints and Varnishes". The cured coating film was prepared into 5cm × 2cm × 0.2cm samples, and the limiting oxygen index was tested in an oxygen index tester to examine its flame retardant properties.

[0158] The antibacterial effect of the coatings was tested in accordance with "GB / T 21866 Antibacterial Coatings (Films) - Determination of Antibacterial Properties and Antibacterial Effect". The antibacterial rate of formulations one through twenty-four was 100%.

[0159] As shown in Table 2, the acrylate containing phosphazene and hydroxyl functional groups of the present invention combines the acrylic acid structure with phosphazene, and the structure also contains hydroxyl functional groups (-OH). The hydroxyl group is an active reactive group and can continue to react with epoxy, isocyanate and other functional groups. The isocyanate containing quaternary ammonium salt structure of the present invention is an important component of thermosetting resin. The quaternary ammonium salt structure is introduced into the isocyanate structure system. The quaternary ammonium salt has antibacterial and disinfecting effects. The isocyanate structure can undergo chemical cross-linking reaction with the aforementioned acrylate structural units containing phosphazene and hydroxyl functional groups. The coating prepared by the present invention has both flame retardant and antibacterial effects.

[0160] Table 2 Performance Test Results

[0161]

[0162]

[0163] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An acrylate containing phosphazene and hydroxyl functional groups, having the structure shown in Formula A: Formula A, In formula A, R1~R 12 Independently alkyl chain C y H 2y+1 , where y is an integer from 0 to 20.

2. The acrylate containing phosphazene and hydroxyl functional groups according to claim 1, characterized in that, It has any of the structures shown in A1 to A6: 。 3. The method for preparing acrylate according to claim 1 or 2, characterized in that, Includes the following steps: Pentaerythritol di(substituted acrylate), hexachlorophosphine, sodium hydride, and an organic solvent are mixed and subjected to a substitution reaction to obtain the acrylic resin containing phosphazene and hydroxyl functional groups.

4. The preparation method according to claim 3, characterized in that, The equivalent ratio of pentaerythritol di(substituted acrylate) to hexachlorophosphine is 1:0.05~0.

5.

5. The preparation method according to claim 3, characterized in that, The equivalent ratio of the pentaerythritol di(substituted acrylate) to sodium hydride is 1:1~2.

6. An isocyanate containing a quaternary ammonium salt structure, having the structure shown in any one of formulas B1 to B4: 。 7. The method for preparing the isocyanate containing a quaternary ammonium salt structure according to claim 6, characterized in that, Includes the following steps: 3,6-dihydroxy-1,4-dibenzyl alcohol was mixed with terminal dibromo-substituted alkanes and organic solvents to carry out a substitution reaction, yielding an intermediate compound. The intermediate compound, the trisubstituted amine, and the solvent were mixed and subjected to an amination reaction to obtain the monomer compound; The monomeric compound, cyclohexane-1,4-diisocyanate, catalyst, and organic solvent were mixed and subjected to a nucleophilic addition reaction to obtain the isocyanate containing the quaternary ammonium salt structure.

8. A photothermal dual-curing coating, characterized in that, The components include the following components by mass percentage: The acrylate containing phosphazene and hydroxyl functional groups as described in claim 1 or 2 comprises 5% to 30%, the isocyanate containing quaternary ammonium salt structure as described in claim 6 comprises 5% to 40%, filler comprises 3% to 50%, defoamer comprises 0.1% to 5%, thickener comprises 0.5% to 10%, solvent comprises 20% to 70%, tin reagent comprises 0.1% to 5%, and photoinitiator comprises 0.1% to 5%, the sum of the mass percentages of all components is 100%.

9. The application of the photothermal dual-curing coating as described in claim 8 in metal coating.

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