A waterborne acrylic isocyanate resin, a preparation method and application thereof, and a waterborne paint

Abstract

The application provides a water-based acrylic isocyanate resin, a preparation method and application thereof, and a water-based paint, and belongs to the technical field of paints.The application provides a water-based acrylic isocyanate resin, wherein a phosphorus-containing flame retardant is introduced into the water-based acrylic isocyanate resin, and an ionic liquid functional group (imidazole ion) is combined to obtain the water-based acrylic isocyanate resin with the flame retardant property.The water-based paint provided by the application has good flame retardant property, low VOC (volatile organic compound), and environmental protection, and can be applied to the coating of wooden wares.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to a waterborne acrylic isocyanate resin, its preparation method and application, and waterborne coatings. Background Technology

[0002] Wood coatings are a type of coating used for the protection and finishing of wood materials. Due to environmental concerns and restrictions on VOC emissions, the development of oil-based paints has been limited, leading to the emergence of water-based wood coatings. Water-based polyurethane wood coatings have been widely developed and used due to their low VOC content and environmental friendliness. However, the drawbacks of water-based polyurethane wood coatings have gradually become apparent. As a type of wood coating, the flammability of wood materials and the resulting fires have attracted widespread attention, making it essential to improve the flame-retardant properties of water-based polyurethane materials. Summary of the Invention

[0003] In view of this, the purpose of this invention is to provide a waterborne acrylic isocyanate resin, its preparation method and application, and waterborne coatings. The waterborne acrylic isocyanate resin provided by this invention has good flame retardant properties.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides an aqueous acrylic isocyanate resin having the structure shown in Formula I:

[0006]

[0007] In Equation I, n is an integer from 0 to 10, m is from 1 to 100, and * represents a connection site;

[0008] It is a substituent group in the triisocyanate structure.

[0009] Preferably, the The structure is as follows:

[0010]

[0011] Preferably, the aqueous acrylic isocyanate resin has a structure shown in formula Y-1-1, Y-2-1, Y-3-1, Y-4-1, Y-5-1 or Y-6-1:

[0012]

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

[0014] Compound A, P2S5, and an organic solvent were mixed and subjected to a first substitution reaction to obtain compound B;

[0015] Compound B was subjected to a first reflux reaction in hydrochloric acid to obtain compound C;

[0016] Compound C, compound D, sulfuric acid, and an organic solvent were mixed and subjected to a dehydration reaction to obtain compound E;

[0017] The compound E, imidazole, and anhydrous ethanol were mixed and subjected to a second substitution reaction to obtain compound G;

[0018] The compound G, ethylene bromide, and anhydrous ethanol were mixed and subjected to a second reflux reaction to obtain compound H;

[0019] Compound H, compound I, and an organic solvent were mixed and subjected to a third substitution reaction to obtain compound J;

[0020] The compound J, isocyanate compound K, and organic solvent were mixed and subjected to an amination reaction to obtain polymerization precursor compound L;

[0021] The polymerization precursor compound L, the initiator and the solvent are mixed and subjected to a polymerization reaction to obtain the aqueous acrylic isocyanate resin.

[0022] The structures of compounds A, B, C, D, E, G, H, I, J, K, and L are shown in the following formulas:

[0023]

[0024] Preferably, the molar ratio of compound A to P2S5 is 1:1, and P2S5 is added in two equal portions.

[0025] Preferably, the molar ratio of compounds C and D is 0.4:1.

[0026] The present invention also provides the application of the waterborne acrylic isocyanate resin described in the above technical solution in the field of waterborne coatings.

[0027] The present invention also provides an aqueous coating comprising the following components in weight percentage:

[0028] The above technical solution comprises 20%–60% waterborne acrylic isocyanate resin, 10%–40% glycol, 1%–10% barium sulfate, 0.1%–10% thickener, 0.1%–10% defoamer, 1%–50% solvent, 0.1%–5% photoinitiator, and 0.1%–5% tin laurylate.

[0029] Preferably, the diol comprises an aliphatic diol.

[0030] The present invention also provides the application of the water-based coatings described in the above technical solution in wood coating.

[0031] This invention provides an aqueous acrylic isocyanate resin having the structure shown in Formula I. This invention introduces a phosphorus-containing flame retardant into the aqueous acrylic isocyanate resin and combines it with an ionic liquid functional group (imidazolium ion) to obtain an aqueous acrylic isocyanate resin with flame retardant properties.

[0032] This invention provides a water-based coating with good flame retardant properties, low VOC, and environmental friendliness, which can be applied to the coating of wood products. Detailed Implementation

[0033] This invention provides an aqueous acrylic isocyanate resin having the structure shown in Formula I:

[0034]

[0035] In Equation I, n is an integer from 0 to 10, m is from 1 to 100, and * represents a connection site;

[0036] It is a substituent group in the triisocyanate structure.

[0037] In this invention, the The preferred structure is as follows:

[0038]

[0039] In this invention, the structure of the aqueous acrylic isocyanate resin is preferably as shown in formulas Y1 to Y6:

[0040]

[0041] In this invention, the aqueous acrylic isocyanate resin preferably has the structure shown in formula Y-1-1, Y-2-1, Y-3-1, Y-4-1, Y-5-1 or Y-6-1:

[0042]

[0043] The present invention also provides a method for preparing the waterborne acrylic isocyanate resin described in the above technical solution, comprising the following steps:

[0044] Compound A, P2S5, and an organic solvent were mixed and subjected to a first substitution reaction to obtain compound B;

[0045] Compound B was subjected to a first reflux reaction in hydrochloric acid to obtain compound C;

[0046] Compound C, compound D, sulfuric acid, and an organic solvent were mixed and subjected to a dehydration reaction to obtain compound E;

[0047] The compound E, imidazole, and anhydrous ethanol were mixed and subjected to a second substitution reaction to obtain compound G;

[0048] The compound G, ethylene bromide, and anhydrous ethanol were mixed and subjected to a second reflux reaction to obtain compound H;

[0049] Compound H, compound I, and an organic solvent were mixed and subjected to a third substitution reaction to obtain compound J;

[0050] The compound J, isocyanate compound K, and organic solvent were mixed and subjected to an amination reaction to obtain polymerization precursor compound L;

[0051] The polymerization precursor compound L, the initiator and the solvent are mixed and subjected to a polymerization reaction to obtain the aqueous acrylic isocyanate resin.

[0052] The structures of compounds A, B, C, D, E, G, H, I, J, K, and L are shown in the following formulas:

[0053]

[0054] In this invention, the principle of the preparation method is shown in the following formula:

[0055]

[0056] In this invention, compound A, P2S5, and an organic solvent are mixed to carry out a first substitution reaction to obtain compound B.

[0057] In this invention, the molar ratio of compound A to P2S5 is preferably 1:1, and P2S5 is preferably added in two equal portions.

[0058] In this invention, the organic solvent is preferably toluene.

[0059] In this invention, the preferred ratio of compound A to organic solvent is 1 mol: 1000 mL.

[0060] In a specific embodiment of the present invention, preferably, compound A, organic solvent, and a first portion of P2S5 are added to a flask equipped with a mechanical stirrer, a condenser, and a nitrogen inlet and outlet. The temperature is 60°C, nitrogen is introduced, and the mixture is stirred for 2 hours. After the stirring is completed, the temperature is lowered to 40°C, a second portion of P2S5 is added, nitrogen is introduced, and the reaction is carried out for 24 hours. Heating is stopped, the mixture is cooled to room temperature, and the solvent is removed under reduced pressure. The resulting oily liquid is added to chloroform and then shaken and filtered. The resulting filtrate is washed three times with a saturated sodium bicarbonate solution, dried, concentrated, and the solid is recrystallized with acetonitrile to obtain compound B.

[0061] After obtaining compound B, the present invention performs a first reflux reaction of compound B in hydrochloric acid to obtain compound C.

[0062] In this invention, the concentration of the hydrochloric acid is preferably 1 mol / L.

[0063] In this invention, the preferred ratio of compound B to hydrochloric acid is 0.5 mol: 800 mL.

[0064] In this invention, the preferred time for the first reflux reaction is 4 hours.

[0065] In a specific embodiment of the present invention, it is preferable to add the compound B and hydrochloric acid to a flask equipped with a mechanical stirrer, a condenser, and a nitrogen inlet and outlet to carry out a first reflux reaction. After the first reflux reaction is completed, the obtained product is cooled to room temperature, extracted with dichloromethane, washed three times with water, dried, concentrated, and the solid is recrystallized with ethanol to obtain compound C.

[0066] After obtaining compound C, the present invention mixes compound C, compound D, sulfuric acid and organic solvent to carry out a dehydration reaction to obtain compound E.

[0067] In this invention, the molar ratio of compounds C and D is preferably 0.4:1.

[0068] In this invention, the organic solvent is preferably toluene.

[0069] In this invention, the preferred ratio of compound C to concentrated sulfuric acid is 0.4 mol: 10 mL, and the preferred mass fraction of concentrated sulfuric acid is 98%.

[0070] In a specific embodiment of the present invention, compounds C and D are preferably dissolved in toluene, concentrated sulfuric acid is added, and the reaction is refluxed using a water separator to remove water. After reacting for 12 hours, the mixture is cooled to room temperature, washed with saturated sodium bicarbonate solution until neutral, dried, concentrated, and the solid is recrystallized from toluene to obtain compound E.

[0071] After obtaining compound E, the present invention mixes compound E, imidazole (compound F) and anhydrous ethanol to carry out a second substitution reaction to obtain compound G.

[0072] In this invention, the molar ratio of compound E to imidazole is preferably 3:5.

[0073] In this invention, the preferred ratio of compound E to anhydrous ethanol is 0.3 mol: 500 mL.

[0074] In this invention, the second substitution reaction is preferably carried out over a period of 8 hours.

[0075] In a specific embodiment of the present invention, it is preferable to dissolve the compound E and imidazole in anhydrous ethanol to carry out the second reflux reaction, and after the reaction is completed, concentrate under reduced pressure to remove the solvent, and recrystallize with toluene to obtain compound G.

[0076] After obtaining compound G, the present invention mixes compound G, ethylene bromide and anhydrous ethanol and carries out a second reflux reaction to obtain compound H.

[0077] In this invention, the molar ratio of compound G to ethylene bromide is preferably 1:2.

[0078] In this invention, the preferred ratio of compound G to anhydrous ethanol is 0.25 mol: 500 mL.

[0079] In a specific embodiment of the present invention, it is preferable to dissolve the compound G and ethylene bromide in anhydrous ethanol, stir and reflux overnight, remove the solvent under reduced pressure, and recrystallize the solid with anhydrous ethanol to obtain compound H.

[0080] After obtaining compound H, the present invention mixes compound H, compound I and an organic solvent to carry out a third substitution reaction to obtain compound J.

[0081] In this invention, the molar ratio of compound H to I is preferably 1:1.

[0082] In this invention, the organic solvent is preferably toluene.

[0083] In this invention, the preferred ratio of compound H to toluene is 0.2 mol: 200 mL.

[0084] In a specific embodiment of the present invention, it is preferable to dissolve compounds H and I in toluene and stir overnight, concentrate under reduced pressure to remove the solvent, and recrystallize the solid with ethanol to obtain compound J.

[0085] After obtaining compound J, the present invention mixes compound J, isocyanate compound K and organic solvent to carry out an amination reaction to obtain polymerization precursor compound L.

[0086] In this invention, the molar ratio of compound J to K is preferably 1:1.

[0087] In this invention, the organic solvent is preferably toluene.

[0088] In this invention, the preferred ratio of compound J to toluene is 0.1 mol: 250 mL.

[0089] In this invention, the temperature of the amination reaction is preferably 80°C, and the time is preferably 4 hours.

[0090] In a specific embodiment of the present invention, compounds J and K are preferably added to toluene, stirred at 80°C for 4 hours, concentrated under reduced pressure, solvent removed, and recrystallized with ethanol to obtain polymerization precursor compound L.

[0091] After obtaining the polymerization precursor compound L, the present invention mixes the polymerization precursor compound L, an initiator and a solvent to carry out a polymerization reaction to obtain the waterborne acrylic isocyanate resin.

[0092] In this invention, the solvent is preferably anhydrous methanol.

[0093] In this invention, the initiator is preferably azobisisobutyronitrile (AIBN), and the initiator is preferably added in the form of an initiator solution, which is preferably prepared by dissolving 0.1 g of AIBN in 10 mL of methanol.

[0094] In this invention, the preferred temperature for the polymerization reaction is 85°C.

[0095] In a specific embodiment of the present invention, the compound L is preferably dissolved in anhydrous methanol, and an initiator is added dropwise under stirring and the reaction is stirred overnight. After the reaction is completed, the solvent is removed by concentration to obtain the aqueous acrylic isocyanate resin.

[0096] The present invention also provides the application of the waterborne acrylic isocyanate resin described in the above technical solution in the field of waterborne coatings.

[0097] The present invention also provides an aqueous coating comprising the following components in weight percentage:

[0098] The above technical solution comprises 20%–60% waterborne acrylic isocyanate resin, 10%–40% glycol, 1%–10% barium sulfate, 0.1%–10% thickener, 0.1%–10% defoamer, 1%–50% solvent, 0.1%–5% photoinitiator, and 0.1%–5% tin laurylate.

[0099] In this invention, the waterborne acrylic isocyanate resin in the waterborne coating is preferably 25% to 50% by mass, more preferably 20%, 25%, 30%, 35%, 40%, 45%, 50% or 60%.

[0100] In this invention, the mass percentage of diol in the water-based coating is preferably 15% to 35%, more preferably 15%, 20%, 25%, 30%, 35% or 40%.

[0101] In this invention, the diol preferably includes aliphatic diols, more preferably one or more of ethylene glycol, propylene glycol, butanediol, cyclohexanediol, and hexanediol. In this invention, the diol functions to react with isocyanates, acting as a capping agent.

[0102] In this invention, the preferred mass percentage of barium sulfate in the water-based coating is 3% to 5%.

[0103] In this invention, the mass percentage of thickener in the water-based coating is preferably 2% to 5%.

[0104] In this invention, the thickener is preferably ViscoPlus 300.

[0105] In this invention, the defoamer content in the water-based coating is preferably 0.3% to 5% by mass.

[0106] In this invention, the defoamer is preferably TEGO-81.

[0107] In this invention, the solvent content in the water-based coating is preferably 23.5% to 40% by mass.

[0108] In this invention, the solvent is preferably water and / or ethanol. When the solvent is a mixture of water and ethanol, the mass ratio of water to ethanol in the mixture is preferably 1-8:1-8.

[0109] In this invention, the photoinitiator in the water-based coating is preferably 1% to 3% by mass.

[0110] 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).

[0111] In this invention, the mass percentage of tin laurylate in the water-based coating is preferably 0.3% to 3%.

[0112] The present invention also provides the application of the water-based coatings described in the above technical solution in wood coating.

[0113] 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.

[0114] In this invention, the application preferably includes a curing process, which preferably involves heating in an 80°C tunnel oven for 10 minutes, followed by UV-LED irradiation for 10 minutes.

[0115] 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.

[0116] Example 1: Synthesis of waterborne acrylic isocyanate resin Y-1-1, the principle of which is shown in the following formula:

[0117]

[0118] 276 g (1 mol) of compound (1-1) and 1000 mL of toluene were added to a 2 L flask equipped with a mechanical stirrer, condenser, and nitrogen inlet / outlet. Then, 111 g (0.5 mol) of P2S5 was added. The mixture was heated to 60 °C, and nitrogen gas was introduced. The mixture was stirred for 2 h. After 2 h, the temperature was lowered to 40 °C, and a second 111 g (0.5 mol) of P2S5 was added. Nitrogen gas was introduced, and the mixture was reacted for 24 h. Heating was stopped, and the mixture was cooled to room temperature. The solvent was removed under reduced pressure. The resulting oily liquid was added to 500 mL of chloroform and then filtered through a shaker. The filtrate was washed three times with saturated sodium bicarbonate solution, dried, concentrated, and the solid was recrystallized from acetonitrile to obtain 227 g of compound (1-2). 1 HNMR (500MHz, CDCl3) δ7.31 (s, 5H), 7.23 (ddd, J = 16.4, 9.1, 3.0Hz, 2H), 6.84-6.73 (m, 1H), 6.71-6.58 (m, 2H), 5.14 (s, 2H), 4.80 (s, 2H), 3.57 (s, 3H).

[0119] 146 g (0.5 mol) of compound (2-1) was added to a 2 L flask equipped with a mechanical stirrer, condenser, and nitrogen inlet and outlet. The mixture was refluxed in 800 mL of 1 mol / L hydrochloric acid for 4 h. After cooling to room temperature, the mixture was extracted with dichloromethane, washed three times with water, dried, concentrated, and the solid was recrystallized from ethanol to obtain 83 g of compound (1-3). 1 H NMR (500MHz, CDCl3) δ7.29-7.15(m,2H),6.85-6.72(m,1H),6.71-6.60(m,2H),5.30(s,2H),2.02(s,1H).

[0120] 75.2 g (0.4 mol) of compound (1-3) and 125 g (1 mol) of 2-bromoethanol were dissolved in 500 mL of toluene. 10 mL of concentrated sulfuric acid was added, and the mixture was refluxed using a water separator to remove water. After reacting for 12 h, the mixture was cooled to room temperature, washed with saturated sodium bicarbonate solution until neutral, dried, concentrated, and the solid was recrystallized from toluene to obtain 105.4 g of compound (1-4). 1 H NMR (500MHz, CDCl3) δ7.23 (ddd, J=16.4, 9.1, 3.0Hz, 2H), 6.83-6.72 (m, 1H), 6.71-6.61(m,2H),5.30(s,2H),4.03(t,J=8.7Hz,2H),3.56(t,J=8.7Hz,2H).

[0121] 88.5 g (0.3 mol) of compound (1-4) and 34 g (0.5 mol) of imidazole were dissolved in 500 mL of anhydrous ethanol and refluxed for 8 h. The solvent was removed by concentration under reduced pressure and recrystallized from toluene to give 79.4 g of compound (1-5). 1 H NMR(500MHz, CDCl3)δ7.92(s,1H),7.37-7.05(m,3H),6.85-6.71(m,2H),6.71-6.6 2(m,2H),5.30(s,2H),4.35(td,J=14.8,1.0Hz,2H),4.01(td,J=14.8,1.2Hz,2H).

[0122] 70.5 g (0.25 mol) of compound (1-5) and 53 g (0.5 mol) of ethylene bromide were dissolved in 500 mL of anhydrous ethanol and stirred under reflux overnight. The solvent was removed under reduced pressure, and the solid was recrystallized from anhydrous ethanol to give 105.6 g of intermediate compound (1-6). 1 H NMR (500MHz, CDCl3) δ7.31-7.11(m,2H),6.83-6.72(m,1H),6.70-6.55(m,2H),6.19(s,1H),5.45(d,J=7.5Hz,1H),5.30(s,2H), 4.79(d,J=7.5Hz,1H), 4.35(t,J=8.4Hz,2H), 4.16(s,1H), 4.01(t,J=8.4Hz,2H), 3.89(d,J=24.7Hz,1H), 3.19(d,J=24.7Hz,1H).

[0123] 38.9 g (0.2 mol) of compounds (1-6) and 26.8 g (0.2 mol) of hydroxyl-containing acryloyl chloride compounds were dissolved in 200 mL of toluene and stirred overnight. The solvent was removed by concentration under reduced pressure, and the solid was recrystallized from ethanol to obtain 54.8 g of compounds (1-8). 1 H NMR (500MHz, CDCl3) δ7.39-7.09(m,2H),6.85-6.72(m,1H),6.71-6.60(m,2H),6.26(dt,J= 4.1,2.0Hz,1H),5.91(d,J=14.1Hz,3H),5.67(dt,J=4.1,1.9Hz,1H),5.23(d,J=7.5Hz,1H) ,4.96(d,J=7.5Hz,1H),4.35(t,J=8.6Hz,2H),4.08(s,1H),4.01(t,J=8.6Hz,2H),3.94(t, J=9.6Hz,2H),3.74(d,J=24.7Hz,1H),3.08(d,J=24.9Hz,1H),2.55(tt,J=9.6,1.9Hz,2H).

[0124] 48.7 g (0.1 mol) of compound (1-8) and 24.3 g (0.1 mol) of isocyanate compound (1-9) were added to 250 mL of toluene, and the mixture was stirred at 80 °C for 4 h. The mixture was concentrated under reduced pressure, the solvent was removed, and the mixture was recrystallized from ethanol to give 65.4 g of polymerization precursor compound (1-10). 1 H NMR (500MHz, CDCl3) δ7.28-7.14(m,2H),6.82(d,J=3.0Hz,2H),6.80-6.71(m,2H),6.69-6.60(m,2H) ,6.50(s,1H),6.24(dt,J=4.1,2.0Hz,1H),5.93(d,J=7.5Hz,1H),5.90(s,2H),5.65(dt,J=4.1,1.9Hz ,1H),5.57(s,1H),5.17(d,J=7.5Hz,1H),4.93(s,1H),4.41-4.29(m,6H),4.24(dd,J=17.9,8.4Hz,4H ), 4.11 (d, J = 24.7Hz, 1H), 4.00 (t, J = 9.1Hz, 2H), 3.19 (d, J = 24.7Hz, 1H), 2.48 (tt, J = 9.4, 2.0Hz, 2H).

[0125] 36.5 g (0.05 mol) of acrylate monomer compound (1-10) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.1 g AIBN dissolved in 10 mL of methanol) was added dropwise. The reaction was stirred at 85 °C overnight. After the reaction was completed, the solvent was removed by concentration to obtain 31.5 g of the target acrylic isocyanate resin material Y-1-1.

[0126] 1 H NMR (500MHz, CDCl3) δ7.51-7.08(m,5H),6.94-6.62(m,3H),5.89-5.63(m,2H),5.37 (d,J=24.7Hz,1H),5.26-4.97(m,2H),4.65-4.47(m,5H),4.21(d,J=4.9Hz,3H),4.1 0(t,J=14.4Hz,2H),3.90(d,J=24.7Hz,1H),3.84-3.78(m,3H),3.77-3.71(m,1H),3 .08(d,J=24.7Hz,1H),2.06(t,J=14.4Hz,1H),1.69(t,J=14.4Hz,1H),0.93(s,2H).

[0127] Example 2: Synthesis of waterborne acrylic isocyanate resin Y-2-1, the principle of which is shown in the following formula:

[0128]

[0129] 48.7 g (0.1 mol) of compound (1-8) and 20.7 g (0.1 mol) of isocyanate compound (2-1) were added to 250 mL of toluene, and the mixture was stirred at 80 °C for 4 h. The mixture was concentrated under reduced pressure, the solvent was removed, and the mixture was recrystallized from ethanol to give 58.4 g of polymerization precursor compound (2-2). 1H NMR (500MHz, CDCl3) δ7.33-7.11(m,2H),6.85-6.71(m,1H),6.71-6.53(m,2H),6.26(dt,J=4.1 ,2.0Hz,1H),5.92(s,2H),5.83(d,J=7.5Hz,1H),5.71-5.56(m,2H),5.26(d,J=7.5Hz,1H),5.0 9(p,J=14.7Hz,1H),4.36(dd,J=14.3,5.1Hz,3H),4.19(t,J=15.0Hz,2H),3.12(d,J=24.7Hz,1 H),2.75(t,J=15.2Hz,1H),2.65-2.42(m,6H),2.28(t,J=15.2Hz,1H),2.11(t,J=15.1Hz,2H).

[0130] 34.6 g (0.05 mol) of acrylate monomer compound (2-2) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.1 g AIBN dissolved in 10 mL of methanol) was added dropwise. The reaction was stirred overnight at 85 °C. After the reaction was completed, the solvent was removed by concentration to obtain 28.7 g of the target acrylic isocyanate resin material Y-2-1. 1 H NMR (500MHz, CDCl3) δ7.44-7.05(m,5H),6.09(s,1H),5.86(d,J=7.5Hz,1H),5.57(d,J=7.5Hz,1H),5.13(d,J=24.7Hz,1H),4. 60(s,1H),4.38(d,J=24.7Hz,1H),4.21-3.52(m,9H),3.37-3.02(m,3H),2.37-2.08(m,3H),2.04-1.45(m,5H),1.06(s,2H).

[0131] Example 3: Synthesis of waterborne acrylic isocyanate resin Y-3-1, the principle of which is shown in the following formula:

[0132]

[0133] 48.7 g (0.1 mol) of compound (1-8) and 41 g (0.1 mol) of isocyanate compound (3-1) were added to 250 mL of toluene, and the mixture was stirred at 80 °C for 4 h. The mixture was concentrated under reduced pressure, the solvent was removed, and the mixture was recrystallized from ethanol to give 71.5 g of polymerization precursor compound (3-2). 1HNMR(500MHz, CDCl3)δ7.38-7.01(m,14H),6.84-6.71(m,1H),6.71-6.60(m,2H),5.92(s, 2H),5.85(s,1H),5.67(dt,J=4.1,2.0Hz,1H),5.40(d,J=7.4Hz,1H),5.14(d,J=7.5Hz,1H) ,5.03(s,1H),4.58(s,1H),4.35(t,J=8.4Hz,2H),4.27-4.14(m,6H),4.11(s,2H),4.01(t, J=8.4Hz,2H),3.84(d,J=24.7Hz,1H),2.95(d,J=24.7Hz,1H),2.56(tt,J=9.8,2.0Hz,2H).

[0134] 44.8 g (0.05 mol) of acrylate monomer compound (3-2) was dissolved in 500 mL of anhydrous methanol. Under stirring, an amount of catalytic initiator, azobisisobutyronitrile (AIBN) (0.1 g AIBN dissolved in 10 mL of methanol) was added dropwise. The reaction was stirred overnight at 85 °C. After the reaction was completed, the solvent was removed by concentration to obtain 38.7 g of the target acrylic isocyanate resin material Y-3-1. 1 HNMR(500MHz, CDCl3)δ7.55-7.35(m,8H),7.30(t,J=12.5Hz,9H),6.14(s,1H),5.74(s,1H),5.45(s,1H),5.21(s,1H),5.14(s,2H),4.56(s, 4H),4.40(s,1H),4.24(d,J=18.0Hz,3H),4.09(s,2H),3.95(s,1H),3 .88-3.69(m,4H),3.17(s,1H),2.25(s,1H),1.70(s,1H),1.26(s,2H).

[0135] Example 4: Synthesis of waterborne acrylic isocyanate resin Y-4-1, the principle of which is shown in the following formula:

[0136]

[0137] 48.7 g (0.1 mol) of compound (1-8) and 42.7 g (0.1 mol) of isocyanate compound (4-1) were added to 250 mL of toluene, and the mixture was stirred at 80 °C for 4 h. The mixture was concentrated under reduced pressure, the solvent was removed, and the mixture was recrystallized from ethanol to give 65.4 g of polymerization precursor compound (4-2). 1H NMR (500MHz, CDCl3) δ7.55-7.30 (m, 8H), 7.23 (d, J = 5.0Hz, 6H), 6.78 (s, 1 H),6.67(s,2H),6.26(s,1H),6.13(s,1H),5.92(s,2H),5.67(s,1H),5.56 (s,1H),5.50(s,1H),5.37(s,1H),5.05(s,1H),4.71(s,1H),4.34(d,J=1 0.0Hz, 6H), 4.23 (d, J = 2.2Hz, 4H), 4.01 (s, 2H), 3.22 (s, 1H), 2.55 (s, 2H).

[0138] 45.6 g (0.05 mol) of acrylate monomer compound (4-2) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.1 g AIBN dissolved in 10 mL of methanol) was added dropwise. The reaction was stirred overnight at 85 °C. After the reaction was completed, the solvent was removed by concentration to obtain 42.6 g of the target acrylic isocyanate resin material Y-4-1. 1 H NMR (500MHz, CDCl3) δ7.58-7.30(m,8H),7.25(t,J=12.1Hz,9H),6.10(s,1H),5.70(s,1H),5.43(s,1H),5.17(s,1H),5.10(s,2H),4.49(s, 4H),4.36(s,1H),4.20(d,J=17.0Hz,3H),4.05(s,2H),3.90(s,1H),3 .85-3.67(m,4H),3.15(s,1H),2.21(s,1H),1.75(s,1H),1.28(s,2H).

[0139] Example 5: Synthesis of waterborne acrylic isocyanate resin Y-5-1, the principle of which is shown in the following formula:

[0140]

[0141] 48.7 g (0.1 mol) of compound (1-8) and 60.5 g (0.1 mol) of isocyanate compound (5-1) were added to 250 mL of toluene, and the mixture was stirred at 80 °C for 4 h. The mixture was then concentrated under reduced pressure, the solvent was removed, and the mixture was recrystallized from ethanol to give 78.7 g of polymerization precursor compound (5-2). 13C NMR (125MHz, CDCl3) δ180.95,157.23,148.02,138.47,136.55,135.94,135.84,135.64,134.52,131.32,131.21,129.93,12 9.28,127.96,125.60,120.54,111.38,108.56,80.56,62.40,61.32,44.57,44.37,43.99,43.71,36.16,30.17,26.66,8.14.

[0142] 54.6 g (0.05 mol) of acrylate monomer compound (5-2) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.1 g AIBN dissolved in 10 mL of methanol) was added dropwise. The reaction was stirred overnight at 85 °C. After the reaction was completed, the solvent was removed by concentration to obtain 31.5 g of the target acrylic isocyanate resin material Y-5-1. 1 H NMR (500MHz, CDCl3) δ7.61-7.42(m,8H),7.36(t,J=12.0Hz,9H),6.11(s,1H),5.72(s,1H),5.40(s,1H),5.20(s,1H),5.12(s,2H),4.57(s, 4H),4.42(s,1H),4.21(d,J=18.0Hz,3H),4.13(s,2H),3.98(s,1H),3 .87-3.65(m,4H),3.15(s,1H),2.23(s,1H),1.72(s,1H),1.29(s,2H).

[0143] Example 6: Synthesis of waterborne acrylic isocyanate resin Y-6-1, the principle of which is shown in the following formula:

[0144]

[0145] 48.7 g (0.1 mol) of compound (1-8) and 41.0 g (0.1 mol) of isocyanate compound (6-1) were added to 250 mL of toluene, and the mixture was stirred at 80 °C for 4 h. The mixture was concentrated under reduced pressure, the solvent was removed, and the mixture was recrystallized from ethanol to give 65.4 g of polymerization precursor compound (6-2). 1HNMR (500MHz, CDCl3) δ7.33 (d, J = 15.0Hz, 3H), 7.28-7.06 (m, 2H), 6.85-6.71 (m, 1H), 6.70-6. 48(m,2H),6.25(dt,J=4.1,1.9Hz,1H),5.91(s,2H),5.84-5.75(m,2H),5.66(dt,J=4.1,2.0H z,1H),5.49(s,1H),5.26(d,J=7.5Hz,1H),4.71(s,1H),4.50(s,2H),4.38-4.17(m,8H),4.00 (t,J=7.6Hz,2H),3.91(d,J=24.7Hz,1H),3.07(d,J=24.9Hz,1H),2.61(tt,J=9.8,2.0Hz,2H).

[0146] 44.8 g (0.05 mol) of acrylate monomer compound (1-10) was dissolved in 500 mL of anhydrous methanol. Under stirring, a catalytic amount of initiator azobisisobutyronitrile (AIBN) (0.1 g AIBN dissolved in 10 mL of methanol) was added dropwise. The reaction was stirred overnight at 85 °C. After the reaction was completed, the solvent was removed by concentration to obtain 35.4 g of the target acrylic isocyanate resin material Y-6-1. 13 C NMR (125MHz, CDCl3) δ180.97,180.90,157.89,148.52,147.52,140.77,13 8.91,138.47,133.37,131.37,131.27,131.22,131.20,129.93,126.87,12 6.80,125.65,125.55,122.19,120.54,119.94,108.56,81.66,80.90,62. 95,61.34,61.30,52.65,44.02,43.96,42.25,37.11,37.08,31.66,17.23.

[0147] Examples 7 Waterborne Coating Formulations 1-18 are shown in Tables 1-18. All contents in Tables 1-18 are mass contents.

[0148] Table 1. Waterborne Coating Formulation 1

[0149]

[0150] Table 2. Waterborne Coating Formulation 2

[0151]

[0152] Table 3. Waterborne Coating Formulations (Formulation 3)

[0153]

[0154]

[0155] Table 4. Waterborne Coating Formulation 4

[0156]

[0157] Table 5. Waterborne Coating Formulation 5

[0158]

[0159] Table 6. Waterborne Coating Formulation 6

[0160]

[0161]

[0162] Table 7. Waterborne Coating Formulation 7

[0163]

[0164] Table 8. Waterborne Coating Formulations

[0165]

[0166] Table 9. Waterborne Coating Formulations

[0167]

[0168] Table 10 Waterborne Coating Formulation 10

[0169]

[0170] Table 11 Waterborne Coating Formulation 11

[0171]

[0172]

[0173] Table 12 Waterborne Coating Formulation 12

[0174]

[0175] Table 13 Waterborne Coating Formulation 13

[0176]

[0177] Table 14 Waterborne Coating Formulation 14

[0178]

[0179]

[0180] Table 15 Waterborne Coating Formulation 15

[0181]

[0182] Table 16 Waterborne Coating Formulations

[0183]

[0184] Table 17 Waterborne Coating Formulations for Formula 17

[0185]

[0186] Table 18 Waterborne Coating Formulations

[0187]

[0188] Waterborne Coating Performance Testing

[0189] Painting

[0190] Clean the surface of the wood substrate with deionized water to remove dirt from the ceramic surface, and dry. Spray the substrate surface with water-based coatings of formulations 1-18, heat in a tunnel oven at 80°C for 10 minutes, and then irradiate with UV-LED for 10 minutes to allow it to crosslink and cure.

[0191] The hardness, adhesion, solvent resistance (number of alcohol washes), and VOC emission of the water-based coatings formulated 1–18 were tested, and the results are shown in Table 19. The hardness of the cured film was tested according to GB / T 6739—1996 "Determination of Hardness of Coating Film by Pencil Method", with a test range of 4B–6H; adhesion was tested according to GB / T 9286—1998; yellowing resistance was tested according to GB-T 9761-2008 "Visual Colorimetry of Paints and Varnishes"; solvent resistance was tested according to Method A (immersion method) of GB 9274—1988 "Determination of Resistance to Liquid Media in Paints and Varnishes"; and VOC emission was tested according to GB / T 23986—2009 "Determination of Volatile Organic Compound (VOC) Content in Paints and Varnishes by Gas Chromatography". The cured coating film was prepared into 5cm × 2cm × 0.2cm samples, and the limiting oxygen index was tested in an oxygen index tester. As shown in Table 19, the present invention designs and synthesizes a series of water-based acrylic isocyanate resins with flame-retardant properties. The resulting water-based coatings have good flame-retardant effects, low VOC, and are environmentally friendly, and can be applied to wood coatings.

[0192] Table 19 Performance Test Results

[0193]

[0194] 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 aqueous acrylic isocyanate resin having a structure shown in Formula I: Formula I, n in formula I is an integer from 0 to 10, m is an integer from 1 to 100, represents a connection site; The structure is as follows: 。 2. The aqueous isocyanate acrylate resin according to claim 1, characterized in that, The aqueous acrylic isocyanate resin has a structure shown in Formula Y-1-1, Y-2-1, Y-3-1, Y-4-1, Y-5-1 or Y-6-1: 、 、 、 、 、 。 3. The method for preparing the aqueous isocyanate acrylate resin according to claim 1 or 2, characterized by, comprising the following steps: mixing compound A-1, P2S5 and an organic solvent to perform a first substitution reaction to obtain compound B; performing a first reflux reaction on the compound B in hydrochloric acid to obtain compound C; mixing the compound C, compound D, sulfuric acid and an organic solvent to perform a dehydration reaction to obtain compound E; mixing the compound E, imidazole and anhydrous ethanol to perform a second substitution reaction to obtain compound G; mixing the compound G, bromoethylene and anhydrous ethanol to perform a second reflux reaction to obtain compound H; mixing the compound H, compound I and an organic solvent to perform a third substitution reaction to obtain compound J; mixing the compound J, isocyanate compound K and an organic solvent to perform an amine group reaction to obtain polymerization precursor compound L; mixing the polymerization precursor compound L, an initiator and a solvent to perform a polymerization reaction to obtain the aqueous acrylic isocyanate resin; the structures of the compounds A-1, B, C, D, E, G, H, I, J, K and L are shown in the following formulae: 、 、 、 、 、 、 、 、 、 、 。 4. The production method according to claim 3, characterized by, the molar ratio of the compound A-1 to P2S5 is 1:1, and the P2S5 is added averagely for two times.

5. The preparation method according to claim 3, characterized in that, the molar ratio of the compound C to D is 0.4:

1. 6.The aqueous acrylic isocyanate resin of claim 1 or 2 is applied in the field of water-based coatings.

7. An aqueous coating, characterized in that comprising the following components with mass percentage: the aqueous acrylic isocyanate resin of claim 1 or 2 20% to 60%, a diol 10% to 40%, barium sulfate 1% to 10%, a thickening agent 0.1% to 10%, an antifoaming agent 0.1% to 10%, a solvent 1% to 50%, a photoinitiator 0.1% to 5% and tin laurate 0.1% to 5%.

8. The aqueous coating of claim 7, wherein, the diol comprises an aliphatic diol. 9.The water-based coating of claim 7 or 8 is applied in wood coating.

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