CN117304380A - Water-based acrylic isocyanate resin, preparation method and application thereof, and water-based paint - Google Patents

Water-based acrylic isocyanate resin, preparation method and application thereof, and water-based paint Download PDF

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Publication number
CN117304380A
CN117304380A CN202311290210.4A CN202311290210A CN117304380A CN 117304380 A CN117304380 A CN 117304380A CN 202311290210 A CN202311290210 A CN 202311290210A CN 117304380 A CN117304380 A CN 117304380A
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compound
isocyanate resin
water
acrylic isocyanate
reaction
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陈绪芹
孟鸿
贺耀武
王丹
李婷婷
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Foshan New Quantum Environmental Protection Material Co ltd
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Foshan New Quantum Environmental Protection Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a water-based acrylic isocyanate resin, a preparation method and application thereof, and a water-based paint, belonging to the technical field of paint. The invention 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 flame retardant property. The invention provides the water-based paint which has good flame retardant property, low VOC and environmental protection, and can be applied to the coating of woodware.

Description

Water-based acrylic isocyanate resin, preparation method and application thereof, and water-based paint
Technical Field
The invention relates to the technical field of coatings, in particular to a water-based acrylic isocyanate resin, a preparation method and application thereof, and a water-based coating.
Background
The wood lacquer is a kind of paint for protecting and coating wood materials, and under the environment-friendly call sound, the development of oily lacquer is restricted due to the limitation emission of VOC, and the water-based wood lacquer is generated. The waterborne polyurethane wood lacquer is widely developed and applied because of the characteristics of low VOC, environmental friendliness and the like. Meanwhile, the defects of the aqueous polyurethane wood lacquer are gradually revealed, the aqueous polyurethane wood lacquer is widely focused on the condition that the wood lacquer is easy to burn and causes fire disaster, and the improvement of the flame retardant property of the aqueous polyurethane material is necessary.
Disclosure of Invention
In view of the above, the invention aims to provide a water-based acrylic isocyanate resin, a preparation method and application thereof, and a water-based paint. The water-based acrylic isocyanate resin provided by the invention has a good flame retardant effect.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a water-based acrylic isocyanate resin, which has a structure shown in a formula I:
in the formula I, n is an integer of 0-10, m is 1-100, and represents a connecting site;
is a substituent group of a triisocyanate structure.
Preferably, the saidThe structure of (2) is as follows:
preferably, the aqueous acrylic isocyanate resin has a structure represented by the formula Y-1-1, Y-2-1, Y-3-1, Y-4-1, Y-5-1 or Y-6-1:
the invention also provides a preparation method of the aqueous acrylic isocyanate resin, which comprises the following steps:
compound A, P 2 S 5 Mixing with an organic solvent to perform a first substitution reaction to obtain a compound B;
carrying out a first reflux reaction on the compound B in hydrochloric acid to obtain a compound C;
mixing the compound C, the compound D, sulfuric acid and an organic solvent for dehydration reaction to obtain a compound E;
mixing the compound E, imidazole and absolute ethyl alcohol for a second substitution reaction to obtain a compound G;
mixing the compound G, bromoethylene and absolute ethyl alcohol for a second reflux reaction to obtain a compound H;
mixing the compound H, the compound I and an organic solvent for a third substitution reaction to obtain a compound J;
mixing the compound J, an isocyanate compound K and an organic solvent for amination reaction to obtain a polymerization precursor compound L;
mixing the polymerization precursor compound L, an initiator and a solvent for polymerization reaction to obtain the aqueous acrylic isocyanate resin;
the structures of the compounds A, B, C, D, E, G, H, I, J, K and L are shown in the following formula:
preferably, the compounds A and P 2 S 5 The molar ratio of P is 1:1, the molar ratio of P is 1:1 2 S 5 The average was divided into two additions.
Preferably, the molar ratio of compounds C and D is 0.4:1.
the invention also provides application of the aqueous acrylic isocyanate resin in the field of aqueous paint.
The invention also provides a water-based paint, which comprises the following components in percentage by mass:
the aqueous acrylic isocyanate resin according to the technical scheme comprises 20% -60% of glycol 10% -40%, 1% -10% of barium sulfate, 0.1% -10% of thickening agent, 0.1% -10% of defoamer, 1% -50% of solvent, 0.1% -5% of photoinitiator and 0.1% -5% of tin laurate.
Preferably, the diol comprises an aliphatic diol.
The invention also provides application of the water-based paint in wood coating.
The invention provides a water-based acrylic acid isocyanate resin, which has a structure shown in a formula I.
The invention provides the water-based paint which has good flame retardant property, low VOC and environmental protection, and can be applied to the coating of woodware.
Detailed Description
The invention provides a water-based acrylic isocyanate resin, which has a structure shown in a formula I:
in the formula I, n is an integer of 0-10, m is 1-100, and represents a connecting site;
is a substituent group of a triisocyanate structure.
In the present invention, theThe structure of (2) is preferably as follows:
in the present invention, the structure of the aqueous acrylic isocyanate resin is preferably as shown in the formulas Y1 to 6:
in the present invention, the aqueous acrylic isocyanate resin preferably has a structure represented by the formula Y-1-1, Y-2-1, Y-3-1, Y-4-1, Y-5-1 or Y-6-1:
the invention also provides a preparation method of the aqueous acrylic isocyanate resin, which comprises the following steps:
compound A, P 2 S 5 Mixing with an organic solvent to perform a first substitution reaction to obtain a compound B;
carrying out a first reflux reaction on the compound B in hydrochloric acid to obtain a compound C;
mixing the compound C, the compound D, sulfuric acid and an organic solvent for dehydration reaction to obtain a compound E;
mixing the compound E, imidazole and absolute ethyl alcohol for a second substitution reaction to obtain a compound G;
mixing the compound G, bromoethylene and absolute ethyl alcohol for a second reflux reaction to obtain a compound H;
mixing the compound H, the compound I and an organic solvent for a third substitution reaction to obtain a compound J;
mixing the compound J, an isocyanate compound K and an organic solvent for amination reaction to obtain a polymerization precursor compound L;
mixing the polymerization precursor compound L, an initiator and a solvent for polymerization reaction to obtain the aqueous acrylic isocyanate resin;
the structures of the compounds A, B, C, D, E, G, H, I, J, K and L are shown in the following formula:
in the invention, the principle of the preparation method is shown as the following formula:
the invention provides a compound A, P 2 S 5 And mixing with an organic solvent to perform a first substitution reaction to obtain a compound B.
In the present invention, the compounds A and P 2 S 5 Preferably 1:1, said P 2 S 5 Preferably in two additions on average.
In the present invention, the organic solvent is preferably toluene.
In the present invention, the ratio of the compound A to the organic solvent is preferably 1mol:1000mL.
In a specific embodiment of the present invention, the compound A, the organic solvent and the first part P are preferably added in a flask equipped with a mechanical stirrer, a condenser, a nitrogen inlet and outlet 2 S 5 Introducing nitrogen gas at 60deg.C, stirring for 2 hr, cooling to 40deg.C, adding second part P 2 S 5 Introducing nitrogen to react for 24 hours, stopping heating, cooling to room temperature, removing the solvent under reduced pressure, adding chloroform into the obtained oily liquid, oscillating and filtering, washing the obtained filtrate with saturated sodium bicarbonate solution for three times, drying, concentrating, and recrystallizing the solid with acetonitrile to obtain the compound B.
After the compound B is obtained, the compound B is subjected to a first reflux reaction in hydrochloric acid to obtain a compound C.
In the present invention, the concentration of the hydrochloric acid is preferably 1mol/L.
In the present invention, the amount ratio of the compound B to hydrochloric acid is preferably 0.5mol:800mL.
In the present invention, the time of the first reflux reaction is preferably 4 hours.
In the specific embodiment of the present invention, the compound B and hydrochloric acid are preferably added to a flask equipped with a mechanical stirrer, a condenser, a nitrogen inlet and outlet to perform a first reflux reaction, and after the first reflux reaction is completed, the obtained product is cooled to room temperature, extracted with dichloromethane, washed 3 times with water, dried, concentrated, and the solid is recrystallized with ethanol to obtain the compound C.
After the compound C is obtained, the compound C, the compound D, sulfuric acid and an organic solvent are mixed for dehydration reaction to obtain the compound E.
In the present invention, the molar ratio of the compounds C and D is preferably 0.4:1.
in the present invention, the organic solvent is preferably toluene.
In the present invention, the ratio of the compound C to the concentrated sulfuric acid is preferably 0.4mol:10mL, the mass fraction of the concentrated sulfuric acid is preferably 98%.
In a specific embodiment of the present invention, the compounds C and D are preferably dissolved in toluene, concentrated sulfuric acid is added, a water knockout vessel is added to reflux the reaction for water diversion, after the reaction for 12 hours, the reaction is cooled to room temperature, washed with saturated sodium bicarbonate solution to neutrality, dried, concentrated, and the solid is recrystallized with toluene to obtain the compound E.
After the compound E is obtained, the compound E, imidazole (compound F) and absolute ethyl alcohol are mixed for carrying out a second substitution reaction to obtain a compound G.
In the present invention, the molar ratio of the compound E to imidazole is preferably 3:5.
in the present invention, the amount ratio of the compound E to the absolute ethanol is preferably 0.3mol:500mL.
In the present invention, the time of the second substitution reaction is preferably 8 hours.
In a specific embodiment of the present invention, it is preferable that the compound E and imidazole are dissolved in absolute ethanol to perform the second reflux reaction, and after completion, the solvent is removed by concentration under reduced pressure, and recrystallized from toluene to obtain the compound G.
After the compound G is obtained, the compound G, bromoethylene and absolute ethyl alcohol are mixed for a second reflux reaction to obtain the compound H.
In the present invention, the molar ratio of the compound G to vinyl bromide is preferably 1:2.
in the present invention, the ratio of the compound G to the absolute ethanol is preferably 0.25mol:500mL.
In a specific embodiment of the present invention, the compound G and vinyl bromide are preferably dissolved in absolute ethanol, refluxed with stirring overnight, the solvent is removed under reduced pressure, and the solid is recrystallized from absolute ethanol to give compound H.
After the compound H is obtained, the compound H, the compound I and the organic solvent are mixed for carrying out a third substitution reaction to obtain the compound J.
In the present invention, the molar ratio of the compound H to I is preferably 1:1.
in the present invention, the organic solvent is preferably toluene.
In the present invention, the ratio of the amount of the compound H to toluene is preferably 0.2mol:200mL.
In a specific embodiment of the present invention, it is preferable to dissolve the compounds H and I in toluene, stir overnight, concentrate under reduced pressure to remove the solvent, and recrystallize the solid from ethanol to give compound J.
After the compound J is obtained, the compound J, the isocyanate compound K and the organic solvent are mixed for amination reaction to obtain a polymerization precursor compound L.
In the present invention, the molar ratio of the compound J to K is preferably 1:1.
in the present invention, the organic solvent is preferably toluene.
In the present invention, the ratio of the amount of the compound J to toluene is preferably 0.1mol:250mL.
In the present invention, the temperature of the amination reaction is preferably 80℃and the time is preferably 4 hours.
In the embodiment of the present invention, the compound J, K is preferably added to toluene, reacted at 80℃with stirring for 4 hours, concentrated under reduced pressure, the solvent is removed, and recrystallized from ethanol to obtain the polymerization precursor compound L.
After the polymerization precursor compound L is obtained, the water-based acrylic isocyanate resin is obtained by mixing the polymerization precursor compound L, an initiator and a solvent for polymerization reaction.
In the present invention, the solvent is preferably anhydrous methanol.
In the present invention, the initiator is preferably Azobisisobutyronitrile (AIBN), and the initiator is preferably added in the form of an initiator solution, preferably prepared by dissolving 0.1g of AIBN in 10mL of methanol.
In the present invention, the temperature of the polymerization reaction is preferably 85 ℃.
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 to react overnight under stirring, and after the reaction is completed, the solvent is removed by concentration to obtain the aqueous acrylic isocyanate resin.
The invention also provides application of the aqueous acrylic isocyanate resin in the field of aqueous paint.
The invention also provides a water-based paint, which comprises the following components in percentage by mass:
the aqueous acrylic isocyanate resin according to the technical scheme comprises 20% -60% of glycol 10% -40%, 1% -10% of barium sulfate, 0.1% -10% of thickening agent, 0.1% -10% of defoamer, 1% -50% of solvent, 0.1% -5% of photoinitiator and 0.1% -5% of tin laurate.
In the present invention, the aqueous acrylic isocyanate resin in the aqueous coating material preferably accounts for 25 to 50% by mass, more preferably 20%, 25%, 30%, 35%, 40%, 45%, 50% or 60% by mass.
In the present invention, the mass percentage of the diol in the aqueous coating material is preferably 15% to 35%, more preferably 15%, 20%, 25%, 30%, 35% or 40%.
In the present invention, the diol preferably includes an aliphatic diol, and more preferably includes one or more of ethylene glycol, propylene glycol, butylene glycol, cyclohexanediol, and hexylene glycol. In the present invention, the diol functions to react with isocyanate to act as a cap.
In the invention, the weight percentage of the barium sulfate in the water-based paint is preferably 3-5%.
In the invention, the mass percentage of the thickener in the water-based paint is preferably 2-5%.
In the present invention, the thickener is preferably ViscoPlus 300.
In the invention, the mass percentage of the defoaming agent in the water-based paint is preferably 0.3-5%.
In the present invention, the antifoaming agent is preferably TEGO-81.
In the invention, the mass percentage of the solvent in the water-based paint is preferably 23.5-40%.
In the present invention, the solvent is preferably water and/or ethanol, and when the solvent is a mixture of water and ethanol, the mass ratio of water to ethanol in the mixture is preferably 1 to 8:1 to 8.
In the invention, the mass percentage of the photoinitiator in the water-based paint is preferably 1-3%.
In the present invention, the photoinitiator is preferably 1-hydroxycyclohexyl phenyl ketone (Irgacure-184), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (Lucirin TPO), or 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocur 1173).
In the invention, the mass percentage of the tin laurate in the water-based paint is preferably 0.3-3%.
The invention also provides application of the water-based paint in wood coating.
The specific mode of the application of the present invention is not particularly limited, and modes well known to those skilled in the art can be adopted.
In the present invention, the application preferably comprises a curing process, preferably: the mixture was heated with a tunnel oven at 80℃for 10 minutes and then irradiated with UV-LEDs for 10 minutes.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1 Synthesis of aqueous acrylic isocyanate resin Y-1-1, the principle is shown as follows:
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276g (1 mol) of compound (1-1), 1000mL of toluene, and a first 111g (0.5 mol) of P were placed in a 2L flask equipped with a mechanical stirrer, a condenser, and a nitrogen inlet and outlet 2 S 5 The temperature was 60℃and nitrogen was introduced and stirred for 2 hours. After 2h the temperature was reduced to 40℃and a second 111g (0.5 mol) of P was added 2 S 5 Nitrogen was introduced to react for 24 hours. Heating was stopped, cooled to room temperature, the solvent was removed under reduced pressure, and the resulting oily liquid was added to 500mL of chloroform and suction filtration was performed with shaking. The filtrate was washed three times with saturated sodium bicarbonate solution, dried, concentrated, and the solid was recrystallized from acetonitrile 227g of compound (1-2). 1 HNMR(500MHz,CDCl 3 )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).
146g (0.5 mol) of compound (2-1) was put into a 2L flask equipped with a mechanical stirrer, a condenser and a nitrogen inlet/outlet, and the mixture was refluxed in 800mL of 1mol/L hydrochloric acid for 4 hours, cooled to room temperature, extracted with methylene chloride, washed 3 times with water, dried, concentrated, and the solid was recrystallized from ethanol to 83g of compound (1-3). 1 H NMR(500MHz,CDCl 3 )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).
75.2g (0.4 mol) of Compound (1-3), 125g (1 mol) of 2-bromoethanol were dissolved in 500mL of toluene, 10mL of concentrated sulfuric acid was added, the reaction was refluxed with a water separator to separate water, after 12 hours of reaction, cooled to room temperature, washed with saturated sodium bicarbonate solution to neutrality, dried, concentrated, and the solid was recrystallized from toluene to 105.4g of Compound (1-4). 1 H NMR(500MHz,CDCl 3 )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).
88.5g (0.3 mol) of Compound (1-4), 34g (0.5 mol) of imidazole were dissolved in 500mL of absolute ethanol and reacted under reflux for 8 hours, the solvent was removed by concentration under reduced pressure, and 79.4g of Compound (1-5) was obtained by recrystallization from toluene. 1 H NMR(500MHz,CDCl 3 )δ7.92(s,1H),7.37-7.05(m,3H),6.85-6.71(m,2H),6.71-6.62(m,2H),5.30(s,2H),4.35(td,J＝14.8,1.0Hz,2H),4.01(td,J＝14.8,1.2Hz,2H).
70.5g (0.25 mol) of Compound (1-5) and 53g (0.5 mol) of bromoethylene were dissolved in 500mL of absolute ethanol, stirred and refluxed overnight, the solvent was removed under reduced pressure, and the solid was recrystallized from absolute ethanol to give 105.6g of intermediate compound (1-6). 1 H NMR(500MHz,CDCl 3 )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).
38.9g (0.2 mol) of Compound (1-6), 26.8g (0.2 mol) of hydroxyl group-containing acrylic acid chloride compound were dissolved in 200mL of toluene and stirred overnight, the solvent was removed by concentration under reduced pressure, and the solid was recrystallized from ethanol to 54.8g of Compound (1-8). 1 H NMR(500MHz,CDCl 3 )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).
48.7g (0.1 mol) of compound (1-8), 24.3g (0.1 mol) of the isocyanate compound (1-9) was added to 250mL of toluene, reacted at 80℃with stirring for 4 hours, concentrated under reduced pressure, the solvent was removed, and recrystallized from ethanol to obtain 65.4g of the polymerization precursor compound (1-10). 1 H NMR(500MHz,CDCl 3 )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).
36.5g (0.05 mol) of the acrylate monomer compound (1-10) was dissolved in 500mL of anhydrous methanol, and a catalytic amount of the initiator azobisisobutyronitrile AIBN (0.1 g AIBN was dissolved in 10mL of methanol) was added dropwise with stirring, and the reaction was stirred overnight at 85℃and after the completion of the reaction, the solvent was concentrated and removed to obtain 31.5g of the objective acrylic isocyanate resin material Y-1-1.
1 H NMR(500MHz,CDCl 3 )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),4.10(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).。
Example 2 Synthesis of aqueous acrylic isocyanate resin Y-2-1, the principle is shown as follows:
48.7g (0.1 mol) of Compound (1-8), 20.7g (0.1 mol) of isocyanate Compound (2-1) were added to 250mL of toluene, reacted at 80℃for 4 hours with stirring, concentrated under reduced pressure, the solvent was removed, and recrystallized from ethanol to give 58.4g of Polymer precursor Compound (2-2). 1 H NMR(500MHz,CDCl 3 )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),5.09(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,1H),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).
34.6g (0.05 mol) of the acrylate monomer compound (2-2) was dissolved in 500mL of anhydrous methanol, and a catalytic amount of the initiator azobisisobutyronitrile AIBN (0.1 g AIBN was dissolved in 10mL of methanol) was added dropwise with stirring, and the reaction was stirred overnight at 85℃and after the completion of the reaction, the solvent was concentrated and removed to obtain 28.7g of the objective acrylic isocyanate resin material Y-2-1. 1 H NMR(500MHz,CDCl 3 )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).。
Example 3 Synthesis of aqueous acrylic isocyanate resin Y-3-1, the principle is shown as follows:
48.7g (0.1 mol) of Compound (1-8), 41g (0.1 mol) of isocyanate Compound (3-1) were added to 250mL of toluene, and the mixture was reacted at 80℃for 4 hours with stirring, concentrated under reduced pressure, the solvent was removed, and recrystallized from ethanol to give 71.5g of Polymer precursor Compound (3-2). 1 H NMR(500MHz,CDCl 3 )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).
44.8g (0.05 mol) of the acrylate monomer compound (3-2) was dissolved in 500mL of anhydrous methanol, and a catalytic amount of the initiator azobisisobutyronitrile AIBN (0.1 g AIBN was dissolved in 10mL of methanol) was added dropwise with stirring, and the reaction was stirred overnight at 85℃and after the completion of the reaction, the solvent was concentrated and removed to obtain 38.7g of the objective acrylic isocyanate resin material Y-3-1. 1 HNMR(500MHz,CDCl 3 )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).
Example 4 Synthesis of aqueous acrylic isocyanate resin Y-4-1, the principle is shown as follows:
48.7g (0.1 mol) of Compound (1-8), 42.7g (0.1 mol) of isocyanate Compound (4-1) were added to 250mL of toluene, reacted at 80℃for 4 hours with stirring, concentrated under reduced pressure, the solvent was removed, and recrystallized from ethanol to give 65.4g of Polymer precursor Compound (4-2). 1 H NMR(500MHz,CDCl 3 )δ7.55-7.30(m,8H),7.23(d,J＝5.0Hz,6H),6.78(s,1H),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＝10.0Hz,6H),4.23(d,J＝2.2Hz,4H),4.01(s,2H),3.22(s,1H),2.55(s,2H).
45.6g (0.05 mol) of the acrylate monomer compound (4-2) was dissolved in 500mL of anhydrous methanol, and a catalytic amount of the initiator azobisisobutyronitrile AIBN (0.1 g AIBN was dissolved in 10mL of methanol) was added dropwise with stirring, and the reaction was stirred overnight at 85℃and after the completion of the reaction, the solvent was concentrated and removed to obtain 42.6g of the objective acrylic isocyanate resin material Y-4-1. 1 H NMR(500MHz,CDCl 3 )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).
Example 5 Synthesis of aqueous acrylic isocyanate resin Y-5-1, the principle is shown as follows:
48.7g (0.1 mol) of Compound (1-8), 60.5g (0.1 mol) of isocyanate Compound (5-1) were added to 250mL of toluene, reacted at 80℃with stirring for 4 hours, concentrated under reduced pressure, the solvent was removed, and ethanol was usedRecrystallisation gives 78.7g of polymeric precursor compound (5-2). 13 C NMR(125MHz,CDCl 3 )δ180.95,157.23,148.02,138.47,136.55,135.94,135.84,135.64,134.52,131.32,131.21,129.93,129.28,127.96,125.60,120.54,111.38,108.56,80.56,62.40,61.32,44.57,44.37,43.99,43.71,36.16,30.17,26.66,8.14.
54.6g (0.05 mol) of the acrylate monomer compound (5-2) was dissolved in 500mL of anhydrous methanol, and a catalytic amount of the initiator azobisisobutyronitrile AIBN (0.1 g AIBN was dissolved in 10mL of methanol) was added dropwise with stirring, and the reaction was stirred overnight at 85℃and after the completion of the reaction, the solvent was concentrated and removed to obtain 31.5g of the objective acrylic isocyanate resin material Y-5-1. 1 H NMR(500MHz,CDCl 3 )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).
Example 6 Synthesis of aqueous acrylic isocyanate resin Y-6-1, the principle is shown as follows:
48.7g (0.1 mol) of Compound (1-8), 41.0g (0.1 mol) of isocyanate Compound (6-1) were added to 250mL of toluene, reacted at 80℃for 4 hours with stirring, concentrated under reduced pressure, the solvent was removed, and recrystallized from ethanol to give 65.4g of Polymer precursor Compound (6-2). 1 HNMR(500MHz,CDCl 3 )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＝4.1,2.0Hz,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).
44.8g (0.05 mol) of acrylate monomer compound (1-10) are dissolved in 500mL of absolute methanol, and a catalytic amount of initiator azobisisobutyronitrile AIBN (0.1 g AIBN is dissolved in 10mL of methanol) is added dropwise under stirring, stirred at 85 ℃ for reaction overnight, and after the reaction is finished, concentrated and removedSolvent, 35.4g of the objective acrylic isocyanate material Y-6-1 was obtained. 13 C NMR(125MHz,CDCl 3 )δ180.97,180.90,157.89,148.52,147.52,140.77,138.91,138.47,133.37,131.37,131.27,131.22,131.20,129.93,126.87,126.80,125.65,125.55,122.19,120.54,119.94,108.56,81.66,80.90,62.95,61.34,61.30,52.65,44.02,43.96,42.25,37.11,37.08,31.66,17.23.
Example 7 Water-based paint formulations 1 to 18 are shown in tables 1 to 18, and the contents in tables 1 to 18 are mass contents.
Table 1 aqueous coating formulation of formulation 1
Table 2 aqueous coating formulation of formulation 2
Table 3 aqueous coating formulation of formulation 3
Table 4 aqueous coating formulation of formulation 4
Table 5 aqueous coating formulation of formulation 5
Table 6 aqueous coating formulation of formulation 6
Table 7 aqueous coating formulation of formulation 7
Table 8 aqueous coating formulation of formulation 8
Table 9 aqueous coating formulation of formulation 9
Table 10 aqueous coating formulation of formulation 10
Table 11 aqueous coating formulation of formulation 11
Table 12 aqueous coating formulation of formulation 12
Table 13 aqueous coating formulation of formulation 13
Table 14 aqueous coating formulation of formulation 14
Table 15 aqueous coating formulation of formulation 15
Table 16 Water-borne coating formulation of formulation 16
Table 17 aqueous coating formulation of formulation 17
Table 18 aqueous coating formulation of formulation 18
Water-based paint performance test
Coating
And (3) cleaning the surface of the wood substrate by deionized water, removing dirt on the surface of the ceramic, and drying. Spraying the water paint with the formula of 1-18 on the surface of a substrate, heating for 10 minutes by using a tunnel furnace with the temperature of 80 ℃, and then irradiating for 10 minutes by using a UV-LED to crosslink and solidify the substrate.
The hardness, adhesion, solvent resistance (number of alcohol scrubs) and VOC emissions of the coatings obtained from the aqueous paints of formulas 1 to 18 were tested and the results are shown in table 19. The hardness of the cured film is implemented according to GB/T6739-1996 pencil test method for hardness of coating film, and the test range is 4B-6H; adhesion testing was performed according to national standard GB/T9286-1998; the yellowing resistance test was carried out according to GB-T9761-2008 visual colorimetry of paints and varnishes, and the solvent resistance test was carried out according to the A method (soaking method) in GB 9274-1988 determination of liquid Medium resistance of paints and varnishes; and VOC emissions testing was performed using GB/T23986-2009 gas chromatography for determination of Volatile Organic Compounds (VOC) content of paints and varnishes. The cured film of the coating was prepared into a specimen of 5 cm. Times.2 cm. Times.0.2 cm, and the limiting oxygen index was measured in an oxygen index tester. As can be seen from Table 19, the water-based acrylic isocyanate resin with flame retardant property is designed and synthesized in the invention, and the prepared water-based paint has good flame retardant effect, low VOC and environmental protection, and can be applied to the coating of woodware.
TABLE 19 Performance test results
The foregoing 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 modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.

Claims (10)

1. An aqueous acrylic isocyanate resin having a structure represented by formula I:
in the formula I, n is an integer of 0-10, m is 1-100, and represents a connecting site;
is a substituent group of a triisocyanate structure.
2. The aqueous acrylic isocyanate resin according to claim 1, wherein theThe structure of (2) is as follows:
3. the aqueous acrylic isocyanate resin according to claim 2, wherein said aqueous acrylic isocyanate resin has a structure represented by the formula Y-1-1, Y-2-1, Y-3-1, Y-4-1, Y-5-1 or Y-6-1:
4. a method for producing the aqueous acrylic isocyanate resin according to any one of claims 1 to 3, comprising the steps of:
compound A, P 2 S 5 Mixing with an organic solvent to perform a first substitution reaction to obtain a compound B;
carrying out a first reflux reaction on the compound B in hydrochloric acid to obtain a compound C;
mixing the compound C, the compound D, sulfuric acid and an organic solvent for dehydration reaction to obtain a compound E;
mixing the compound E, imidazole and absolute ethyl alcohol for a second substitution reaction to obtain a compound G;
mixing the compound G, bromoethylene and absolute ethyl alcohol for a second reflux reaction to obtain a compound H;
mixing the compound H, the compound I and an organic solvent for a third substitution reaction to obtain a compound J;
mixing the compound J, an isocyanate compound K and an organic solvent for amination reaction to obtain a polymerization precursor compound L;
mixing the polymerization precursor compound L, an initiator and a solvent for polymerization reaction to obtain the aqueous acrylic isocyanate resin;
the structures of the compounds A, B, C, D, E, G, H, I, J, K and L are shown in the following formula:
5. the process of claim 4, wherein the compounds A and P 2 S 5 The molar ratio of (2) is 1:1, said P 2 S 5 The average was divided into two additions.
6. The process according to claim 4, wherein the molar ratio of compounds C and D is 0.4:1.
7. use of the aqueous acrylic isocyanate resin according to any one of claims 1 to 3 in the field of aqueous coatings.
8. The water-based paint is characterized by comprising the following components in percentage by mass:
the aqueous acrylic isocyanate resin according to any one of claims 1 to 3, wherein the aqueous acrylic isocyanate resin comprises 20 to 60% of a diol, 10 to 40% of a diol, 1 to 10% of barium sulfate, 0.1 to 10% of a thickener, 0.1 to 10% of a defoamer, 1 to 50% of a solvent, 0.1 to 5% of a photoinitiator and 0.1 to 5% of tin laurate.
9. The aqueous coating of claim 8 wherein the glycol comprises an aliphatic glycol.
10. Use of the aqueous coating according to claim 8 or 9 in wood coating.
CN202311290210.4A 2023-10-07 2023-10-07 Water-based acrylic isocyanate resin, preparation method and application thereof, and water-based paint Pending CN117304380A (en)

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