Water-resistant polyacrylic cardanol ester emulsion, preparation method and application in ink

Abstract

The application relates to the technical field of inks, and discloses a water-resistant cardanol polyacrylate emulsion, a preparation method and application in inks. A functional monomer containing a fluorine-containing hydrophobic segment and a urea-based pyrimidone structure is prepared, the functional monomer is introduced into acrylate monomers together with cardanol polyacrylate to form a polymer through polymerization, the water resistance, adhesion and mechanical properties of an emulsion coating film are improved through the synergistic effect of the crosslinking degree and the hydrophobic group, and the prepared cardanol polyacrylate emulsion can be applied to inks as a base resin.

Description

Technical Field

[0001] This invention relates to the field of ink technology, specifically to a water-resistant polyacrylic acid cashew phenol ester emulsion, its preparation method, and its application in inks. Background Technology

[0002] Water-based inks are inks prepared using water as a solvent. Water-based inks emit zero or near-zero volatile organic compounds (VOCs), exhibiting green, environmentally friendly, non-toxic, energy-saving, and emission-reducing characteristics, representing a new trend in ink development. The main components of water-based inks are binders, pigments and fillers, water, and additives. The binder is the key component of water-based inks, determining their performance.

[0003] Acrylic resin emulsions are widely used in water-based ink binders due to their advantages such as strong adhesion, good weather resistance, high gloss, and excellent color retention. Acrylic polymers mainly consist of copolymers of acrylates and their derivatives. Other unsaturated monomers with double bond structures can also act as comonomers. Comonomers carrying different functional groups participate in the polymerization reaction, determining the chemical properties, mechanical properties, and adhesive properties of the polymer emulsion.

[0004] Cashew phenol is made from natural cashew shell oil through refining. It has a unique structure. The rigid benzene ring in its molecular structure can provide a certain strength to the resin system and improve the thermal stability of the resin system. The long aliphatic side chains it contains can play an "internal plasticizing" role, which can toughen the polymer and give the polymer a certain hydrophobic property.

[0005] Therefore, it is necessary to use cashew phenol as a raw material to prepare a polyacrylic acid cashew phenol ester emulsion, which is expected to improve the water resistance, adhesion and mechanical properties of polyacrylate emulsions, and thus be applied to water-based inks with excellent performance. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a water-resistant polyacrylic acid cashew phenol ester emulsion, its preparation method, and its application in inks. By preparing a functional monomer containing fluorinated hydrophobic segments and ureidopyrimidinone structures, and introducing it together with acrylic cashew phenol ester into the acrylic ester monomer to form a polymer, the water resistance, adhesion, and mechanical properties of the emulsion film are improved by increasing the degree of crosslinking and the synergistic effect of the hydrophobic groups. The prepared polyacrylic acid cashew phenol ester emulsion can be used as a base resin in inks.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion includes the following steps:

[0009] Step (1): Mix dodecafluoroheptyl methacrylate, ethanolamine, and methanol, react, and after the reaction is complete, distill under reduced pressure to obtain fluoroalcohol;

[0010] Step (2): Mix fluoroalcohol, maleic anhydride and tetrabutylammonium bromide evenly at room temperature, heat up and react. After the reaction is complete, cool down and add glycidyl methacrylate and p-hydroxyanisole. Heat up again and continue the reaction. After the reaction is complete, cool down and add isophorone diisocyanate and react again. After the reaction is complete, the intermediate product is obtained.

[0011] 2-Amino-4-hydroxy-6-methylpyrimidine and dimethyl sulfoxide were mixed and dissolved, cooled, and an intermediate product was added to react. After the reaction was completed, the mixture was filtered under reduced pressure and dried to obtain a fluorine-containing functional monomer.

[0012] Step (3): Mix methyl methacrylate, n-butyl acrylate, acrylic acid, cashew acrylate, and fluorinated functional monomers to obtain acrylate monomers;

[0013] Cashew acrylate is prepared by the following steps:

[0014] Cashew nut phenol, triethylamine, and dichloromethane were mixed, and a dichloromethane solution of acryloyl chloride was added dropwise. After the reaction was completed, the mixture was filtered and distilled under reduced pressure to obtain cashew nut phenol ester.

[0015] Step (4): Stir the emulsifier and water to dissolve them, add the acrylate monomer, and continue stirring to obtain the monomer pre-emulsion;

[0016] The monomer pre-emulsion was divided into two parts. The emulsifier, water, and sodium bicarbonate were stirred and mixed to dissolve. The first part of the monomer pre-emulsion was added and reacted. After the reaction was completed, the second part of the monomer pre-emulsion and ammonium persulfate aqueous solution were added dropwise. After the addition was completed, the reaction continued. After the reaction was completed, the mixture was cooled, the pH was adjusted to neutral, and the mixture was filtered to obtain water-resistant polyacrylic acid cashew phenol ester emulsion.

[0017] Preferably, in step (1): the molar ratio of dodecafluoroheptyl methacrylate to ethanolamine is 1:1; the mass ratio of dodecafluoroheptyl methacrylate to methanol is 1:2-3; and the reaction conditions are: reaction in a nitrogen atmosphere at 20-30°C for 20-30 hours.

[0018] Preferably, in step (2): the mass ratio of fluorohydrin, maleic anhydride, glycidyl methacrylate, and isophorone diisocyanate is 4.6:0.8-1:1.2-1.4:2-2.2; the amount of tetrabutylammonium bromide added is 0.8-1 wt% of the total mass of fluorohydrin and maleic anhydride; and the mass of p-hydroxyanisole added is 0.5-0.8 wt% of the total mass of glycidyl methacrylate.

[0019] Preferably, in step (2), the reaction conditions are: reacting at 100-105℃ for 3-4 hours; adding glycidyl methacrylate and p-hydroxyanisole at 90-92℃; continuing the reaction at 105℃ for 2-4 hours; and reacting again at room temperature for 2-3 hours.

[0020] Preferably, in step (2), the mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, intermediate product, and dimethyl sulfoxide is 30:3.8-4.1:100; the reaction conditions are: reaction at room temperature for 2-3 hours.

[0021] Preferably, in step (3), the acrylate monomer comprises the following components by mass: 15-20 parts methyl methacrylate, 20-25 parts n-butyl acrylate, 8-10 parts acrylic acid, 5-9 parts cashew acrylate, and 2-6 parts fluorinated functional monomer.

[0022] Preferably, in step (3), when preparing cashew phenol ester acrylate: the solid-liquid ratio of cashew phenol, triethylamine, and dichloromethane is 15g:1-1.5g:10-20mL; the molar ratio of cashew phenol and acryloyl chloride is 1:1-1.2; the dichloromethane solution of acryloyl chloride is prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2-3; the reaction conditions are: reacting at 20-25℃ for 2-4h.

[0023] Preferably, in step (4), the water-resistant polyacrylic acid cashew phenol ester emulsion comprises the following components by mass: 2.2-2.7 parts emulsifier, 50-60 parts water, 40-50 parts acrylate monomer, 1-1.5 parts sodium bicarbonate, and 20-25 parts ammonium persulfate aqueous solution; the ammonium persulfate aqueous solution has a concentration of 2 wt%.

[0024] The monomer preemulsion comprises the following components: 1-1.5 parts emulsifier, 20-30 parts water, and 40-50 parts acrylate monomer; the stirring conditions are: stirring at 100-300 r / min for 20-30 min; the mass ratio of the first monomer preemulsion to the second monomer preemulsion is 1-2:8-9.

[0025] Preferably, in step (4), the reaction conditions are: reacting for 30 minutes at a temperature of 75-85℃ and a stirring speed of 100-300r / min; the dropping time of the second monomer pre-emulsion is 2.5-3h, and the dropping time of the initiator solution is 2.6-3.1h; the reaction conditions are: continuing the reaction at a temperature of 75-85℃ for 2-3h.

[0026] Preferably, a water-resistant polyacrylic acid cashew phenol ester emulsion is prepared using the method described above for preparing water-resistant polyacrylic acid cashew phenol ester emulsion.

[0027] Preferably, an application of the water-resistant polyacrylic acid cashew phenol ester emulsion as described above in inks.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] In this invention, a functional monomer containing fluorinated hydrophobic segments and ureidopyrimidinone structures is prepared and introduced together with cashew phenol acrylate into an acrylate monomer to form a polymer. By increasing the degree of crosslinking and the synergistic effect of the hydrophobic groups, the water resistance, adhesion and mechanical properties of the emulsion film are improved. The prepared polyacrylic acid cashew phenol ester emulsion can be used as a base resin in inks.

[0030] This invention improves the synthesis of fluoroalcohols via the Michael addition reaction of dodecafluoroheptyl methacrylate and ethanolamine. The fluoroalcohol is then reacted sequentially with maleic anhydride, glycidyl methacrylate, and isophorone diisocyanate to generate an intermediate containing multiple active carbon-carbon double bonds. The isocyanate group is then combined with 2-amino-4-hydroxy-6-methylpyrimidine to introduce a ureidopyrimidinone structure, resulting in a fluorinated functional monomer with hydrophobic segments, a ureidopyrimidinone structure, and multiple active carbon-carbon double bonds. This fluorinated functional monomer, cashew acrylate, and other acrylate monomers are then synthesized into a polyacrylic acid cashew acrylate emulsion via a semi-continuous seed emulsion polymerization method. The synergistic effect of the components improves the water resistance, adhesion, and mechanical properties of the emulsion film.

[0031] Cashew phenol has an unsaturated fatty chain similar to that of vegetable oleic acid, and also has a rigid benzene ring structure. Therefore, cashew phenol ester acrylate, which is produced by reacting cashew phenol with acryloyl chloride, can improve the water resistance, adhesion and mechanical properties of the material. In the fluorinated functional monomer, the fluorinated hydrophobic segment improves the hydrophobicity and heat resistance of the material. The presence of multiple active carbon-carbon double bonds further improves the crosslinking degree of the material. 2-Amino-4-hydroxy-6-methylpyrimidine, as a pyrimidine derivative, can form multiple hydrogen bonds, and improve water resistance and mechanical properties by constructing a physical crosslinking system. Attached Figure Description

[0032] Figure 1 This is a line graph showing the water absorption rate of the polyacrylic acid cashew phenol ester emulsions prepared in Examples 1-5 and Comparative Examples 1-2 of this invention during performance testing.

[0033] Figure 2 This is a bar chart showing the tensile strength of the polyacrylic acid cashew phenol ester emulsions prepared in Examples 1-5 and Comparative Examples 1-2 of this invention during performance testing.

[0034] Figure 3This is a schematic diagram of the reaction for preparing fluorools in this invention;

[0035] Figure 4 This is a schematic diagram of the reaction for preparing intermediate products in this invention. Detailed Implementation

[0036] The present invention will be further illustrated below through specific embodiments. The following embodiments are specific implementations of the present invention, but the implementation of the present invention is not limited to the following embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and are included within the protection scope of the present invention.

[0037] Example 1

[0038] This embodiment discloses a method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion, comprising the following steps:

[0039] Step (1): Mix dodecafluoroheptyl methacrylate, ethanolamine and methanol, and react them at 30°C for 24 hours under a nitrogen atmosphere. After the reaction is completed, remove methanol by vacuum distillation to obtain fluoroalcohol.

[0040] The molar ratio of dodecafluoroheptyl methacrylate to ethanolamine is 1:1; the mass ratio of dodecafluoroheptyl methacrylate to methanol is 1:2.

[0041] Step (2): Mix fluoroethanol, maleic anhydride and tetrabutylammonium bromide evenly at room temperature, heat to 105℃ and react for 3 hours. After the reaction is completed, cool down to 90℃ and add glycidyl methacrylate and p-hydroxyanisole. Heat up to 105℃ again and continue to react for 3 hours. After the reaction is completed, cool down to room temperature and add isophorone diisocyanate and react again for 3 hours. After the reaction is completed, the intermediate product is obtained.

[0042] The mass ratio of fluorohydrin, maleic anhydride, glycidyl methacrylate, and isophorone diisocyanate is 4.6:1:1.4:2.2; the amount of tetrabutylammonium bromide added is 1 wt% of the combined mass of fluorohydrin and maleic anhydride; and the mass of p-hydroxyanisole added is 0.5 wt% of the mass of glycidyl methacrylate.

[0043] 2-Amino-4-hydroxy-6-methylpyrimidine and dimethyl sulfoxide were mixed and dissolved at 170°C, cooled to room temperature, and the intermediate was added and reacted at room temperature for 2 hours. After the reaction was completed, the mixture was filtered under reduced pressure and dried at 80°C for 8 hours to obtain a fluorine-containing functional monomer.

[0044] The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, the intermediate product, and dimethyl sulfoxide is 30:4.1:100.

[0045] Step (3): Mix 20 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl acrylate, 8 parts by weight of acrylic acid, 5 parts by weight of cashew acrylate and 2 parts by weight of fluorinated functional monomer to obtain acrylate monomer.

[0046] Cashew acrylate is prepared by the following steps:

[0047] Cashew nut shellacryl, triethylamine, and dichloromethane were mixed at a solid-liquid ratio of 15 g:1 g:10 mL. A dichloromethane solution of acryloyl chloride was added dropwise, and the mixture was reacted at 25 °C for 2 h. After the reaction was completed, the mixture was filtered, and the filtrate was collected and the dichloromethane solvent was removed by vacuum distillation to obtain cashew nut shellacryl ester. The molar ratio of cashew nut shellacryl to acryloyl chloride was 1:1.1. The dichloromethane solution of acryloyl chloride was prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2.

[0048] Step (4): Stir 1 part emulsifier and 20 parts water to mix and dissolve. Add 40 parts acrylate monomer under stirring at 200 r / min and continue stirring for 30 min to obtain monomer pre-emulsion.

[0049] The monomer preemulsion was divided into two parts, with a mass ratio of 2:8 between the first and second parts. 1.2 parts emulsifier, 30 parts water, and 1 part sodium bicarbonate were stirred and dissolved. The first part of the monomer preemulsion was then added, and the mixture was reacted at 80℃ and 200 rpm for 30 minutes. After the reaction, the second part of the monomer preemulsion and 20 parts of 2wt% ammonium persulfate aqueous solution were added dropwise. The second part of the monomer preemulsion was added over 2.5 hours, and the initiator solution was added over 2.6 hours. After the addition was complete, the reaction was continued at 80℃ for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, the pH was adjusted to 7, and the mixture was filtered to obtain a water-resistant polyacrylic acid cashew phenol ester emulsion.

[0050] Example 2

[0051] This embodiment discloses a method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion, comprising the following steps:

[0052] Step (1): Mix fluoroethanol, maleic anhydride and tetrabutylammonium bromide evenly at room temperature, heat to 105℃ and react for 3 hours. After the reaction is completed, cool down to 90℃ and add glycidyl methacrylate and p-hydroxyanisole. Heat up to 105℃ again and continue to react for 3 hours. After the reaction is completed, cool down to room temperature and add isophorone diisocyanate and react again for 3 hours. After the reaction is completed, the intermediate product is obtained.

[0053] The preparation of the fluorohydrin was the same as in Example 1; the mass ratio of fluorohydrin, maleic anhydride, glycidyl methacrylate, and isophorone diisocyanate was 4.6:1:1.4:2.2; the amount of tetrabutylammonium bromide added was 1 wt% of the sum of the masses of the fluorohydrin and maleic anhydride; the mass of p-hydroxyanisole added was 0.5 wt% of the mass of glycidyl methacrylate.

[0054] 2-Amino-4-hydroxy-6-methylpyrimidine and dimethyl sulfoxide were mixed and dissolved at 170°C, cooled to room temperature, and the intermediate was added and reacted at room temperature for 2 hours. After the reaction was completed, the mixture was filtered under reduced pressure and dried at 80°C for 8 hours to obtain a fluorine-containing functional monomer.

[0055] The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, the intermediate product, and dimethyl sulfoxide is 30:4.1:100.

[0056] Step (2): Mix 20 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl acrylate, 8 parts by weight of acrylic acid, 6 parts by weight of cashew acrylate and 3 parts by weight of fluorine-containing functional monomer to obtain acrylate monomer.

[0057] Cashew acrylate is prepared by the following steps:

[0058] Cashew nut shellacryl, triethylamine, and dichloromethane were mixed at a solid-liquid ratio of 15 g:1 g:10 mL. A dichloromethane solution of acryloyl chloride was added dropwise, and the mixture was reacted at 25 °C for 2 h. After the reaction was completed, the mixture was filtered, and the filtrate was collected and the dichloromethane solvent was removed by vacuum distillation to obtain cashew nut shellacryl ester. The molar ratio of cashew nut shellacryl to acryloyl chloride was 1:1.1. The dichloromethane solution of acryloyl chloride was prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2.

[0059] Step (3): Stir 1 part emulsifier and 20 parts water to dissolve them. Add 40 parts acrylate monomer under stirring at 200 r / min and continue stirring for 30 min to obtain monomer pre-emulsion.

[0060] The monomer preemulsion was divided into two parts, with a mass ratio of 2:8 between the first and second parts. 1.2 parts emulsifier, 30 parts water, and 1 part sodium bicarbonate were stirred and dissolved. The first part of the monomer preemulsion was then added, and the mixture was reacted at 80℃ and 200 rpm for 30 minutes. After the reaction, the second part of the monomer preemulsion and 20 parts of 2wt% ammonium persulfate aqueous solution were added dropwise. The second part of the monomer preemulsion was added over 2.5 hours, and the initiator solution was added over 2.6 hours. After the addition was complete, the reaction was continued at 80℃ for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, the pH was adjusted to 7, and the mixture was filtered to obtain a water-resistant polyacrylic acid cashew phenol ester emulsion.

[0061] Example 3

[0062] This embodiment discloses a method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion, comprising the following steps:

[0063] Step (1): Mix fluoroethanol, maleic anhydride and tetrabutylammonium bromide evenly at room temperature, heat to 105℃ and react for 3 hours. After the reaction is completed, cool down to 90℃ and add glycidyl methacrylate and p-hydroxyanisole. Heat up to 105℃ again and continue to react for 3 hours. After the reaction is completed, cool down to room temperature and add isophorone diisocyanate and react again for 3 hours. After the reaction is completed, the intermediate product is obtained.

[0064] The preparation of the fluorohydrin was the same as in Example 1; the mass ratio of fluorohydrin, maleic anhydride, glycidyl methacrylate, and isophorone diisocyanate was 4.6:1:1.4:2.2; the amount of tetrabutylammonium bromide added was 1 wt% of the sum of the masses of the fluorohydrin and maleic anhydride; the mass of p-hydroxyanisole added was 0.5 wt% of the mass of glycidyl methacrylate.

[0065] 2-Amino-4-hydroxy-6-methylpyrimidine and dimethyl sulfoxide were mixed and dissolved at 170°C, cooled to room temperature, and the intermediate was added and reacted at room temperature for 2 hours. After the reaction was completed, the mixture was filtered under reduced pressure and dried at 80°C for 8 hours to obtain a fluorine-containing functional monomer.

[0066] The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, the intermediate product, and dimethyl sulfoxide is 30:4.1:100.

[0067] Step (2): Mix 20 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl acrylate, 8 parts by weight of acrylic acid, 7 parts by weight of cashew acrylate and 4 parts by weight of fluorine-containing functional monomer to obtain acrylate monomer.

[0068] Cashew acrylate is prepared by the following steps:

[0069] Cashew nut shellacryl, triethylamine, and dichloromethane were mixed at a solid-liquid ratio of 15 g:1 g:10 mL. A dichloromethane solution of acryloyl chloride was added dropwise, and the mixture was reacted at 25 °C for 2 h. After the reaction was completed, the mixture was filtered, and the filtrate was collected and the dichloromethane solvent was removed by vacuum distillation to obtain cashew nut shellacryl ester. The molar ratio of cashew nut shellacryl to acryloyl chloride was 1:1.1. The dichloromethane solution of acryloyl chloride was prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2.

[0070] Step (3): Stir 1 part emulsifier and 20 parts water to dissolve them. Add 40 parts acrylate monomer under stirring at 200 r / min and continue stirring for 30 min to obtain monomer pre-emulsion.

[0071] The monomer preemulsion was divided into two parts, with a mass ratio of 2:8 between the first and second parts. 1.2 parts emulsifier, 30 parts water, and 1 part sodium bicarbonate were stirred and dissolved. The first part of the monomer preemulsion was then added, and the mixture was reacted at 80℃ and 200 rpm for 30 minutes. After the reaction, the second part of the monomer preemulsion and 20 parts of 2wt% ammonium persulfate aqueous solution were added dropwise. The second part of the monomer preemulsion was added over 2.5 hours, and the initiator solution was added over 2.6 hours. After the addition was complete, the reaction was continued at 80℃ for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, the pH was adjusted to 7, and the mixture was filtered to obtain a water-resistant polyacrylic acid cashew phenol ester emulsion.

[0072] Example 4

[0073] This embodiment discloses a method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion, comprising the following steps:

[0074] Step (1): Mix fluoroethanol, maleic anhydride and tetrabutylammonium bromide evenly at room temperature, heat to 105℃ and react for 3 hours. After the reaction is completed, cool down to 90℃ and add glycidyl methacrylate and p-hydroxyanisole. Heat up to 105℃ again and continue to react for 3 hours. After the reaction is completed, cool down to room temperature and add isophorone diisocyanate and react again for 3 hours. After the reaction is completed, the intermediate product is obtained.

[0075] The preparation of the fluorohydrin was the same as in Example 1; the mass ratio of fluorohydrin, maleic anhydride, glycidyl methacrylate, and isophorone diisocyanate was 4.6:1:1.4:2.2; the amount of tetrabutylammonium bromide added was 1 wt% of the sum of the masses of the fluorohydrin and maleic anhydride; the mass of p-hydroxyanisole added was 0.5 wt% of the mass of glycidyl methacrylate.

[0076] 2-Amino-4-hydroxy-6-methylpyrimidine and dimethyl sulfoxide were mixed and dissolved at 170°C, cooled to room temperature, and the intermediate was added and reacted at room temperature for 2 hours. After the reaction was completed, the mixture was filtered under reduced pressure and dried at 80°C for 8 hours to obtain a fluorine-containing functional monomer.

[0077] The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, the intermediate product, and dimethyl sulfoxide is 30:4.1:100.

[0078] Step (2): Mix 20 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl acrylate, 8 parts by weight of acrylic acid, 8 parts by weight of cashew acrylate and 5 parts by weight of fluorine-containing functional monomer to obtain acrylate monomer.

[0079] Cashew acrylate is prepared by the following steps:

[0080] Cashew nut shellacryl, triethylamine, and dichloromethane were mixed at a solid-liquid ratio of 15 g:1 g:10 mL. A dichloromethane solution of acryloyl chloride was added dropwise, and the mixture was reacted at 25 °C for 2 h. After the reaction was completed, the mixture was filtered, and the filtrate was collected and the dichloromethane solvent was removed by vacuum distillation to obtain cashew nut shellacryl ester. The molar ratio of cashew nut shellacryl to acryloyl chloride was 1:1.1. The dichloromethane solution of acryloyl chloride was prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2.

[0081] Step (3): Stir 1 part emulsifier and 20 parts water to dissolve them. Add 40 parts acrylate monomer under stirring at 200 r / min and continue stirring for 30 min to obtain monomer pre-emulsion.

[0082] The monomer preemulsion was divided into two parts, with a mass ratio of 2:8 between the first and second parts. 1.2 parts emulsifier, 30 parts water, and 1 part sodium bicarbonate were stirred and dissolved. The first part of the monomer preemulsion was then added, and the mixture was reacted at 80℃ and 200 rpm for 30 minutes. After the reaction, the second part of the monomer preemulsion and 20 parts of 2wt% ammonium persulfate aqueous solution were added dropwise. The second part of the monomer preemulsion was added over 2.5 hours, and the initiator solution was added over 2.6 hours. After the addition was complete, the reaction was continued at 80℃ for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, the pH was adjusted to 7, and the mixture was filtered to obtain a water-resistant polyacrylic acid cashew phenol ester emulsion.

[0083] Example 5

[0084] This embodiment discloses a method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion, comprising the following steps:

[0085] Step (1): Mix fluoroethanol, maleic anhydride and tetrabutylammonium bromide evenly at room temperature, heat to 105℃ and react for 3 hours. After the reaction is completed, cool down to 90℃ and add glycidyl methacrylate and p-hydroxyanisole. Heat up to 105℃ again and continue to react for 3 hours. After the reaction is completed, cool down to room temperature and add isophorone diisocyanate and react again for 3 hours. After the reaction is completed, the intermediate product is obtained.

[0086] The preparation of the fluorohydrin was the same as in Example 1; the mass ratio of fluorohydrin, maleic anhydride, glycidyl methacrylate, and isophorone diisocyanate was 4.6:1:1.4:2.2; the amount of tetrabutylammonium bromide added was 1 wt% of the sum of the masses of the fluorohydrin and maleic anhydride; the mass of p-hydroxyanisole added was 0.5 wt% of the mass of glycidyl methacrylate.

[0087] 2-Amino-4-hydroxy-6-methylpyrimidine and dimethyl sulfoxide were mixed and dissolved at 170°C, cooled to room temperature, and the intermediate was added and reacted at room temperature for 2 hours. After the reaction was completed, the mixture was filtered under reduced pressure and dried at 80°C for 8 hours to obtain a fluorine-containing functional monomer.

[0088] The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, the intermediate product, and dimethyl sulfoxide is 30:4.1:100.

[0089] Step (2): Mix 20 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl acrylate, 8 parts by weight of acrylic acid, 9 parts by weight of cashew acrylate and 6 parts by weight of fluorine-containing functional monomer to obtain acrylate monomer.

[0090] Cashew acrylate is prepared by the following steps:

[0091] Cashew nut shellacryl, triethylamine, and dichloromethane were mixed at a solid-liquid ratio of 15 g:1 g:10 mL. A dichloromethane solution of acryloyl chloride was added dropwise, and the mixture was reacted at 25 °C for 2 h. After the reaction was completed, the mixture was filtered, and the filtrate was collected and the dichloromethane solvent was removed by vacuum distillation to obtain cashew nut shellacryl ester. The molar ratio of cashew nut shellacryl to acryloyl chloride was 1:1.1. The dichloromethane solution of acryloyl chloride was prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2.

[0092] Step (3): Stir 1 part emulsifier and 20 parts water to dissolve them. Add 40 parts acrylate monomer under stirring at 200 r / min and continue stirring for 30 min to obtain monomer pre-emulsion.

[0093] The monomer preemulsion was divided into two parts, with a mass ratio of 2:8 between the first and second parts. 1.2 parts emulsifier, 30 parts water, and 1 part sodium bicarbonate were stirred and dissolved. The first part of the monomer preemulsion was then added, and the mixture was reacted at 80℃ and 200 rpm for 30 minutes. After the reaction, the second part of the monomer preemulsion and 20 parts of 2wt% ammonium persulfate aqueous solution were added dropwise. The second part of the monomer preemulsion was added over 2.5 hours, and the initiator solution was added over 2.6 hours. After the addition was complete, the reaction was continued at 80℃ for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, the pH was adjusted to 7, and the mixture was filtered to obtain a water-resistant polyacrylic acid cashew phenol ester emulsion.

[0094] Comparative Example 1

[0095] This comparative example discloses a method for preparing a polyacrylic acid cashew phenol ester emulsion, comprising the following steps:

[0096] Step (1): Mix fluoroalcohol, maleic anhydride and tetrabutylammonium bromide evenly at room temperature, heat to 105℃ and react for 3h. After the reaction is completed, cool down to 90℃ and add glycidyl methacrylate and p-hydroxyanisole. Heat up to 105℃ again and continue to react for 3h. After the reaction is completed, cool down to room temperature and add 3-methylbenzyl isocyanate and react for 3h again. After the reaction is completed, a fluorinated functional monomer is obtained.

[0097] The preparation of the fluorohydrin was the same as in Example 1; the mass ratio of fluorohydrin, maleic anhydride, glycidyl methacrylate, and 3-methylbenzyl isocyanate was 4.6:1:1.4:2.8; the amount of tetrabutylammonium bromide added was 1 wt% of the sum of the masses of the fluorohydrin and maleic anhydride; the mass of p-hydroxyanisole added was 0.5 wt% of the mass of glycidyl methacrylate.

[0098] Step (2): Mix 20 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl acrylate, 8 parts by weight of acrylic acid, 5 parts by weight of cashew acrylate and 2 parts by weight of fluorinated functional monomer to obtain acrylate monomer.

[0099] Cashew acrylate is prepared by the following steps:

[0100] Cashew nut shellacryl, triethylamine, and dichloromethane were mixed at a solid-liquid ratio of 15 g:1 g:10 mL. A dichloromethane solution of acryloyl chloride was added dropwise, and the mixture was reacted at 25 °C for 2 h. After the reaction was completed, the mixture was filtered, and the filtrate was collected and the dichloromethane solvent was removed by vacuum distillation to obtain cashew nut shellacryl ester. The molar ratio of cashew nut shellacryl to acryloyl chloride was 1:1.1. The dichloromethane solution of acryloyl chloride was prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2.

[0101] Step (3): Stir 1 part emulsifier and 20 parts water to dissolve them. Add 40 parts acrylate monomer under stirring at 200 r / min and continue stirring for 30 min to obtain monomer pre-emulsion.

[0102] The monomer preemulsion was divided into two parts, with a mass ratio of 2:8 between the first and second parts. 1.2 parts of emulsifier, 30 parts of water, and 1 part of sodium bicarbonate were stirred and dissolved. The first part of the monomer preemulsion was then added, and the mixture was reacted at 80℃ and 200 r / min for 30 min. After the reaction was completed, the second part of the monomer preemulsion and 20 parts of 2wt% ammonium persulfate aqueous solution were added dropwise. The second part of the monomer preemulsion was added dropwise over 2.5 h, and the initiator solution was added dropwise over 2.6 h. After the addition was completed, the mixture was reacted again at 80℃ for 2 h. After the reaction was completed, the mixture was cooled to room temperature, the pH was adjusted to 7, and the mixture was filtered to obtain a polyacrylic acid cashew phenol ester emulsion.

[0103] Comparative Example 2

[0104] This comparative example discloses a method for preparing a polyacrylic acid cashew phenol ester emulsion, comprising the following steps:

[0105] Step (1): 2-amino-4-hydroxy-6-methylpyrimidine and dimethyl sulfoxide are mixed and dissolved at 170°C, cooled to room temperature, and 3-isopropyl-dimethylbenzyl isocyanate is added and reacted at room temperature for 2 hours. After the reaction is completed, the mixture is filtered under reduced pressure and dried at 80°C for 8 hours to obtain the functional monomer.

[0106] The mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, 3-isopropyl-dimethylbenzyl isocyanate, and dimethyl sulfoxide is 30:4.1:100.

[0107] Step (2): Mix 20 parts by weight of methyl methacrylate, 25 parts by weight of n-butyl acrylate, 8 parts by weight of acrylic acid, 5 parts by weight of cashew acrylate and 2 parts by weight of functional monomer to obtain acrylate monomer.

[0108] Cashew acrylate is prepared by the following steps:

[0109] Cashew nut shellacryl, triethylamine, and dichloromethane were mixed at a solid-liquid ratio of 15 g:1 g:10 mL. A dichloromethane solution of acryloyl chloride was added dropwise, and the mixture was reacted at 25 °C for 2 h. After the reaction was completed, the mixture was filtered, and the filtrate was collected and the dichloromethane solvent was removed by vacuum distillation to obtain cashew nut shellacryl ester. The molar ratio of cashew nut shellacryl to acryloyl chloride was 1:1.1. The dichloromethane solution of acryloyl chloride was prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2.

[0110] Step (3): Stir 1 part emulsifier and 20 parts water to dissolve them. Add 40 parts acrylate monomer under stirring at 200 r / min and continue stirring for 30 min to obtain monomer pre-emulsion.

[0111] The monomer preemulsion was divided into two parts, with a mass ratio of 2:8 between the first and second parts. 1.2 parts of emulsifier, 30 parts of water, and 1 part of sodium bicarbonate were stirred and dissolved. The first part of the monomer preemulsion was then added, and the mixture was reacted at 80℃ and 200 r / min for 30 min. After the reaction was completed, the second part of the monomer preemulsion and 20 parts of 2wt% ammonium persulfate aqueous solution were added dropwise. The second part of the monomer preemulsion was added dropwise over 2.5 h, and the initiator solution was added dropwise over 2.6 h. After the addition was completed, the mixture was reacted again at 80℃ for 2 h. After the reaction was completed, the mixture was cooled to room temperature, the pH was adjusted to 7, and the mixture was filtered to obtain a polyacrylic acid cashew phenol ester emulsion.

[0112] In the above examples and comparative examples, the emulsifier was prepared by mixing octylphenol polyoxyethylene ether and sodium dodecyl sulfate in a mass ratio of 2:1.

[0113] Test case

[0114] The polyacrylic acid cashew phenol ester emulsions prepared in Examples 1-5 and Comparative Examples 1-2 were coated onto a substrate and cured at 60°C for 48 hours before performance testing. Specific test results are shown in Table 1.

[0115] Table 1

[0116] Water absorption rate (%) Tensile strength (MPa) Adhesion (Grade) hardness Example 1 6.7 24.6 1 2H Example 2 6.5 25.1 1 2H Example 3 6.1 25.7 1 2H Example 4 5.8 26.3 1 2H Example 5 5.5 26.8 1 2H Comparative Example 1 9.8 15.7 2 2H Comparative Example 2 18.7 23.5 1 H

[0117] The tests for each indicator in Table 1 were conducted according to the following standards: The water absorption rate was tested by coating a 2mm thick polyacrylic acid cashew phenol ester emulsion onto a polytetrafluoroethylene substrate. The film was then formed at 50% humidity and 25°C. After complete drying, the film was removed and its mass was recorded as m1. The film was then immersed in water at 25°C for 24 hours. The surface water was absorbed using filter paper, and the mass was recorded as m2. The water absorption rate was calculated as: Water absorption rate = [(m2-m1) / m1] × 100%. Tensile strength was determined according to GB / T1040 "Plastics - Tensile Testing Method". Adhesion was determined according to GB / T9286 "Paints and Varnishes - Cross-cut Test". Hardness was determined according to GB / T 6739 "Paints and Varnishes - Pencil Method for Determining Hardness of Paint Films".

[0118] As can be seen from the test results in Table 1, the latex film formed by curing the polyacrylic acid cashew phenol ester emulsion prepared in this invention exhibits excellent water resistance, adhesion, and mechanical properties. This is because the invention prepares a fluorinated functional monomer with hydrophobic segments, a ureidopyrimidinone structure, and multiple active carbon-carbon double bonds. The polyacrylic acid cashew phenol ester emulsion, synthesized by combining the fluorinated functional monomer, acrylic cashew phenol ester, and other acrylate monomers, improves the water resistance, adhesion, and mechanical properties of the film after emulsion formation through the synergistic effect of each component. Cashew phenol has an unsaturated fatty chain similar to vegetable oleic acid, and also has a rigid benzene ring structure. Therefore, acrylic cashew phenol ester prepared by reacting cashew phenol with acryloyl chloride can improve the water resistance, adhesion, and mechanical properties of the material. In the fluorinated functional monomer, the fluorinated hydrophobic segments improve the hydrophobicity and heat resistance of the material. The presence of multiple active carbon-carbon double bonds further improves the crosslinking degree of the material. 2-Amino-4-hydroxy-6-methylpyrimidine, as a pyrimidine derivative, can form multiple hydrogen bonds, thereby improving water resistance and mechanical properties by constructing a physical crosslinking system.

[0119] The fluorinated functional monomer prepared in Comparative Example 1 did not contain 2-amino-4-hydroxy-6-methylpyrimidine, and lacked the effect of the ureidopyrimidinone structure on improving the crosslinking degree of the system. Therefore, the water resistance, adhesion and mechanical properties of Comparative Example 1 were not as good as those of the Example.

[0120] In Comparative Example 2, a functional monomer was prepared by reacting 2-amino-4-hydroxy-6-methylpyrimidine with 3-isopropyl-dimethylbenzyl isocyanate. However, it lacked the effect of fluorinated hydrophobic segments and multiple active carbon carbon double bonds on improving the hydrophobic function and crosslinking degree of the system. Therefore, the water resistance and mechanical properties of Comparative Example 2 were not as good as those of the Example.

[0121] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion, characterized in that, Includes the following steps: Step (1): Mix dodecafluoroheptyl methacrylate, ethanolamine, and methanol, react, and after the reaction is complete, distill under reduced pressure to obtain fluoroalcohol; The molar ratio of dodecylfluoroheptyl methacrylate to ethanolamine is 1:1; the mass ratio of dodecylfluoroheptyl methacrylate to methanol is 1:2-3; the reaction conditions are: reaction under nitrogen atmosphere at 20-30℃ for 20-30 h. Fluorohydrin, maleic anhydride, and tetrabutylammonium bromide were mixed evenly at room temperature, heated, and reacted. After the reaction was completed, the temperature was lowered, glycidyl methacrylate and p-hydroxyanisole were added, the temperature was raised again, and the reaction continued. After the reaction was completed, the temperature was lowered, isophorone diisocyanate was added, and the reaction was repeated. After the reaction was completed, the intermediate product was obtained. 2-Amino-4-hydroxy-6-methylpyrimidine and dimethyl sulfoxide were mixed and dissolved, cooled, and an intermediate product was added to react. After the reaction was completed, the mixture was filtered under reduced pressure and dried to obtain a fluorine-containing functional monomer. Step (2): Mix methyl methacrylate, n-butyl acrylate, acrylic acid, cashew acrylate, and fluorine-containing functional monomers to obtain acrylate monomers; Step (3): Stir the emulsifier and water to dissolve them, add the acrylate monomer, and continue stirring to obtain the monomer pre-emulsion; The monomer pre-emulsion was divided into two parts. The emulsifier, water, and sodium bicarbonate were stirred and mixed to dissolve. The first part of the monomer pre-emulsion was added and reacted. After the reaction was completed, the second part of the monomer pre-emulsion and ammonium persulfate aqueous solution were added dropwise. After the addition was completed, the reaction continued. After the reaction was completed, the mixture was cooled, the pH was adjusted to neutral, and the mixture was filtered to obtain water-resistant polyacrylic acid cashew phenol ester emulsion.

2. The method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion according to claim 1, characterized in that, In step (1): the mass ratio of fluorohydrin, maleic anhydride, glycidyl methacrylate, and isophorone diisocyanate is 4.6:0.8-1:1.2-1.4:2-2.2; the amount of tetrabutylammonium bromide added is 0.8-1 wt% of the total mass of fluorohydrin and maleic anhydride; the mass of p-hydroxyanisole added is 0.5-0.8 wt% of the mass of glycidyl methacrylate; the reaction conditions are: reacting at 100-105℃ for 3-4 h; the addition temperature of glycidyl methacrylate and p-hydroxyanisole is 90-92℃; the continued reaction conditions are: reacting at 105℃ for 2-4 h; the second reaction conditions are: reacting again at room temperature for 2-3 h.

3. The method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion according to claim 1, characterized in that, In step (1), the mass ratio of 2-amino-4-hydroxy-6-methylpyrimidine, intermediate product, and dimethyl sulfoxide is 30:3.8-4.1:100; the reaction conditions are: reaction at room temperature for 2-3 hours.

4. The method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion according to claim 1, characterized in that, In step (2), the acrylate monomers include the following components by mass: 15-20 parts methyl methacrylate, 20-25 parts n-butyl acrylate, 8-10 parts acrylic acid, 5-9 parts cashew acrylate, and 2-6 parts fluorinated functional monomers.

5. The method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion according to claim 1, characterized in that, In step (2), cashew acrylate is prepared by the following steps: Cashew nut phenol, triethylamine, and dichloromethane were mixed, and a dichloromethane solution of acryloyl chloride was added dropwise. After the reaction was completed, the mixture was filtered and distilled under reduced pressure to obtain cashew nut phenol ester. The solid-liquid ratio of cashew phenol, triethylamine, and dichloromethane is 15g:1-1.5g:10-20mL; the molar ratio of cashew phenol and acryloyl chloride is 1:1-1.2; the dichloromethane solution of acryloyl chloride is prepared by mixing acryloyl chloride and dichloromethane at a solid-liquid ratio of 1:2-3; the reaction conditions are: reacting at 20-25℃ for 2-4h.

6. The method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion according to claim 1, characterized in that, In step (3), the water-resistant polyacrylic acid cashew phenol ester emulsion comprises the following components by mass: 2.2-2.7 parts emulsifier, 50-60 parts water, 40-50 parts acrylate monomer, 1-1.5 parts sodium bicarbonate, and 20-25 parts ammonium persulfate aqueous solution; the ammonium persulfate aqueous solution has a concentration of 2 wt%. The monomer preemulsion comprises the following components: 1-1.5 parts emulsifier, 20-30 parts water, and 40-50 parts acrylate monomer; the stirring conditions are: stirring at 100-300 r / min for 20-30 min; the mass ratio of the first monomer preemulsion to the second monomer preemulsion is 1-2:8-9.

7. The method for preparing a water-resistant polyacrylic acid cashew phenol ester emulsion according to claim 1, characterized in that, In step (3), the reaction conditions are: reacting for 30 minutes at a temperature of 75-85℃ and a stirring speed of 100-300r / min; the dropping time of the second monomer pre-emulsion is 2.5-3h, and the dropping time of the initiator solution is 2.6-3.1h; the reaction conditions are: continuing the reaction at a temperature of 75-85℃ for 2-3h.

8. A water-resistant polyacrylic acid cashew phenol ester emulsion prepared by the method described in any one of claims 1-7.

9. The application of the water-resistant polyacrylic acid cashew phenol ester emulsion as described in claim 8 in inks.

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