Biomass-modified hydroxyl acrylic dispersions resistant to boiling water cooking and methods of making the same

Abstract

The application belongs to the technical field of organic coating and specifically relates to a boiling water resistant biomass modified hydroxyl acrylic dispersion and a preparation method thereof, which is prepared by the following components: four components A, B, C and D; wherein the component A comprises ethylene glycol butyl ether, propylene glycol methyl ether, trimethylbenzene, cashew phenol epoxy resin, styrene, methyl methylpropionate, butyl acrylate, hydroxyethyl acrylate and dibenzoyl peroxide; the component B comprises methyl methylpropionate, butyl acrylate, hydroxyethyl acrylate, dibenzoyl peroxide and acrylic acid; the component C comprises propylene glycol methyl ether and tert-butyl peroxy-2-ethylhexanoate; and the component D comprises dimethyl ethanolamine and deionized water. The cashew phenol epoxy resin is used as a modifier to polymerize and emulsify the acrylic acid to obtain an epoxy modified acrylic dispersion, which can form a high-density reticular cross-linking structure with amino resin when applied as a coating, thereby effectively improving the boiling water resistance.

Description

Technical Field

[0001] This invention belongs to the field of organic coating technology, specifically relating to a biomass-modified hydroxy acrylic dispersion resistant to boiling water and its preparation method. Background Technology

[0002] With increasingly stringent VOC emission regulations and growing public awareness of environmental protection, solvent-based amino baking paints are gradually being replaced by water-based amino baking paints. Among water-based amino baking paint systems, water-dispersion acrylic amino baking paints are widely used in vehicles, home appliances, machinery, hardware accessories, and many other fields due to their excellent gloss, hardness, weather resistance, water resistance, and chemical resistance.

[0003] However, the water-dispersible amino baking paints currently on the market still have problems such as complex resin synthesis process, high cost, and poor boiling water resistance after baking. In the article "Preparation of High-Performance Hydroxy Acrylic Aqueous Dispersions and Their Application in Amino Baking Paints", the boiling water resistance requirement for amino baking paints is only 30 minutes. However, in current practical applications, it is often necessary to achieve performance indicators of boiling water resistance of more than 2 hours without bubbling, loss of gloss, or cracking. Summary of the Invention

[0004] This invention provides a biomass-modified hydroxy acrylic dispersion resistant to boiling water and its preparation method, in order to solve the problem that water-dispersed acrylic amino baking paint is not resistant to boiling water.

[0005] To address the aforementioned technical problems, this invention provides a biomass-modified hydroxyacrylic acid dispersion resistant to boiling water, comprising four components: A, B, C, and D; wherein component A includes: ethylene glycol butyl ether, propylene glycol methyl ether, thiomethylbenzene, cashew phenol epoxy resin, styrene, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, and benzoyl peroxide; component B includes: methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, benzoyl peroxide, and acrylic acid; component C includes: propylene glycol methyl ether and tert-butyl peroxide-2-ethylhexanoate; and component D includes: dimethyl ethanolamine and deionized water.

[0006] Furthermore, the cashew phenol epoxy resin includes cashew phenol diglycidyl ether.

[0007] Furthermore, the structural formula of the cashew phenol diglycidyl ether is as follows:

[0008] Where n is 0, 2, 4, or 6.

[0009] Furthermore, it includes a macromolecular hydroxyl core and a carboxyl shell.

[0010] Further, the mass fractions of the substances in component A are as follows: 3-5 parts ethylene glycol butyl ether; 1-5 parts propylene glycol methyl ether; 3-5 parts tricresyl; 3-10 parts cashew phenol epoxy resin; 1-10 parts styrene; 1-15 parts methyl methacrylate; 10-15 parts butyl acrylate; 1-10 parts hydroxyethyl acrylate; and 0.5-2 parts benzoyl peroxide.

[0011] Furthermore, the mass fractions of the substances in component B are: methyl methacrylate 1-3 parts, butyl acrylate 3-8 parts, hydroxyethyl acrylate 0.8-2 parts, benzoyl peroxide 0.1-0.8 parts, and acrylic acid 1-2 parts.

[0012] Furthermore, the mass fractions of the substances in component C are: 1-2 parts of propylene glycol methyl ether; and 0.02-0.1 parts of tert-butyl peroxide-2-ethylhexanoate.

[0013] Furthermore, the mass fractions of the substances in component D are: 1-2 parts dimethylethanolamine; 35-50 parts deionized water.

[0014] On another aspect, the present invention also provides a method for preparing the biomass-modified hydroxyl acrylic acid dispersion as described above, comprising the following steps: (1) adding cashew phenol epoxy resin to a four-necked flask, stirring uniformly at a speed of 500-600 r / min for 20-25 min and heating to 90-95°C; (2) adding component A slowly dropwise from a constant pressure dropping funnel over 3-4 h, mixing evenly, and keeping warm at 90-95°C for 1 h; (3) adding component B from a constant pressure dropping funnel over 3-4 h. (3) Slowly drip in, mix evenly, and keep warm at 90-95℃ for 1h; (4) Add component C and drip in within 1-3min, and keep warm at 95-100℃ for 2h; to obtain cashew phenol epoxy graft modified acrylic resin; (5) Add dimethyl ethanolamine from component D, stir evenly at 500-600r / min for 20-25min, increase the speed to 800-1000r / min and then add deionized water to disperse for 1h to obtain a biomass modified hydroxy acrylic dispersion resistant to boiling water.

[0015] Furthermore, the environmental temperature for preparing the biomass-modified hydroxyacrylic acid dispersion resistant to boiling water is below 100°C throughout the entire process.

[0016] The beneficial effects of this invention are that the biomass-modified hydroxy acrylic dispersion resistant to boiling water and its preparation method are obtained by polymerizing and emulsifying acrylic acid with cashew phenol epoxy resin as a modifier to obtain an epoxy-modified acrylic dispersion. When used as a coating, it can be combined with amino resin to form a high-density network cross-linked structure, effectively improving boiling water resistance.

[0017] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention.

[0018] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described in detail below. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] This invention provides a biomass-modified hydroxyacrylic acid dispersion resistant to boiling water, comprising the following components: cashew phenol epoxy resin and four components: A, B, C, and D; wherein component A includes: BCS, PM, 100#, cashew phenol epoxy resin, ST, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, and benzoyl peroxide; component B includes: methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, benzoyl peroxide, and acrylic acid; component C includes: PM and tert-butyl peroxide-2-ethylhexanoate; and component D includes: dimethylethanolamine and deionized water.

[0021] In this embodiment, specifically, component A is first synthesized into epoxy-modified acrylic acid, component B grafts carboxyl hydrophilic groups onto component A, and component C is added for subsequent titration.

[0022] In this embodiment, specifically, the cashew nut shell epoxy resin includes cashew nut shell diglycidyl ether, preferably cashew nut shell diglycidyl ether from Changshu Naisu Biomaterials Technology Co., Ltd. Cashew nut shell oil is a plant polyene product extracted by heating and deacidifying natural cashew nut shell oil. It does not consume human food resources and can replace phenol in the synthesis of bifunctional epoxy resins. Cashew nut shell oil has long side chains with olefin double bonds, resulting in low polarity and low viscosity. Compared to bisphenol A epoxy resin, it has better flexibility and water resistance.

[0023] In this embodiment, specifically, the structural formula of the cashew phenol diglycidyl ether is:

[0024] Where n is 0, 2, 4, or 6, the 15C long side chain of cashew phenol is natural and is a mixture of branches with different alkene double bonds. When n = 0, the long branch is a saturated chain; when n = 2, it is one unsaturated double bond; when n = 4, it is two unsaturated double bonds; and when n = 6, it is three unsaturated double bonds.

[0025] In this embodiment, specifically, the viscosity (25°C, mPa·s) of the cashew phenol diglycidyl ether is 80-140, the epoxy equivalent is 260-280, and the non-volatile content is ≥99.7%.

[0026] In this embodiment, specifically, it includes a macromolecular hydroxyl core and a carboxyl shell. The hydroxyl dispersion of this structure and the self-crosslinking interpenetrating network structure formed during the baking process of the amino resin can meet the application requirements of high-end fields.

[0027] In this embodiment, specifically, the mass fractions of the substances in component A are as follows: ethylene glycol butyl ether 3-5 parts; propylene glycol methyl ether 1-5 parts; thiol 3-5 parts; cashew phenol epoxy resin 3-10 parts; styrene 1-10 parts; methyl methacrylate 1-15 parts; butyl acrylate 10-15 parts; hydroxyethyl acrylate 1-10 parts; benzoyl peroxide 0.5-2 parts.

[0028] In this embodiment, specifically, the ethylene glycol butyl ether is preferably BCS, the propylene glycol methyl ether is preferably PM, the trimethylbenzene is preferably 100#, the cashew phenol epoxy resin is preferably 602A, and the styrene is preferably ST.

[0029] In this embodiment, specifically, the mass fractions of the substances in component B are: methyl methacrylate 1-5 parts; butyl acrylate 3-8 parts; hydroxyethyl acrylate 0.8-2 parts; benzoyl peroxide 0.1-0.8 parts; and acrylic acid 1-2 parts.

[0030] In this embodiment, specifically, the mass fractions of the substances in component C are: 1-2 parts of propylene glycol methyl ether; and 0.02-0.1 parts of tert-butyl peroxide-2-ethylhexanoate.

[0031] In this embodiment, specifically, the mass fractions of the substances in component D are: 1-2 parts of dimethylethanolamine and 35-50 parts of deionized water.

[0032] In this embodiment, specifically, styrene and methyl methacrylate are used as hard monomers, butyl acrylate as a soft monomer, acrylic acid and hydroxyethyl acrylate as functional monomers, and cashew phenol epoxy resin as a modifier. Polymerization and emulsification are performed to obtain an epoxy-modified acrylic dispersion. The addition of amino resin can improve the network crosslinking density.

[0033] In this embodiment, specifically, styrene provides the resin's hardness and rigidity, methyl methacrylate provides the resin's hardness and rigidity, butyl acrylate provides the resin's toughness, acrylic acid provides carboxyl functional groups in the resin molecule, and hydroxyethyl acrylate provides hydroxyl functional groups in the resin molecule.

[0034] In this embodiment, specifically, bisphenol A epoxy resin is first dissolved in an alcohol ether solvent containing styrene, methyl methacrylate, butyl acrylate, and hydroxyethyl acrylate. At a temperature below 100°C, the double bonds of the acrylic monomers and the branched bonds of cashew phenols copolymerize, or the hydroxyl groups in the acrylic resin react with some of the epoxy groups in the epoxy resin. The epoxy groups in the epoxy resin molecules react to form hydroxyl groups that are attached to the acrylic resin molecular chain, thus preparing an interpenetrating polymer network to achieve epoxy modification. Then, acrylic acid is introduced; the carboxyl groups on the acrylic acid provide hydrophilic groups, which are neutralized by dimethylethanolamine to form a salt. Water is added for emulsification and phase inversion, forming an epoxy-modified acrylic dispersion.

[0035] On another aspect, the present invention also provides a method for preparing the biomass-modified hydroxyl acrylic acid dispersion as described above, comprising the following steps: (1) adding cashew phenol epoxy resin to a four-necked flask, stirring uniformly at 500 r / min for 20 min and heating to 90-95°C; (2) adding component A slowly dropwise from a constant pressure dropping funnel over 4 h, mixing evenly, and keeping warm at 90-95°C for 1 h; (3) adding component B from a constant pressure dropping funnel over 4 h. Slowly drip in, mix evenly, and keep warm at 90-95℃ for 1h; (4) Add component C and drip in within 1-3min, and keep warm at 95-100℃ for 2h; obtain cashew phenol epoxy graft modified acrylic resin; (5) Add dimethyl ethanolamine from component D, stir evenly at 600r / min for 20min, increase the speed to 1000r / min and then add deionized water to disperse for 1h, to obtain a biomass modified hydroxy acrylic dispersion resistant to boiling water.

[0036] In this embodiment, specifically, the environmental temperature for preparing the boiling-resistant biomass-modified hydroxyacrylic acid dispersion is ≤100℃ throughout the entire process.

[0037] Example 1

[0038] The recipe is as follows:

[0039]

[0040]

[0041] Example 2

[0042] The recipe is as follows:

[0043] 1 BCS 3 —— —— —— 3 2 PM 1 —— 1 —— 2 3 100# 5 —— —— —— 5 4 Cashew phenol epoxy resin 602A 8 —— —— —— 8 5 ST 5 —— —— —— 5 6 Methyl methacrylate 8.5 1.9 —— —— 10.4 7 Butyl acrylate 8.6 2.7 —— —— 11.3 8 Hydroxyethyl acrylate 6.5 1.3 —— —— 7.8 9 Benzoyl peroxide 1 0.44 —— —— 1.44 10 acrylic acid —— 1 —— —— 1 11 tert-butyl peroxide-2-ethylhexanoate —— —— 0.06 —— 0.06 12 Dimethylethanolamine —— —— —— 1 1 13 Deionized water —— —— —— 44 44 total 100

[0044] Example 3

[0045] The recipe is as follows:

[0046] 1 BCS 3 —— —— —— 3 2 PM 1 —— 1 —— 2 3 100# 5 —— —— —— 5 4 Cashew phenol epoxy resin 602A 4 —— —— —— 4 5 ST 5 —— —— —— 5 6 Methyl methacrylate 12 2 —— —— 14 7 Butyl acrylate 8.5 3.5 —— —— 12 8 Hydroxyethyl acrylate 6.5 1.3 —— —— 7.5 9 Benzoyl peroxide 1 0.4 —— —— 1.44 10 acrylic acid —— 1 —— —— 1 11 tert-butyl peroxide-2-ethylhexanoate —— —— 0.06 —— 0.06 12 Dimethylethanolamine —— —— —— 1 1 13 Deionized water —— —— —— 44 44 total 100

[0047] Example 4

[0048] The recipe is as follows:

[0049] 1 BCS 3 —— —— —— 3 2 PM 1 —— 1 —— 2 3 100# 5 —— —— —— 5 4 Cashew phenol epoxy resin 602A 4 —— —— —— 4 5 ST 5 —— —— —— 5 6 Methyl methacrylate 8.5 2.2 —— —— 10.7 7 Butyl acrylate 12 3.2 —— —— 15.2 8 Hydroxyethyl acrylate 6.5 1.3 —— —— 7.8 9 Benzoyl peroxide 1 0.4 —— —— 1.44 10 acrylic acid —— 1 —— —— 1 11 tert-butyl peroxide-2-ethylhexanoate —— —— 0.06 —— 0.06 12 Dimethylethanolamine —— —— —— 1 1 13 Deionized water —— —— —— 44 44 total 100

[0050] A biomass-modified hydroxyacrylic acid dispersion resistant to boiling water was prepared according to the preparation method described above:

[0051]

[0052] The biomass-modified hydroxyacrylic acid dispersion that is resistant to boiling water was tested, and the test results are as follows.

[0053] Paint formulation:

[0054]

[0055] In this embodiment, specifically, the cashew phenol epoxy-modified hydroxypropyl dispersion is the aforementioned biomass-modified hydroxyacrylic acid dispersion that is resistant to boiling water.

[0056] Performance (150℃*30min)

[0057]

[0058]

[0059] In this embodiment, specifically, the solid content of the coating is 45%, and the storage time of the coating is 1 year.

[0060] In summary, the boiling-resistant biomass-modified hydroxy acrylic dispersion and its preparation method of the present invention obtain an epoxy-modified acrylic dispersion by polymerizing and emulsifying acrylic acid with cashew phenol epoxy resin as a modifier. When used as a coating, it can be combined with amino resin to form a high-density network cross-linked structure, effectively improving boiling water resistance.

[0061] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A biomass-modified hydroxyl acrylic acid dispersion resistant to boiling water, characterized in that, It is prepared from the following components: The four components are: A, B, C, and D; among which: The A component comprises: 3-5 parts of ethylene glycol butyl ether, 1-5 parts of propylene glycol methyl ether, 3-5 parts of thiol, 3-10 parts of cashew phenol epoxy resin, 1-10 parts of styrene, 1-15 parts of methyl methacrylate, 10-15 parts of butyl acrylate, 1-10 parts of hydroxyethyl acrylate, and 0.5-2 parts of benzoyl peroxide. The cashew phenol epoxy resin is cashew phenol diglycidyl ether, and the structural formula of the cashew phenol diglycidyl ether is as follows: , where n is 0, 2, 4, or 6; The B component comprises: 1-5 parts methyl methacrylate, 3-8 parts butyl acrylate, 0.8-2 parts hydroxyethyl acrylate, 0.1-0.8 parts benzoyl peroxide, and 1-2 parts acrylic acid; The component C includes: propylene glycol methyl ether and tert-butyl peroxide-2-ethylhexanoate; The component D includes: dimethylethanolamine and deionized water; Component A is first used to synthesize epoxy-modified acrylic acid, component B grafts carboxyl hydrophilic groups onto component A, and component C is added for subsequent titration.

2. The biomass-modified hydroxyl acrylic acid dispersion resistant to boiling water as described in claim 1, characterized in that, The mass fractions of the substances in component C are: 1-2 parts of propylene glycol methyl ether; 0.02 to 0.1 parts of tert-butyl peroxide-2-ethylhexanoate.

3. The biomass-modified hydroxyl acrylic acid dispersion resistant to boiling water as described in claim 1, characterized in that, The mass fractions of the substances in component D are: 1-2 parts of dimethylethanolamine; 35-50 parts deionized water.

4. A method for preparing a biomass-modified hydroxyl acrylic acid dispersion resistant to boiling water as described in any one of claims 1-3, characterized in that, Includes the following steps: (1) Add cashew phenol epoxy resin to a four-necked flask, stir evenly at a speed of 500-600 r / min for 20-25 min and heat to 90-95℃; (2) Add component A slowly by dripping it into a constant pressure dropping funnel over 3-4 hours, mix thoroughly, and keep warm at 90-95℃ for 1 hour; (3) Add component B slowly dropwise from a constant pressure dropping funnel over 3-4 hours, mix thoroughly, and keep warm at 90-95°C for 1 hour; (4) Add component C and drip it over 1-3 min, and keep it at 95-100℃ for 2 h; to obtain cashew phenol epoxy grafted modified acrylic resin; (5) Add dimethylethanolamine from component D, stir evenly at a speed of 500-600 r / min for 20-25 min, increase the speed to 800-1000 r / min, add deionized water and disperse for 1 h to obtain a biomass-modified hydroxyacrylic acid dispersion resistant to boiling water.

5. The preparation method according to claim 4, characterized in that, The environmental temperature for preparing the biomass-modified hydroxyacrylic acid dispersion resistant to boiling water is ≤100℃ throughout the entire process.

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