CN113480711B - Vegetable oil modified universal color paste grinding resin and preparation method and application thereof - Google Patents
Vegetable oil modified universal color paste grinding resin and preparation method and application thereof Download PDFInfo
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- CN113480711B CN113480711B CN202011554104.9A CN202011554104A CN113480711B CN 113480711 B CN113480711 B CN 113480711B CN 202011554104 A CN202011554104 A CN 202011554104A CN 113480711 B CN113480711 B CN 113480711B
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- vegetable oil
- color paste
- oil modified
- modified universal
- grinding resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/6715—Unsaturated monofunctional alcohols or amines
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The invention relates to the technical field of preparation of water-based paint, in particular to vegetable oil modified universal color paste grinding resin, a preparation method thereof and application of the grinding resin to the water-based paint, wherein the preparation method comprises the following steps: preparing linear acrylic resin; preparing an isocyanate-terminated vegetable oil; the prepared linear acrylic resin and the vegetable oil blocked by isocyanate are used for preparing the vegetable oil modified universal color paste grinding resin with a comb-shaped structure. The vegetable oil modified universal color paste grinding resin provided by the invention is synthesized by adopting isocyanate and hydroxyl to react, so that the reactivity of cardanol is improved, a comb-shaped structure is synthesized by a stepwise polymerization mode and used for water-based paint, the comb-shaped structure formed by a long carbon chain of cardanol provides a good physical effect for dispersing pigment, and the cardanol modified universal color paste grinding resin is more stable in a water phase after being neutralized by alkali. The prepared color paste has no sedimentation, no flooding and no coarse color after being placed at 50 ℃ for 3 months and at normal temperature for 1 year.
Description
Technical Field
The invention relates to the technical field of water-based paint preparation, in particular to vegetable oil modified universal color paste grinding resin, a preparation method thereof and application of the grinding resin in water-based paint.
Background
Since the aqueous paint appeared, the defects embodied at the application end are endless, especially the problem of storage stability of the aqueous paint becomes one of the important factors restricting the development of the aqueous paint, and because of the complexity of the components of the aqueous paint, the stability of the universal color paste puts forward a higher requirement.
Moreover, as petroleum resources are increasingly depleted and international oil prices are continuously rising, the search for renewable raw materials to prepare novel coatings has been a necessary trend for technical personnel in the field to research.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides vegetable oil modified universal color paste grinding resin, a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a method for preparing a vegetable oil modified universal mill base grinding resin, comprising the following steps:
s1, preparing linear acrylic resin: adding methyl isobutyl ketone, methyl ethyl ketone and ethylene glycol monobutyl ether into a reaction container, introducing nitrogen, heating to 90 ℃, dropwise adding hydroxyethyl acrylate, acrylic acid, vinyl monomers and an initiator into the reaction container, dripping after 5 hours, keeping the temperature for 2 hours, and cooling to below 45 ℃ to obtain linear acrylic resin;
s2, preparing the vegetable oil blocked by isocyanate: after the cardanol is subjected to vacuum dehydration treatment, the cardanol, acetone and an organic tin catalyst are added into a reaction container, the temperature is raised to 50 ℃, diisocyanate monomers are dripped in the reaction container, dripping is completed within 1.5h, the temperature is kept at 50 ℃ for 1h, the NCO content is tested, and after the NCO content meets the requirement, the acetone is removed in vacuum;
s3, preparing the vegetable oil modified universal color paste grinding resin with the comb-shaped structure: adding the linear acrylic resin prepared in the step S1, the vegetable oil blocked by isocyanate prepared in the step S2 and an organic tin catalyst into a reaction vessel, heating to 80 ℃, keeping the temperature for 10 hours, testing the NCO content, cooling to 50 ℃ when the NCO value is less than 1, adding alkali for neutralization, and continuing stirring for 30min to obtain the vegetable oil modified universal color paste grinding resin.
Preferably, in step S1, the vinyl monomer is one or more of styrene, methyl methacrylate, methyl acrylate, ethyl acrylate, and isooctyl acrylate.
Preferably, in step S1, the initiator is one or more of dibenzoyl peroxide, azobisisobutyronitrile, and OT initiator.
Preferably, in the step S2, the diisocyanate monomer is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
Preferably, in step S3, the alkali is one or a mixture of more than one of ammonia water, sodium hydroxide and potassium hydroxide.
Preferably, in the steps S2 and S3, the organotin catalyst is dibutyltin dilaurate.
In a second aspect of the invention, there is also included a vegetable oil modified universal mill base grind resin prepared by the above method.
The third aspect of the invention also comprises the vegetable oil modified universal color paste, wherein the vegetable oil modified universal color paste is prepared by grinding resin with the vegetable oil modified universal color paste, and further comprises deionized water, a defoaming agent, an inorganic pigment and an inorganic filler.
Advantageous effects of the invention
The vegetable oil modified universal color paste grinding resin and the preparation method and application thereof provided by the invention have the advantages that the vegetable oil modified universal color paste grinding resin comprises the following aspects:
1. the vegetable oil modified universal color paste grinding resin adopts an environment-friendly resource cardanol as a raw material, effectively utilizes renewable resources, and provides an effective way for solving the energy crisis;
2. the vegetable oil modified universal color paste grinding resin has a good dispersing and grinding effect, and the prepared color paste has excellent storage stability;
3. the invention has simple process, and the prepared resin has good storage stability and good compatibility with the coating, and is suitable for industrial production.
4. According to the invention, isocyanate and hydroxyl are adopted for reaction synthesis, so that the reaction activity of cardanol is improved, a comb-shaped structure is synthesized in a stepwise polymerization manner, the cardanol is used for a water-based paint, the comb-shaped structure formed by a long carbon chain of cardanol provides a good physical effect for dispersing pigment, after alkali neutralization, a body system is more stable in a water phase, after color paste is ground, the electrostatic repulsion effect is obvious, and the stability of color paste prepared by using the grinding resin is further improved. The prepared color paste has no sedimentation, no flooding and no inverse coarseness after being placed for 3 months at 50 ℃ and 1 year at normal temperature.
Detailed Description
The technical solutions adopted by the present invention are further described below by examples to help those skilled in the art to better understand the present invention.
The invention adopts the following technical scheme:
a. preparation of Linear acrylic resin
Adding methyl isobutyl ketone, methyl ethyl ketone and ethylene glycol monobutyl ether into a four-neck flask with a stirrer, a thermometer and a condenser, introducing nitrogen, heating to 90 ℃, weighing the used hydroxyethyl acrylate, acrylic acid, other vinyl monomers and initiator according to the formula amount into a monomer tank, dripping for 5 hours, keeping the temperature for 2 hours, cooling to below 45 ℃, and discharging to obtain the linear acrylic resin.
The vinyl monomer comprises one or more of styrene, methyl methacrylate, methyl acrylate, ethyl acrylate and isooctyl acrylate.
The initiator comprises one or more than one of dibenzoyl peroxide, azobisisobutyronitrile and OT initiator.
The chemical reaction structural formula in the preparation process is as follows:
b. preparation of isocyanate-terminated vegetable oils
The isocyanate-terminated vegetable oil is prepared by the following steps: after the cardanol is subjected to vacuum dehydration treatment, the cardanol, acetone and an organic tin catalyst are added into a four-neck flask according to the use amounts, the temperature is raised to 50 ℃, diisocyanate monomers are dropwise added, the dropwise addition is completed within 1.5h, the temperature is kept at 50 ℃ for 1h, the NCO content is tested, and after the requirement is met, the acetone is removed in vacuum.
The diisocyanate monomer comprises one or more than one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
The organic tin catalyst is dibutyltin dilaurate.
The chemical reaction structural formula in the preparation process is as follows:
c. preparation of vegetable oil modified acrylic resin with comb-shaped structure
And (b) adding the linear acrylic resin prepared in the step (a), the vegetable oil blocked by isocyanate prepared in the step (b) and an organic tin catalyst into a four-neck flask, heating to 80 ℃, keeping the temperature at 80 ℃ for 10 hours, testing the NCO content, cooling to 50 ℃ when the NCO value is less than 1, adding alkali for neutralization, and continuously stirring for 30 minutes to obtain the vegetable oil modified universal color paste grinding resin.
The alkali comprises one or more of ammonia water, sodium hydroxide and potassium hydroxide.
In order to test the performance of the prepared vegetable oil modified universal color paste grinding resin, the vegetable oil modified universal color paste grinding resin is prepared into color paste.
The color paste preparation process comprises the following steps: adding vegetable oil modified universal color paste grinding resin, deionized water and a defoaming agent into a drawing cylinder in sequence, dispersing for 15 minutes at a high speed, adding titanium dioxide and kaolin in sequence under a stirring state, continuously dispersing for 30 minutes, and then starting sanding to obtain the universal color paste with the fineness of less than 15 micrometers after 1 hour.
The technical effects of the present invention are further verified by the following examples.
Example 1
a. Preparation of Linear acrylic resin
The specific formula is as follows:
adding methyl isobutyl ketone, methyl ethyl ketone and ethylene glycol butyl ether into a four-neck flask with a stirrer, a thermometer and a condenser according to the formula amount, introducing nitrogen, heating to 90 ℃, weighing the used hydroxyethyl acrylate, acrylic acid and other vinyl monomers and initiator into a monomer tank according to the formula amount, dripping after 5 hours, keeping the temperature for 2 hours, cooling to below 45 ℃, and discharging to obtain the linear acrylic resin.
Example 2
b. Preparation of isocyanate-terminated vegetable oils
The specific formula is as follows:
the isocyanate-terminated vegetable oil is prepared by the following steps: after the cardanol is subjected to vacuum dehydration, adding the cardanol, acetone and an organic tin catalyst into a four-neck flask according to the use amounts, heating to 50 ℃, dropwise adding a diisocyanate monomer, finishing dropwise adding for 1.5h, keeping the temperature at 50 ℃ for 1h, testing the NCO content, and removing the acetone in vacuum after the NCO content meets the requirements.
Example 3
c. Preparation of vegetable oil modified acrylic resin with comb-shaped structure
The specific formula is as follows:
and (b) adding the linear acrylic resin prepared in the step (a), the vegetable oil blocked by isocyanate prepared in the step (b) and an organic tin catalyst into a four-neck flask, heating to 80 ℃, keeping the temperature at 80 ℃ for 10 hours, testing the NCO content, cooling to 50 ℃ when the NCO value is less than 1, adding alkali for neutralization, and continuously stirring for 30 minutes to obtain the vegetable oil modified universal color paste grinding resin.
Example 4
The specific formula is as follows:
adding vegetable oil modified universal color paste grinding resin, deionized water and a defoaming agent into a drawing cylinder in sequence, dispersing for 15 minutes at a high speed, adding titanium dioxide and kaolin in sequence under a stirring state, continuously dispersing for 30 minutes, and then starting sanding to obtain the universal color paste with the fineness of less than 15 micrometers after 1 hour.
Example 5
And (3) sequentially adding general color paste grinding resin, deionized water and a defoaming agent into a drawing cylinder, dispersing for 15 minutes at a high speed, sequentially adding titanium dioxide and kaolin under a stirring state, continuously dispersing for 30 minutes, and then starting sanding to obtain the general color paste with the fineness of less than 15 micrometers after 1 hour.
The stability tests carried out on the universal mill bases prepared in example 4 and in example 5 were compared and the results are shown in table one:
watch 1
The results show that the vegetable oil modified general grinding resin prepared by the invention and the existing commercial general grinding resin have obvious improvement on the stability of the color paste.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be covered by the present invention within the technical scope of the present invention, and the technical solutions and novel concepts according to the present invention should be added with equivalent alternatives or modifications.
Claims (7)
1. The preparation method of the vegetable oil modified universal color paste grinding resin is characterized by comprising the following steps of:
s1, preparing linear acrylic resin: adding methyl isobutyl ketone, methyl ethyl ketone and ethylene glycol monobutyl ether into a reaction container, introducing nitrogen, heating to 90 ℃, dropwise adding hydroxyethyl acrylate, acrylic acid, vinyl monomers and an initiator into the reaction container, dripping after 5 hours, keeping the temperature for 2 hours, and cooling to below 45 ℃ to obtain linear acrylic resin;
s2, preparing the vegetable oil blocked by isocyanate: after the cardanol is subjected to vacuum dehydration treatment, the cardanol, acetone and an organic tin catalyst are added into a reaction vessel, the temperature is raised to 50 ℃, diisocyanate monomers are dropwise added, dripping is completed within 1.5h, after heat preservation is carried out for 1h at 50 ℃, NCO content is tested, and after the NCO content meets the requirements, acetone is removed in vacuum;
s3, preparing the vegetable oil modified universal color paste grinding resin with the comb-shaped structure: adding the linear acrylic resin prepared in the step S1, the vegetable oil blocked by isocyanate prepared in the step S2 and an organic tin catalyst into a reaction container, heating to 80 ℃, keeping the temperature for 10 hours, testing the NCO content, cooling to 50 ℃ when the NCO value is less than 1, adding alkali for neutralization, and continuously stirring for 30min to obtain the vegetable oil modified universal color paste grinding resin;
wherein the vinyl monomer in S1 is one or a mixture of more than one of styrene, methyl methacrylate, methyl acrylate, ethyl acrylate and isooctyl acrylate.
2. The method for preparing vegetable oil modified universal mill base grinding resin according to claim 1, wherein in the step S1, the initiator is one or more of dibenzoyl peroxide, azobisisobutyronitrile and OT initiator.
3. The method for preparing the vegetable oil modified universal mill base grinding resin according to claim 1, wherein in the step S2, the diisocyanate monomer is one or a mixture of more than one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
4. The method for preparing the vegetable oil modified universal mill base grinding resin according to claim 1, wherein in the step S3, the alkali is one or a mixture of more than one of ammonia water, sodium hydroxide and potassium hydroxide.
5. The method for preparing the vegetable oil modified universal mill base grinding resin according to claim 1, wherein in the steps S2 and S3, the organotin catalyst is dibutyltin dilaurate.
6. A vegetable oil modified universal color paste grinding resin prepared by the preparation method of any one of claims 1 to 5.
7. The vegetable oil modified universal color paste comprises deionized water, a defoaming agent, an inorganic pigment and an inorganic filler, and is characterized by also comprising the vegetable oil modified universal color paste grinding resin in claim 6.
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| CN202011554104.9A CN113480711B (en) | 2020-12-24 | 2020-12-24 | Vegetable oil modified universal color paste grinding resin and preparation method and application thereof |
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| CN202011554104.9A CN113480711B (en) | 2020-12-24 | 2020-12-24 | Vegetable oil modified universal color paste grinding resin and preparation method and application thereof |
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| CN114133822B (en) * | 2022-01-06 | 2023-09-29 | 衡水新光新材料科技有限公司 | Solvent-free isocyanate modified bio-based dispersion and preparation method thereof |
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| EP1756625B1 (en) * | 2004-04-21 | 2014-06-04 | Novartis AG | Curable colored inks for making colored silicone hydrogel lenses |
| KR20150089702A (en) * | 2014-01-28 | 2015-08-05 | 제일모직주식회사 | Novel compound, novel polymer, colorant including the same, positive photosensitive resin composition including the same, and color filter |
| CN108473662B (en) * | 2016-01-19 | 2021-12-21 | 陶氏环球技术有限责任公司 | One-component epoxy-modified polyurethane and/or polyurea adhesive having high elongation and excellent thermal stability and assembly process using the same |
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| CN104497778A (en) * | 2015-01-07 | 2015-04-08 | 刘玉 | Non-yellowing wear-resistant cathodic electrophoretic paint and preparation method thereof |
| CN109438656A (en) * | 2018-10-19 | 2019-03-08 | 中国林业科学研究院林产化学工业研究所 | A kind of anacardol based polyurethanes acrylic resin and preparation method and application |
| CN111154329A (en) * | 2019-12-23 | 2020-05-15 | 广东东方一哥新材料股份有限公司 | Waterborne gravure grindable resin and preparation method thereof |
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