CN111154082A - One-step method for preparing quick-drying water-based alkyd resin and preparation method thereof - Google Patents
One-step method for preparing quick-drying water-based alkyd resin and preparation method thereof Download PDFInfo
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- CN111154082A CN111154082A CN201911391490.1A CN201911391490A CN111154082A CN 111154082 A CN111154082 A CN 111154082A CN 201911391490 A CN201911391490 A CN 201911391490A CN 111154082 A CN111154082 A CN 111154082A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
Abstract
The invention relates to a one-step method for preparing quick-drying water-based alkyd resin and a preparation method thereof, and is characterized in that the raw materials comprise the following components: 30-50 parts of linoleic acid, 5-15 parts of dehydrated castor oil, 1-5 parts of soybean oleic acid, 10-30 parts of pentaerythritol, 20-40 parts of trimethylolpropane, 40-70 parts of isophthalic acid, 1-15 parts of benzoic acid, 10-30 parts of dimethylolpropionic acid and 20-30 parts of hydrophilic solvent. The formula of the invention contains dimethylolmethacrylic acid, and utilizes the characteristics of excessive carboxylic acid and large molecular steric hindrance in the formula to form the alkyd resin with side chain carboxyl, and improves the hydrolysis resistance stability, chemical resistance and drying time of the waterborne alkyd resin. The preparation method is a one-step method, all the raw materials are put into polycondensation at one time, the operation is convenient, the process is simple and environment-friendly, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to a one-step quick-drying waterborne alkyd resin and a preparation method thereof, in particular to a quick-drying waterborne alkyd resin and a preparation method thereof.
Background
Since 1927 the advent of alkyd resins, alkyd resins have become one of the most important synthetic resins in the paint industry. Most of the traditional alkyd resins are solvent-based, contain a large amount of organic solvents, and in the construction process, the organic solvents are volatilized and diffused into the atmosphere along with the time, so that the alkyd resins have serious influence on human bodies and ecological environment.
The new regulation of VOC content restriction, which was implemented beginning at 1/2010, has a great impact on the traditional alkyd market, and from the viewpoint of sustainable development of the coating industry, solvent-based alkyd resins have failed to meet the requirements of the environment and the market. The development of modern alkyd resin requires that VOC is reduced to meet the requirement of environmental protection, the waterborne alkyd resin saves a large amount of organic solvent, saves resources, reduces environmental pollution, and the development of the waterborne alkyd resin is great tendency.
Although the water-based alkyd resin has a good development market, the water-based alkyd resin has the defects that ester bonds in a main chain are easy to hydrolyze, so that the coating film has the phenomena of water whitening, fading, falling and the like, and the chemical resistance and hydrolysis resistance stability of the coating film are poor; meanwhile, the water is used as a solvent, and the defects of slow drying speed and insufficient hardness exist.
Most of the traditional alcohol acid water-based chemicals are synthesized by TMA two-step method, i.e. oleic acid or oil is firstly esterified with dihydric alcohol, polyhydric alcohol, monoacid and dibasic acid, the acid value is reduced to a certain value, and then the temperature is reduced to react with TMA until the acid value d of the system reaches a target value. How to develop the water-based alkyd resin which has the advantages of high hardness and quick drying, and has good water resistance and chemical resistance, and the process is simple and convenient, which is a difficult problem in the existing water-based alkyd resin industry.
Disclosure of Invention
The invention aims to provide a quick-drying water-based alkyd resin which is quick to dry, high in hardness, and good in hydrolysis resistance and chemical resistance.
The invention also aims to provide a preparation method of the quick-drying water-based alkyd resin.
The quick-drying water-based alkyd resin prepared by the one-step method is characterized in that the quick-drying water-based alkyd resin comprises the following components in parts by weight: 30-50 parts of linoleic acid, 5-15 parts of dehydrated castor oil, 1-5 parts of soybean oleic acid, 10-30 parts of pentaerythritol, 20-40 parts of trimethylolpropane, 40-70 parts of isophthalic acid, 1-15 parts of benzoic acid, 10-30 parts of dimethylolpropionic acid and 20-30 parts of hydrophilic solvent.
The hydrophilic solvent is selected from: ethylene glycol butyl ether, propylene glycol methyl ether and sec-butyl alcohol quick-drying type or a mixture of more than two of the ethylene glycol butyl ether, the propylene glycol methyl ether and the sec-butyl alcohol quick-drying type.
The raw material of the quick-drying water-based alkyd resin also comprises 0.01-0.1 part by weight of catalyst.
The catalyst is one or more than two of organic tin, phosphorous acid and lead oxide phosphate.
A preparation method of the quick-drying water-based alkyd resin is characterized by comprising the following steps: the preparation method comprises the following steps:
a) weighing all raw materials in a container, wherein the raw materials comprise 30-50 parts by weight of linoleic acid, 5-15 parts by weight of dehydrated castor oil, 1-5 parts by weight of soybean oleic acid and 10-30 parts by weight of pentaerythritol; 20-40 parts of trimethylolpropane, 40-70 parts of phthalic anhydride, 1-15 parts of benzoic acid and 10-30 parts of dimethylolpropionic acid;
b) mixing the raw materials of a) in an inert atmosphere, heating the mixture to 230 ℃ at the speed of 0.1-0.3 ℃/min, wherein the heating time is 3-5 hours, keeping the temperature of the distillation column less than 102 ℃, and keeping the water yield at 75-90%; sampling and testing the acid value until the acid value is maintained at 30-60 mgKOH/g;
c) adding 20-30 parts by weight of hydrophilic solvent into the mixture obtained in the step b), uniformly stirring, cooling to 25-100 ℃, 50-100 ℃, 75-100 ℃, 85-100 ℃ or 90-100 ℃, and filtering to obtain the quick-drying water-based alkyd resin.
The method also comprises a step d) of adding the quick-drying water-based alkyd resin prepared in the step c) into triethylamine to neutralize until the pH value is 8-8.5, adding 0.01-0.1 part by weight of drier or other additives, and diluting and blending with water to form the spray paint.
The invention has the beneficial effects that:
1) the formula of the quick-drying water-based alkyd resin comprises dimethylol methacrylic acid, and the alkyd resin with side chain carboxyl is formed by utilizing the characteristics of excessive carboxylic acid and large molecular steric hindrance in the formula, so that the hydrolysis resistance stability, the chemical resistance and the drying time of the water-based alkyd resin are improved, and the quick-drying water-based alkyd resin can be used for woodware and metal paint.
2) The formula of the quick-drying water-based alkyd resin comprises benzoic acid and isophthalic acid, wherein the benzene ring structure is introduced, and hydrolysis of an ester bond of the alkyd resin is effectively inhibited through a steric hindrance effect.
3) The preparation method of the quick-drying water-based alkyd resin is a one-step method, all raw materials are put into polycondensation at one time, the operation is convenient, the process is simple and environment-friendly, and the preparation method is suitable for industrial production.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Not to be reiterated herein, but to the extent of space.
Detailed Description
The inventors of the present application have extensively and intensively studied and developed for the first time a quick-drying water-based alkyd polyester having quick drying, high hardness, excellent hydrolysis resistance and chemical resistance, including linoleic acid, dehydrated castor oil, soya oleic acid, pentaerythritol, trimethylolpropane, isophthalic acid, benzoic acid and dimethylolpropionic acid. The dimethylolpropionic acid is added in the polymerization reaction, and the characteristics of the molecular structure and the steric hindrance of the dimethylolpropionic acid are utilized, so that the side chain carboxyl can be added with amine to realize the water-based performance, and the hardness and the drying speed of the resin film are improved. In addition, the hydrolysis resistance and chemical resistance of the resin can be improved to a great extent by introducing a benzene ring structure into a molecular chain. On the basis of this, the present invention has been completed.
The quick-drying water-based alkyd resin comprises 30-50 parts by weight of linoleic acid, 5-15 parts by weight of dehydrated castor oil, 1-5 parts by weight of soybean oleic acid and 10-30 parts by weight of pentaerythritol; 20-40 parts of trimethylolpropane, 40-70 parts of phthalic anhydride, 1-15 parts of benzoic acid and 10-30 parts of dimethylolpropionic acid.
The quick-drying water-based alkyd resin comprises vegetable oil, the dependence on petroleum products is relatively reduced due to the introduction of renewable resource vegetable oil, and the mixed vegetable oleic acid comprises linoleic acid, dehydrated castor oil and soybean oleic acid, wherein the total weight of the linoleic acid, the dehydrated castor oil and the soybean oleic acid accounts for 36-51% of the total weight of the resin composition, namely the oil length is 36-51%.
The invention utilizes the characteristics of molecular structure and steric hindrance of dimethylolpropionic acid, endows side chain carboxyl with the capability of adding amine to realize aquosity, and improves the hardness and drying speed of resin film formation. The waterborne alkyd resin comprises 10-30 parts of dimethylolpropionic acid, and preferably 20-30 parts in order to improve the drying rate and the waterborne property of a coating film.
The hydrolysis resistance and chemical resistance of the resin can be greatly improved by introducing a benzene ring structure into a molecular chain. The quick-drying water-based alkyd resin contains a benzene ring structure brought by benzoic acid and isophthalic acid, and hydrolysis of an ester bond of the alkyd resin is effectively inhibited through a steric hindrance effect. The matching of the polybasic acid and the polyhydric alcohol can generate a mutually cross-linked network structure, so that the bond energy of group linkage in a resin molecular chain is improved, and the water resistance and the chemical resistance of the resin are further improved.
The quick-drying water-based alkyd resin also comprises 20-30 parts by weight of a hydrophilic solvent, wherein the hydrophilic solvent is selected from the following components: one or a mixture of more than two of ethylene glycol butyl ether, propylene glycol methyl ether and sec-butyl alcohol.
The quick-drying water-based alkyd resin also comprises 0.01-0.1 part by weight of catalyst, wherein the catalyst is one or more than two of organic tin, phosphorous acid, phosphoric acid and lead oxide, and the organic tin is preferable, so that the activation energy of the reaction can be reduced, the forward progress of the reaction can be promoted, and the reaction can be promoted at a lower temperature in the esterification process.
Example 1
a: weighing all raw materials in a container, wherein the raw materials comprise 42 parts by weight of linoleic acid, 16 parts by weight of dehydrated castor oil, 2 parts by weight of soybean oleic acid and 16 parts by weight of pentaerythritol; 33 parts by weight of trimethylolpropane, 58 parts by weight of isophthalic acid, 13.5 parts by weight of benzoic acid and 18 parts by weight of dimethylolpropionic acid, 0.02 part by weight of organotin;
b: mixing the above raw materials under inert atmosphere, and heating the mixture at 0.1-0.3 deg.C/min
210 ℃ and 230 ℃, the heating time is 3-5 hours, the temperature of the distillation column is kept less than 102 ℃, and the water yield is kept at 75-90%; and are
The acid value was sampled and tested until the acid value was maintained at 45 mgKOH/g. (ii) a
c: and c, adding 65 parts by weight of propylene glycol methyl ether into the mixture obtained in the step b, uniformly stirring, cooling to 50-70 ℃, and filtering to obtain the quick-drying water-based alkyd resin.
Example 2
a: weighing all raw materials in a container, wherein the raw materials comprise 45 parts by weight of linoleic acid, 18 parts by weight of dehydrated castor oil, 3 parts by weight of soybean oleic acid and 15 parts by weight of pentaerythritol; 32 parts by weight of trimethylolpropane, 59 parts by weight of isophthalic acid, 13 parts by weight of benzoic acid and 20 parts by weight of dimethylolpropionic acid, 0.02 part by weight of organotin;
b: mixing the above raw materials under inert atmosphere, and heating the mixture at 0.1-0.3 deg.C/min
210 ℃ and 230 ℃, the heating time is 3-5 hours, the temperature of the distillation column is kept less than 102 ℃, and the water yield is kept at 75-90%; and are
Sampling and testing the acid value until the acid value is maintained at 30-60 mgKOH/g. (ii) a
c: and c, adding 65 parts by weight of propylene glycol methyl ether into the mixture obtained in the step b, uniformly stirring, cooling to 50-70 ℃, and filtering to obtain the quick-drying water-based alkyd resin.
The waterborne alkyd resin prepared in the above embodiment is added with triethylamine to neutralize until the pH value is 8-8.5, and then added with a drier and other additives, diluted with water to adjust viscosity, and sprayed to test the paint film performance. The formulation is shown in table 1:
TABLE 1 paint film formulation with addition of waterborne alkyd resin
The properties of the coating film formed from the coating film composition prepared as described above were measured, and the results are shown in table 2.
TABLE 2 coating film Performance Table
As shown in Table 2, when the waterborne alkyd resin prepared by the method is added into paint, the waterborne alkyd resin has good drying property and good water resistance and chemical reagent resistance, can be used for wood and metal paint, is beneficial to product application and popularization, and has a remarkable promotion effect on the improvement of industrial technology.
Claims (6)
1. The quick-drying water-based alkyd resin prepared by the one-step method is characterized in that the quick-drying water-based alkyd resin comprises the following raw materials: 30-50 parts of linoleic acid, 5-15 parts of dehydrated castor oil, 1-5 parts of soybean oleic acid, 10-30 parts of pentaerythritol, 20-40 parts of trimethylolpropane, 40-70 parts of isophthalic acid, 1-15 parts of benzoic acid, 10-30 parts of dimethylolpropionic acid and 20-30 parts of hydrophilic solvent.
2. A quick-drying waterborne alkyd resin according to claim 2, wherein said hydrophilic solvent is selected from the group consisting of: ethylene glycol butyl ether, propylene glycol methyl ether and sec-butyl alcohol quick-drying type or a mixture of more than two of the ethylene glycol butyl ether, the propylene glycol methyl ether and the sec-butyl alcohol quick-drying type.
3. The quick-drying waterborne alkyd resin of claim 1, wherein the raw materials of the quick-drying waterborne alkyd resin further comprise 0.01 to 0.1 parts by weight of a catalyst.
4. The quick-drying waterborne alkyd resin of claim 3, wherein the catalyst is one or more of organotin, phosphorous acid, lead oxide phosphate.
5. A process for preparing a quick-drying waterborne alkyd resin of any of claims 1 to 4, wherein: the preparation method comprises the following steps:
a) weighing all raw materials in a container, wherein the raw materials comprise 30-50 parts by weight of linoleic acid, 5-15 parts by weight of dehydrated castor oil, 1-5 parts by weight of soybean oleic acid and 10-30 parts by weight of pentaerythritol; 20-40 parts of trimethylolpropane, 40-70 parts of phthalic anhydride, 1-15 parts of benzoic acid and 10-30 parts of dimethylolpropionic acid;
b) mixing the raw materials of a) in an inert atmosphere, heating the mixture to 230 ℃ at the speed of 0.1-0.3 ℃/min, wherein the heating time is 3-5 hours, keeping the temperature of the distillation column less than 102 ℃, and keeping the water yield at 75-90%; sampling and testing the acid value until the acid value is maintained at 30-60 mgKOH/g;
c) adding 20-30 parts by weight of hydrophilic solvent into the mixture obtained in the step b), uniformly stirring, cooling to 25-100 ℃, 50-100 ℃, 75-100 ℃, 85-100 ℃ or 90-100 ℃, and filtering to obtain the quick-drying water-based alkyd resin.
6. The method according to claim 5, further comprising a step d) of neutralizing the quick-drying water-based alkyd resin obtained in step c) with triethylamine until the pH is 8-8.5, adding 0.01-0.1 parts by weight of a drier or other additives, and diluting with water to adjust viscosity to form a spray paint.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3268483A (en) * | 1960-07-25 | 1966-08-23 | Shell Oil Co | Two-step process for preparing alkyd resins having improved physical properties |
| US4978741A (en) * | 1988-01-29 | 1990-12-18 | Questra Chemicals Corp. | Method for preparing essentially haze-free isophthalic acid- and polymethylolalkanoic acid-containing resins |
| CN101875719A (en) * | 2010-07-14 | 2010-11-03 | 江苏三木化工股份有限公司 | Alkyd and preparation method |
| CN105504246A (en) * | 2015-12-26 | 2016-04-20 | 北京金之桥科技发展有限公司 | Epoxy-modified waterborne alkyd resin and preparation method thereof |
| CN110092895A (en) * | 2018-01-31 | 2019-08-06 | 长兴化学工业(中国)有限公司 | A kind of self-drying aqueous alkyd resin and preparation method thereof |
| CN110330596A (en) * | 2019-06-21 | 2019-10-15 | 佛山市顺德区蓝德堡实业有限公司 | A kind of quick-dry type aqueous alkide resin and preparation method thereof |
-
2019
- 2019-12-30 CN CN201911391490.1A patent/CN111154082A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3268483A (en) * | 1960-07-25 | 1966-08-23 | Shell Oil Co | Two-step process for preparing alkyd resins having improved physical properties |
| US4978741A (en) * | 1988-01-29 | 1990-12-18 | Questra Chemicals Corp. | Method for preparing essentially haze-free isophthalic acid- and polymethylolalkanoic acid-containing resins |
| CN101875719A (en) * | 2010-07-14 | 2010-11-03 | 江苏三木化工股份有限公司 | Alkyd and preparation method |
| CN105504246A (en) * | 2015-12-26 | 2016-04-20 | 北京金之桥科技发展有限公司 | Epoxy-modified waterborne alkyd resin and preparation method thereof |
| CN110092895A (en) * | 2018-01-31 | 2019-08-06 | 长兴化学工业(中国)有限公司 | A kind of self-drying aqueous alkyd resin and preparation method thereof |
| CN110330596A (en) * | 2019-06-21 | 2019-10-15 | 佛山市顺德区蓝德堡实业有限公司 | A kind of quick-dry type aqueous alkide resin and preparation method thereof |
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Application publication date: 20200515 |