CN110818887A - Preparation method of odorless scratch-resistant modified alkyd resin - Google Patents
Preparation method of odorless scratch-resistant modified alkyd resin Download PDFInfo
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- CN110818887A CN110818887A CN201911244825.7A CN201911244825A CN110818887A CN 110818887 A CN110818887 A CN 110818887A CN 201911244825 A CN201911244825 A CN 201911244825A CN 110818887 A CN110818887 A CN 110818887A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from 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
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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
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention relates to a preparation method of odorless scratch-resistant modified alkyd resin, wherein the modified alkyd resin is fluorine-containing polyimide modified alkyd resin, and a fluorine-containing polyimide chain segment improves the high-temperature resistance, hardness, scratch resistance, flame retardance and hydrophobicity of the resin, so that the alkyd resin has the characteristics of high temperature resistance, high hardness, flame retardance and water resistance, and can be widely applied to surface coating of woodware, plastics and metal products.
Description
Technical Field
The invention relates to an alkyd resin, in particular to a preparation method of a odorless scratch-resistant modified alkyd resin, and belongs to the technical field of synthesis.
Technical Field
The alkyd resin is a synthetic resin which is widely applied in paint, is one of the most widely applied synthetic resins in China at present, has moderate price, simple construction, rich raw material sources and low acid value, can be dissolved in various organic solvents, is suitable for surface coating of all wood and metal, has good wetting and dispersing properties on pigments, fillers and the like, has bright paint film, strong adhesive force, good durability, excellent flexibility, luster and fullness, can be mutually dissolved with various resins, and can be modified to prepare alkyd resin paints with different properties.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of an odorless scratch-resistant modified alkyd resin.
The invention provides the following technical scheme, and a preparation method of a odorless scratch-resistant modified alkyd resin comprises the following steps in parts by weight:
(1) synthesis of isocyanate-terminated polyimide oligomer: under the condition of introducing nitrogen, adding 40-50 parts of polyisocyanate, 40-50 parts of fluorine-containing dianhydride and 8-14 parts of solvent into a reaction kettle, stirring and heating to 70-85 ℃, stirring and reacting for 3-4h, and continuously removing water generated in the reaction through a water separation device in the reaction process; then adding 2-10 parts of dimethyl sulfoxide and 0.05-0.2 part of accelerator, heating to 120-;
(2) preparing modified alkyd resin: adding 30-60 parts of lauric acid, 40-80 parts of organic acid, 30-60 parts of polyol, 12-25 parts of isocyanate-terminated polyimide oligomer and 8-15 parts of solvent into a synthesis kettle in sequence according to the formula amount, and introducing N2And heating to 120 ℃, then heating to 180 ℃ at a heating rate of 10 ℃/h, preserving heat and refluxing for 1.5h, heating to 190-210 ℃ at 10 ℃/h, preserving heat for 2-5h, cooling to below 100 ℃, slowly adding 8-20 parts of solvent, diluting, stirring for 0.5h, and filtering to obtain the odorless scratch-resistant modified alkyd resin.
The polyisocyanate is at least one of TDI, HDI, MDI, IPDI, HMDI, H12MDI and TMDI.
The fluorine-containing dianhydride is at least one of 6,6 '-bis-trifluoromethyl-2, 3,3',4 '-biphenyl tetracarboxylic dianhydride, 4' -hexafluoroisopropyl phthalic anhydride and triptycene-4, 5-bis-trifluoromethyl-2, 3,6, 7-tetracarboxylic dianhydride.
The solvent is at least one of dimethyl cyclohexane, hydrogenation environment-friendly dearomatization solvent D40, normal octane, ethyl acetate and butyl acetate.
The accelerant is at least one of alkali metal carboxylate, organic metal compound, phosphorus-containing compound and amine, preferably dibutyltin dilaurate, lithium acetate, tri-n-butylphosphonium, stannous octoate, tin naphthenate, lead naphthenate, cobalt naphthenate, dibutyltin maleate, dibutyltin diacetate, triethylamine and benzyl glycidyl ether.
The polyhydric alcohol is at least one of pentaerythritol, glycerol, trimethylolpropane, trimethylolethane, ethylene glycol, propylene glycol, neopentyl glycol and diethylene glycol.
The organic acid is one or the combination of terephthalic acid, isophthalic acid, tert-butyl benzoic acid, adipic acid, sebacic acid and derivatives.
Compared with the prior art, the invention has the following advantages: the alkyd resin is modified by the fluorine-containing polyimide, and the high-temperature resistance, hardness, scratch resistance, flame retardance and hydrophobicity of the resin are improved by the fluorine-containing polyimide chain segment, so that the alkyd resin has the characteristics of high temperature resistance, high hardness, flame retardance and water resistance.
Detailed Description
The preparation of a neat, odor resistant, scratch resistant modified alkyd resin of the present invention is further described below with reference to the examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
A preparation method of odorless scratch-resistant modified alkyd resin comprises the following steps of:
(1) synthesis of isocyanate-terminated polyimide oligomer: adding 50 parts of HDI, 50 parts of triptycene-4, 5-bis (trifluoromethyl) -2,3,6, 7-tetracarboxylic dianhydride and 14 parts of n-octane into a reaction kettle under the condition of introducing nitrogen, stirring and heating to 85 ℃, stirring for reaction for 4 hours, and continuously removing water generated in the reaction through a water separation device in the reaction process; then adding 10 parts of dimethyl sulfoxide and 0.2 part of dibutyltin dilaurate, heating to 150 ℃, carrying out heat preservation and polycondensation for 1h, and carrying out reduced pressure distillation to remove impurities to obtain an isocyanate-terminated polyimide oligomer;
(2) preparing modified alkyd resin: adding 45 parts of lauric acid, 55 parts of terephthalic acid, 40 parts of trimethylolpropane, 20 parts of isocyanate-terminated polyimide oligomer and 10 parts of N-octane into a synthesis kettle in sequence according to the formula amount2And heating to 120 ℃, then heating to 180 ℃ at the heating rate of 10 ℃/h, preserving heat, refluxing for 1.5h, heating to 200 ℃ at the heating rate of 10 ℃/h, preserving heat for 4h, cooling to below 100 ℃, slowly adding 8 parts of n-octane, diluting, stirring for 0.5h, and filtering to obtain the odorless scratch-resistant modified alkyd resin.
Example 2
A preparation method of odorless scratch-resistant modified alkyd resin comprises the following steps of:
(1) synthesis of isocyanate-terminated polyimide oligomer: adding 44 parts of TDI, 48 parts of 4, 4' -hexafluoroisopropyl phthalic anhydride and 12 parts of hydrogenation environment-friendly dearomatization solvent D40 into a reaction kettle under the condition of introducing nitrogen, stirring and heating to 80 ℃, stirring for reaction for 3.5 hours, and continuously removing water generated in the reaction through a water separation device in the reaction process; then adding 7 parts of dimethyl sulfoxide and 0.1 part of stannous octoate, heating to 140 ℃, carrying out heat preservation and polycondensation for 2 hours, and carrying out reduced pressure distillation to remove impurities to obtain an isocyanate-terminated polyimide oligomer;
(2) preparing modified alkyd resin: adding 60 parts of lauric acid, 40 parts of adipic acid, 60 parts of neopentyl glycol, 25 parts of isocyanate-terminated polyimide oligomer and 8 parts of hydrogenation environment-friendly dearomatization solvent D40 into a synthesis kettle according to the formula amount in sequence, and introducing N2And heating to 120 ℃, then heating to 180 ℃ at a heating rate of 10 ℃/h, preserving heat, refluxing for 1.5h, heating to 190 ℃ at 10 ℃/h, preserving heat for 5h, cooling to below 100 ℃, slowly adding 4016 parts of the hydrogenation environment-friendly dearomatization solvent, diluting, stirring for 0.5h, and filtering to obtain the odorless scratch-resistant modified alkyd resin.
Example 3
A preparation method of odorless scratch-resistant modified alkyd resin comprises the following steps of:
(1) synthesis of isocyanate-terminated polyimide oligomer: adding 40 parts of TMDI, 40 parts of 6,6 ' -bis-trifluoromethyl-2, 3,3',4' -biphenyl tetracarboxylic dianhydride and 8 parts of ethyl acetate into a reaction kettle under the condition of introducing nitrogen, stirring and heating to 70 ℃, stirring for reacting for 3 hours, and continuously removing water generated in the reaction through a water separation device in the reaction process; then adding 2 parts of dimethyl sulfoxide and 0.05 part of triethylamine, heating to 120 ℃, carrying out heat preservation and polycondensation for 4 hours, and carrying out reduced pressure distillation to remove impurities to obtain an isocyanate-terminated polyimide oligomer;
(2) preparing modified alkyd resin: adding 30 parts of lauric acid, 80 parts of sebacic acid, 30 parts of pentaerythritol, 12 parts of isocyanate-terminated polyimide oligomer and 15 parts of ethyl acetate into a synthesis kettle in the formula amount in sequence, and introducing N2And (3) heating to 120 ℃, then heating to 180 ℃ at the heating rate of 10 ℃/h, preserving heat, refluxing for 1.5h, heating to 210 ℃ at the heating rate of 10 ℃/h, preserving heat for 2h, cooling to below 100 ℃, slowly adding 20 parts of ethyl acetate, diluting, stirring for 0.5h, and filtering to obtain the odorless scratch-resistant modified alkyd resin.
The odor-free scratch-resistant modified alkyd resins prepared in examples 1-3 have the following relevant specifications:
| appearance of the product | Viscosity (mPa. s) | Acid value (mgKOH/g) | Hydroxyl value (/ mgKOH/g) | |
| Example 1 | Water white | 6500 | <12 | 121 |
| Example 2 | Water white | 5000 | <12 | 150 |
| Example 3 | Water white | 4500 | <12 | 180 |
The neat, scratch resistant modified alkyd resins prepared in examples 1-3 were combined with a commercially available TDI trimer curing agent according to the formula-OH: -NCO =1:1, sprayed on woodware, paint film thickness 100 μm, test paint film properties as follows:
| impact resistance/50 cm | Bending test/mm | Hardness of | Oxygen index of paint film | Contact angle of water with coating film | |
| Example 1 | Coating film is normal | 1 | 3H | 28.0 | 119 degree |
| Example 2 | Coating film is normal | 1 | 3H | 27.5 | 125 degree |
| Example 3 | Coating film is normal | 1 | 3H | 26.0 | 116 degree |
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. The preparation method of the odorless scratch-resistant modified alkyd resin is characterized by comprising the following steps of:
(1) synthesis of isocyanate-terminated polyimide oligomer: under the condition of introducing nitrogen, adding 40-50 parts of polyisocyanate, 40-50 parts of fluorine-containing dianhydride and 8-14 parts of solvent into a reaction kettle, stirring and heating to 70-85 ℃, stirring and reacting for 3-4h, and continuously removing water generated in the reaction through a water separation device in the reaction process; then adding 2-10 parts of dimethyl sulfoxide and 0.05-0.2 part of accelerator, heating to 120-;
(2) preparing modified alkyd resin: adding 30-60 parts of lauric acid, 40-80 parts of organic acid, 30-60 parts of polyol, 12-25 parts of isocyanate-terminated polyimide oligomer and 8-15 parts of solvent into a synthesis kettle in sequence according to the formula amount, and introducing N2And heating to 120 ℃, then heating to 180 ℃ at a heating rate of 10 ℃/h, preserving heat and refluxing for 1.5h, heating to 190-210 ℃ at 10 ℃/h, preserving heat for 2-5h, cooling to below 100 ℃, slowly adding 8-20 parts of solvent, diluting, stirring for 0.5h, and filtering to obtain the odorless scratch-resistant modified alkyd resin.
2. The method of preparing the odorless scratch resistant modified alkyd resin of claim 1, wherein the method comprises the steps of: the polyisocyanate is at least one of TDI, HDI, MDI, IPDI, HMDI, H12MDI and TMDI.
3. The method of preparing the odorless scratch resistant modified alkyd resin of claim 1, wherein the method comprises the steps of: the fluorine-containing dianhydride is at least one of 6,6 '-bis-trifluoromethyl-2, 3,3',4 '-biphenyl tetracarboxylic dianhydride, 4' -hexafluoroisopropyl phthalic anhydride and triptycene-4, 5-bis-trifluoromethyl-2, 3,6, 7-tetracarboxylic dianhydride.
4. The method of preparing the odorless scratch resistant modified alkyd resin of claim 1, wherein the method comprises the steps of: the solvent is at least one of dimethyl cyclohexane, hydrogenation environment-friendly dearomatization solvent D40, normal octane, ethyl acetate and butyl acetate.
5. The method of preparing the odorless scratch resistant modified alkyd resin of claim 1, wherein the method comprises the steps of: the accelerant is at least one of alkali metal carboxylate, organic metal compound, phosphorus-containing compound and amine, preferably dibutyltin dilaurate, lithium acetate, tri-n-butylphosphonium, stannous octoate, tin naphthenate, lead naphthenate, cobalt naphthenate, dibutyltin maleate, dibutyltin diacetate, triethylamine and benzyl glycidyl ether.
6. The method of preparing the odorless scratch resistant modified alkyd resin of claim 1, wherein the method comprises the steps of: the polyhydric alcohol is at least one of pentaerythritol, glycerol, trimethylolpropane, trimethylolethane, ethylene glycol, propylene glycol, neopentyl glycol and diethylene glycol.
7. The method of preparing the odorless scratch resistant modified alkyd resin of claim 1, wherein the method comprises the steps of: the organic acid is one or the combination of terephthalic acid, isophthalic acid, tert-butyl benzoic acid, adipic acid, sebacic acid and derivatives.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911244825.7A CN110818887A (en) | 2019-12-06 | 2019-12-06 | Preparation method of odorless scratch-resistant modified alkyd resin |
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| CN201911244825.7A CN110818887A (en) | 2019-12-06 | 2019-12-06 | Preparation method of odorless scratch-resistant modified alkyd resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044889A (en) * | 2021-12-27 | 2022-02-15 | 合众（佛山）化工有限公司 | High-wear-resistance scratch-resistant modified alkyd resin and preparation method thereof |
| CN114213641A (en) * | 2021-12-20 | 2022-03-22 | 广东鸿昌化工有限公司 | Flame-retardant modified alkyd resin and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578310A (en) * | 2006-11-03 | 2009-11-11 | 拜尔材料科学股份公司 | Solutions of end-capped polyimides or polyamideimides |
| CN102220085A (en) * | 2011-05-09 | 2011-10-19 | 东华大学 | Polyimide coating with high-temperature resistance and preparation method thereof |
| CN103965453A (en) * | 2013-01-30 | 2014-08-06 | 合众（佛山）化工有限公司 | Preparation method of benzene-free nearly smell-less scratch-resistant alkyd resin |
| CN109679495A (en) * | 2018-12-14 | 2019-04-26 | 江南大学 | A kind of preparation method of the modified PDMS silicone resin of fire resistant polyimide |
-
2019
- 2019-12-06 CN CN201911244825.7A patent/CN110818887A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578310A (en) * | 2006-11-03 | 2009-11-11 | 拜尔材料科学股份公司 | Solutions of end-capped polyimides or polyamideimides |
| CN102220085A (en) * | 2011-05-09 | 2011-10-19 | 东华大学 | Polyimide coating with high-temperature resistance and preparation method thereof |
| CN103965453A (en) * | 2013-01-30 | 2014-08-06 | 合众（佛山）化工有限公司 | Preparation method of benzene-free nearly smell-less scratch-resistant alkyd resin |
| CN109679495A (en) * | 2018-12-14 | 2019-04-26 | 江南大学 | A kind of preparation method of the modified PDMS silicone resin of fire resistant polyimide |
Non-Patent Citations (1)
| Title |
|---|
| 李楠: "含氟聚酰亚胺的研究及其在涂料中的应用", 《中国涂料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213641A (en) * | 2021-12-20 | 2022-03-22 | 广东鸿昌化工有限公司 | Flame-retardant modified alkyd resin and preparation method thereof |
| CN114044889A (en) * | 2021-12-27 | 2022-02-15 | 合众（佛山）化工有限公司 | High-wear-resistance scratch-resistant modified alkyd resin and preparation method thereof |
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