CN109369895B - Unsaturated polyester resin for anti-freezing coating and preparation method thereof - Google Patents
Unsaturated polyester resin for anti-freezing coating and preparation method thereof Download PDFInfo
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- CN109369895B CN109369895B CN201811075990.XA CN201811075990A CN109369895B CN 109369895 B CN109369895 B CN 109369895B CN 201811075990 A CN201811075990 A CN 201811075990A CN 109369895 B CN109369895 B CN 109369895B
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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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
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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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to the technical field of unsaturated polyester resin, in particular to unsaturated polyester resin for an anti-freezing coating and a preparation method thereof, wherein the raw materials for preparing the unsaturated polyester resin comprise the following components in parts by weight: 46-55 parts of diethylene glycol, 190 parts of 170-170 parts of propylene glycol, 42-50 parts of dipropylene glycol, 170 parts of phthalic anhydride 150, 80-100 parts of tetrahydrophthalic anhydride, 136 parts of maleic anhydride 120, 15-35 parts of hexamethylene diisocyanate, 0.03-0.06 part of hydroquinone, 0.02-0.03 part of copper naphthenate, 250 parts of 220-220 parts of styrene, 24-32 parts of trimethylolpropane diallyl ether and 18-22 parts of triallyl cyanurate. Aiming at the phenomena that the adhesion force of the coating of the existing furniture coating to the surface of furniture is poor in a low-temperature state and the performance of the coating is seriously reduced in a cold-hot alternating state, the invention provides the unsaturated polyester resin which is used for an anti-freezing coating and has higher stability.
Description
Technical Field
The invention relates to the technical field of unsaturated polyester resin, in particular to unsaturated polyester resin for an anti-freezing coating and a preparation method thereof.
Background
Unsaturated polyester paint is widely applied high-grade wood paint, which is a paint which is prepared by using unsaturated polyester resin prepared by condensation polymerization of dibasic acid (or anhydride) and dihydric alcohol as a main material, crosslinking and curing the unsaturated polyester resin by using a liquid vinyl monomer (such as 18-40 percent of styrene or a mixture of the styrene and methyl methacrylate) solution under the action of an initiator and an accelerator to form a body structure and finally forming a film. The paint has the advantages of hard film layer, wear resistance, water resistance, heat resistance, resistance to various chemicals such as dilute acid, alkali, solvent, oil and the like, good insulativity, plump and thick paint film appearance, higher gloss, light varnish color, high transparency, good gloss and color retention and strong decorativeness.
However, due to the great difference of climate in the north and south of China and four seasons, when the furniture coating products sold on the market meet the low temperature in the north, the surfaces of the furniture produced by the furniture coating products are easy to crack and warp. The coating enterprises, construction units and decoration families suffer from great economic loss and negative influence, and the solution of the product defect is one of the problems in the coating industry.
Disclosure of Invention
The invention aims to provide an unsaturated polyester resin which is used for an anti-freezing coating and has higher stability, aiming at the phenomena that the adhesion force of a coating to the surface of furniture is poor in a low-temperature state and the performance of the coating is seriously reduced in cold and hot alternation in the existing furniture coating.
In order to achieve the purpose, the technical solution of the invention is as follows: the unsaturated polyester resin for the anti-freezing coating comprises the following raw materials in parts by weight: 46-55 parts of diethylene glycol, 190 parts of 170-170 parts of propylene glycol, 42-50 parts of dipropylene glycol, 170 parts of phthalic anhydride 150, 80-100 parts of tetrahydrophthalic anhydride, 136 parts of maleic anhydride 120, 15-35 parts of hexamethylene diisocyanate, 0.03-0.06 part of hydroquinone, 0.02-0.03 part of copper naphthenate, 250 parts of 220-220 parts of styrene, 24-32 parts of trimethylolpropane diallyl ether and 18-22 parts of triallyl cyanurate.
A preparation method of unsaturated polyester resin for an anti-freezing coating comprises the following steps:
(1) putting diethylene glycol, propylene glycol, dipropylene glycol, phthalic anhydride, tetrahydrophthalic anhydride and maleic anhydride into a reaction kettle, starting stirring, heating to 200 +/-5 ℃ under the protection of nitrogen, keeping the temperature, continuously distilling water in the reaction process, performing reduced pressure distillation when reactant acid ester is reduced to 50mgKOH/g, removing water and unreacted organic micromolecules, and cooling to 40 ℃ when the acid value is less than 20KOH/g to obtain primary ester;
(2) adding hexamethylene diisocyanate into the primary ester obtained in the step (1), gradually heating to 60 ℃, and preserving heat for 2 hours to obtain an intermediate product;
(3) and (3) fully mixing and diluting the intermediate product obtained in the step (2) with hydroquinone, copper naphthenate, styrene, triallyl cyanurate and trimethylolpropane diallyl ether at the temperature of between 50 and 60 ℃ to obtain the unsaturated polyester resin for the anti-freezing coating.
The unsaturated polyester resin for the anti-freezing coating is used as a surface coating material of wooden furniture.
Preferably, the unsaturated polyester resin for the anti-freezing coating is prepared from the following raw materials in parts by weight: 52 parts of diethylene glycol, 180 parts of propylene glycol, 46 parts of dipropylene glycol, 160 parts of phthalic anhydride, 90 parts of tetrahydrophthalic anhydride, 128 parts of maleic anhydride, 20 parts of hexamethylene diisocyanate, 0.06 part of hydroquinone, 0.025 part of copper naphthenate, 240 parts of styrene, 30 parts of trimethylolpropane diallyl ether and 20 parts of triallyl cyanurate.
Preferably, the unsaturated polyester resin for the anti-freezing coating is prepared from the following raw materials in parts by weight: 47 parts of diethylene glycol, 175 parts of propylene glycol, 43 parts of dipropylene glycol, 156 parts of phthalic anhydride, 87 parts of tetrahydrophthalic anhydride, 126 parts of maleic anhydride, 33 parts of hexamethylene diisocyanate, 0.04 part of hydroquinone, 0.027 part of copper naphthenate, 235 parts of styrene, 32 parts of trimethylolpropane diallyl ether and 21 parts of triallyl cyanurate.
By adopting the technical scheme, the invention has the beneficial effects that: the invention reduces the expansion caused by the freezing of trace water under the low temperature state by reducing the trace water content of the product, and simultaneously adjusts the molecular group of the unsaturated polyester resin, so that the unsaturated polyester resin used for the coating can keep better mechanical property and chemical property under the environment temperature of minus 30 ℃ to minus 40 ℃, the produced furniture surface does not crack or warp, the use requirement of the north furniture coating is met, and the requirement of the north furniture coating is met.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The unsaturated polyester resin for the anti-freezing coating comprises the following raw materials in parts by weight: 52 parts of diethylene glycol, 180 parts of propylene glycol, 46 parts of dipropylene glycol, 160 parts of phthalic anhydride, 90 parts of tetrahydrophthalic anhydride, 128 parts of maleic anhydride, 20 parts of hexamethylene diisocyanate, 0.06 part of hydroquinone, 0.025 part of copper naphthenate, 240 parts of styrene, 30 parts of trimethylolpropane diallyl ether and 20 parts of triallyl cyanurate.
Example 2
The unsaturated polyester resin for the anti-freezing coating comprises the following raw materials in parts by weight: 47 parts of diethylene glycol, 175 parts of propylene glycol, 43 parts of dipropylene glycol, 156 parts of phthalic anhydride, 87 parts of tetrahydrophthalic anhydride, 126 parts of maleic anhydride, 33 parts of hexamethylene diisocyanate, 0.04 part of hydroquinone, 0.027 part of copper naphthenate, 235 parts of styrene, 32 parts of trimethylolpropane diallyl ether and 21 parts of triallyl cyanurate.
Example 3
The unsaturated polyester resin for the anti-freezing coating comprises the following raw materials in parts by weight: 55 parts of diethylene glycol, 190 parts of propylene glycol, 50 parts of dipropylene glycol, 170 parts of phthalic anhydride, 100 parts of tetrahydrophthalic anhydride, 136 parts of maleic anhydride, 35 parts of hexamethylene diisocyanate, 0.06 part of hydroquinone, 0.03 part of copper naphthenate, 250 parts of styrene, 30 parts of trimethylolpropane diallyl ether and 19 parts of triallyl cyanurate.
The unsaturated polyester resin for an anti-freeze coating according to the present invention was prepared according to the contents of the raw material formulation of examples 1-3 and the following method, comprising the steps of:
(1) putting diethylene glycol, propylene glycol, dipropylene glycol, phthalic anhydride, tetrahydrophthalic anhydride and maleic anhydride into a reaction kettle, starting stirring, heating to 200 +/-5 ℃ under the protection of nitrogen, keeping the temperature, continuously distilling water in the reaction process, performing reduced pressure distillation when reactant acid ester is reduced to 50mgKOH/g, removing water and unreacted organic micromolecules, and cooling to 40 ℃ when the acid value is less than 20 KOH/g;
(2) adding hexamethylene diisocyanate into the mixture in the step (1), gradually heating to 60 ℃, and keeping the temperature for 2 hours;
(3) and (3) fully mixing and diluting the polyester obtained in the step (2) with hydroquinone, copper naphthenate, styrene, triallyl cyanurate and trimethylolpropane diallyl ether at the temperature of between 50 and 60 ℃ to obtain unsaturated polyester resin.
The unsaturated polyester resin for the anti-freezing coating is used as a surface coating material of wooden furniture.
Exposure test: the unsaturated polyester prepared in the embodiment is solidified into a film under the action of an initiator and an accelerator, a wood furniture sample containing the coating is exposed at the temperature of 65 ℃, is gradually cooled to minus 50 ℃, is controlled to be repeatedly cycled between minus 50 ℃ and 65 ℃, is kept constant for 10min at the temperature limit points of minus 50 ℃ and 65 ℃, and is controlled within 20min in the changing process between minus 50 ℃ and 65 ℃. The test is continued until the coating cracks or the surface shows cracking (whichever occurs first). The results show that it is clear that the typical product (commercially available) failed in 100 cycles, but the unsaturated polyester resin antifreeze coating of the present invention shows no cracking or crazing even after 300 cycles.
The chemical and physical properties of the unsaturated polyester resin after film formation were measured and the results are shown in Table 1 (Table 1 shows the average values of properties of the products prepared according to the formulations of examples 1-3).
TABLE 1
| Appearance of the product | Viscosity Pa · s | Gel time min | Acid ester mgKOH/or g | Solid content The content of | Heat distortion temperature ℃ | Bending strength MPa | Tensile strength MPa | Elongation at break Percentage ratio% | Impact toughness KJ- M2 | |
| Testing method Method of | GB/T 8237 | GB/T 7193 | GB/T 7193 | GB/T 6743 | GB/T 7193 | GB/T 1634.1 | GB/T 9341 | GB/T 2567 | GB/T 2567 | GB/T 2567 |
| Numerical value | Light yellow transparent liquid Body | 0.72 | 35 | 42 | 68.4 | 70 | 115 | 75 | 2.2 | 8.23 |
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (4)
1. The unsaturated polyester resin for the anti-freezing coating is characterized by comprising the following raw materials in parts by weight: 46-55 parts of diethylene glycol, 190 parts of 170-170 parts of propylene glycol, 42-50 parts of dipropylene glycol, 170 parts of phthalic anhydride 150, 80-100 parts of tetrahydrophthalic anhydride, 136 parts of maleic anhydride 120, 15-35 parts of hexamethylene diisocyanate, 0.03-0.06 part of hydroquinone, 0.02-0.03 part of copper naphthenate, 250 parts of 220-220 parts of styrene, 24-32 parts of trimethylolpropane diallyl ether and 18-22 parts of triallyl cyanurate;
the preparation method comprises the following steps:
(1) putting diethylene glycol, propylene glycol, dipropylene glycol, phthalic anhydride, tetrahydrophthalic anhydride and maleic anhydride into a reaction kettle, starting stirring, heating to 200 +/-5 ℃ under the protection of nitrogen, keeping the temperature, continuously distilling water in the reaction process, performing reduced pressure distillation when reactant acid ester is reduced to 50mgKOH/g, removing water and unreacted organic micromolecules, and cooling to 40 ℃ when the acid value is less than 20KOH/g to obtain primary ester;
(2) adding hexamethylene diisocyanate into the primary ester obtained in the step (1), gradually heating to 60 ℃, and preserving heat for 2 hours to obtain an intermediate product;
(3) and (3) fully mixing and diluting the intermediate product obtained in the step (2) with hydroquinone, copper naphthenate, styrene, triallyl cyanurate and trimethylolpropane diallyl ether at the temperature of between 50 and 60 ℃ to obtain the unsaturated polyester resin for the anti-freezing coating.
2. The unsaturated polyester resin for an anti-freeze coating according to claim 1, wherein the raw materials for preparing the unsaturated polyester resin comprise the following components in parts by weight: 52 parts of diethylene glycol, 180 parts of propylene glycol, 46 parts of dipropylene glycol, 160 parts of phthalic anhydride, 90 parts of tetrahydrophthalic anhydride, 128 parts of maleic anhydride, 20 parts of hexamethylene diisocyanate, 0.06 part of hydroquinone, 0.025 part of copper naphthenate, 240 parts of styrene, 30 parts of trimethylolpropane diallyl ether and 20 parts of triallyl cyanurate.
3. The unsaturated polyester resin for an anti-freeze coating according to claim 1, wherein the raw materials for preparing the unsaturated polyester resin comprise the following components in parts by weight: 47 parts of diethylene glycol, 175 parts of propylene glycol, 43 parts of dipropylene glycol, 156 parts of phthalic anhydride, 87 parts of tetrahydrophthalic anhydride, 126 parts of maleic anhydride, 33 parts of hexamethylene diisocyanate, 0.04 part of hydroquinone, 0.027 part of copper naphthenate, 235 parts of styrene, 32 parts of trimethylolpropane diallyl ether and 21 parts of triallyl cyanurate.
4. Use of an unsaturated polyester resin for antifreeze coatings according to claim 1, characterized in that: the unsaturated polyester resin for the anti-freezing coating is used as a surface coating material of wooden furniture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811075990.XA CN109369895B (en) | 2018-09-15 | 2018-09-15 | Unsaturated polyester resin for anti-freezing coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811075990.XA CN109369895B (en) | 2018-09-15 | 2018-09-15 | Unsaturated polyester resin for anti-freezing coating and preparation method thereof |
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| CN109369895A CN109369895A (en) | 2019-02-22 |
| CN109369895B true CN109369895B (en) | 2021-02-09 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952343A (en) * | 2008-01-11 | 2011-01-19 | 晓温-威廉姆斯公司 | Metal coating composition |
| CN102212309A (en) * | 2011-04-14 | 2011-10-12 | 兰州理工大学 | Method for preparing unsaturated polyester polyurethane block copolymer solventless coating |
| CN102603992A (en) * | 2012-03-08 | 2012-07-25 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for pultrusion and preparation method for same |
| CN103012746A (en) * | 2012-12-31 | 2013-04-03 | 东莞英铭化工有限公司 | Method for synthesizing freeze-proof unsaturated coating polyester resin |
| CN103755938A (en) * | 2014-01-06 | 2014-04-30 | 南通天和树脂有限公司 | High-ductility unsaturated polyester resin under low-temperature environment |
| CN105906793A (en) * | 2016-06-25 | 2016-08-31 | 成都杰晟蜀邦新材料科技有限公司 | Water-based unsaturated polyester resin and preparation method thereof |
-
2018
- 2018-09-15 CN CN201811075990.XA patent/CN109369895B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952343A (en) * | 2008-01-11 | 2011-01-19 | 晓温-威廉姆斯公司 | Metal coating composition |
| CN102212309A (en) * | 2011-04-14 | 2011-10-12 | 兰州理工大学 | Method for preparing unsaturated polyester polyurethane block copolymer solventless coating |
| CN102603992A (en) * | 2012-03-08 | 2012-07-25 | 宜兴市兴合树脂有限公司 | Unsaturated polyester resin for pultrusion and preparation method for same |
| CN103012746A (en) * | 2012-12-31 | 2013-04-03 | 东莞英铭化工有限公司 | Method for synthesizing freeze-proof unsaturated coating polyester resin |
| CN103755938A (en) * | 2014-01-06 | 2014-04-30 | 南通天和树脂有限公司 | High-ductility unsaturated polyester resin under low-temperature environment |
| CN105906793A (en) * | 2016-06-25 | 2016-08-31 | 成都杰晟蜀邦新材料科技有限公司 | Water-based unsaturated polyester resin and preparation method thereof |
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