CN107629194B - Heat-resistant phenol curing agent for epoxy powder coating and preparation method thereof - Google Patents
Heat-resistant phenol curing agent for epoxy powder coating and preparation method thereof Download PDFInfo
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- CN107629194B CN107629194B CN201710962292.0A CN201710962292A CN107629194B CN 107629194 B CN107629194 B CN 107629194B CN 201710962292 A CN201710962292 A CN 201710962292A CN 107629194 B CN107629194 B CN 107629194B
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Abstract
The invention discloses a heat-resistant phenol curing agent for epoxy powder coating and a preparation method thereof, wherein the heat-resistant phenol curing agent comprises the following steps: (1) preparation of intermediate product (a): bisphenol A type epoxy resin and amino silane are taken as basic raw materials, and are reacted for 3 to 4 hours at the temperature of 150 to 160 ℃ by using quaternary ammonium salt catalyst to prepare an intermediate product (A); (2) preparation of phenolic curing agent (B): and (3) reacting the prepared intermediate product (A) with bisphenol A at the temperature of 110-120 ℃ for 10-12 hours under the catalysis of metallic sodium to prepare the phenolic curing agent (B). The phenolic curing agent prepared by the invention can be used as a curing agent of epoxy powder coating for engineering pipelines, and the prepared coating has excellent toughness and strong heat resistance after being cured.
Description
Technical Field
The invention belongs to the field of heat-resistant phenol curing agents for epoxy powder coatings, and particularly relates to a phenol curing agent for an epoxy powder coating and a preparation method thereof.
Background
The phenolic curing agent is a novel curing agent for the anticorrosion powder coating developed after the phenolic resin cures the epoxy powder coating. The phenolic curing agent can be classified into phenolic resin type, bisphenol A-formaldehyde type, and ZY-1 high molecular phenol type.
The phenolic resin has poor reactivity, the curing temperature of the coating is high, and the cured coating is brittle and has no toughness, so that the phenolic resin is rarely used at present. The bisphenol A-formaldehyde type has higher phenolic hydroxyl group content, higher crosslinking density during curing, higher heat resistance and water boiling resistance of a cured coating film, and the defect that the coating film has poor flexibility and is not applied in certain occasions at present. The ZY-1 type high molecular phenol type is a linear bifunctional phenolic hydroxyl curing agent, and has the advantage of good flexibility of a cured coating film, but the heat resistance and the boiling resistance of the cured coating film are poor due to low phenolic hydroxyl content.
Therefore, it is desirable to develop a curing agent for epoxy powder coatings that combines high flexibility with heat resistance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a heat-resistant phenol curing agent for an epoxy powder coating, which has the following structural formula (I):
in the formula (I), R is represented by the formula (II), n1Is 3, 4 or 5, n2Is 1 or 2, n3Is 0 or 1;
the structural formula (II) is shown below:
in the formula (II), n4About 0.05 to about 0.5.
The invention also provides a preparation method of the heat-resistant phenol curing agent for the epoxy powder coating, which is synthesized by two steps of chemical reactions:
the first step, synthesis of intermediate product (A); and a second step of synthesizing the phenolic curing agent (B).
(1) Preparation of intermediate product (a):
using bisphenol A epoxy resin and amino silane as basic raw materials, and reacting for 3-4 hours at the temperature of 150-160 ℃ by using a quaternary ammonium salt catalyst to prepare an intermediate product (A);
wherein the low molecular weight epoxy resin can be epoxy resin E-55, E-51, E-44 and E-42, preferably E-51;
the amino silane can be 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane and 3-aminopropylmethyldiethoxysilane, preferably 3-aminopropyltriethoxysilane;
the quaternary ammonium salt catalyst comprises 1, 6-bis (dimethylamino) hexane, 1, 8-diazabicyclo [5.4.0] undecene-7 (DBU), benzyldimethylamine, tetramethylammonium chloride, tetraethylammonium chloride and benzyltrimethylammonium chloride, preferably benzyltrimethylammonium chloride;
the amount of the catalyst is 0.2-0.5 wt%, preferably 0.3 wt%;
the reaction molar ratio of the bisphenol A epoxy resin to the amino silane is 1:2-2.5, and preferably 1: 2.
(2) Preparation of phenolic curing agent (B):
reacting the prepared intermediate product (A) with bisphenol A at the temperature of 110-120 ℃ for 10-12 hours under the catalysis of metallic sodium to prepare a phenol curing agent (B);
wherein the molar ratio of the intermediate product (A) to the bisphenol A is 1:1.5-2.2, preferably 1: 2;
the amount of sodium metal is 0.5 to 0.8 wt.%, preferably 0.7 wt.%.
The invention has the following beneficial effects:
the heat-resistant phenol curing agent prepared by the invention can be used as a curing agent of an engineering pipeline epoxy powder coating, and the prepared coating has excellent toughness and super-strong heat resistance after being cured.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In a preferred embodiment of the present invention, E51 and 3-aminopropyltriethoxysilane are used as basic raw materials to prepare intermediate (A), and the intermediate (A) is reacted with bisphenol A to prepare the phenolic curing agent. The detailed implementation steps and reaction formula are as follows:
a three-necked round-bottomed flask equipped with a mechanical stirring device, a nitrogen blanket, a condenser and a temperature control device was prepared, and 1 mole of E-51 and 2 moles of 3-aminopropyltriethoxysilane were added to the flask, along with 1g of benzyltrimethylammonium chloride. Slowly heating to 140 ℃, and stopping the reaction after reacting for 4 hours to obtain an intermediate (A). The reaction formula is as follows:
(2) under the protection of nitrogen, adding 2 mol of dry bisphenol A into the product prepared in the step (1), raising the temperature to 120 ℃, slowly adding 2g of metal sodium, reacting for 12 hours, raising the temperature to 140 ℃, distilling under reduced pressure for 30 minutes, and stopping the reaction. The melt was poured out while hot and cooled to give a pale yellow solid (B). The reaction formula is as follows:
example 2
The phenolic curing agent synthesized by the invention and a reference substance ZY-1 are subjected to epoxy powder coating blending, then the blended mixture is mixed by a high-speed mixer, the mixed material is extruded and tabletted by a double-screw extruder, the extrusion temperature of the extruder is set to be 100 ℃, the tabletted material is crushed by a crusher and then screened by a 180-mesh screen to respectively prepare powder coating formulas 1 and 2, and the details are shown in Table 1. Respectively spraying the coating formulas 1 and 2 on a stainless steel plate by an electrostatic spraying method, baking for 15 minutes at 200 ℃ to finally obtain a dry film with the thickness of 80-85um, and respectively carrying out film coating performance tests on the formulas, wherein the specific table is shown in table 1;
the performance test method and evaluation criteria of the coating film are as follows:
appearance of the coating film: and (5) observing whether the surface of the sample plate is flat or not by naked eyes, and whether the sample plate has the defects of orange peel, pinholes and the like or not.
The impact resistance of the coating film is tested and evaluated according to GB/T1732-1993.
The heat resistance of the coating film is tested and evaluated according to GB/T1740-2007.
The operation process and evaluation of the heat resistance test: the sample plate was placed in an oven previously set at a temperature of (200. + -. 1). degree.C.and the surface of the coating film was inspected for 48 hours of continuous experiments. Level 1: the surface of the coating film is not changed; and 2, stage: the surface of the coating film is slightly discolored and slightly cracked; 3: the surface of the coating film is obviously discolored and has more cracks; and 4, the surface of the coating film is seriously discolored and the coating film falls off.
The flexibility performance test and evaluation of the coating film refer to GB/T1740-2007.
TABLE 1 formulation of powder coating for engineering pipes and results of performance tests
the petrochemical company Yueyang Ba Ling in Hunan province.
Shanxi Zhengyuan petrochemical engineering, Inc.
③ polyacrylate flatting agent produced by German Worlee company.
④, Ningbo Boke chemical Co.
fifthly, production of Guizhou Huajia fine mining company Limited.
sixthly, carbon black produced by Mitsubishi corporation of Japan.
seventhly, Jiangsu Zhengri chemical Co.
As can be seen from the results of the film property tests in Table 1, the phenolic curing agent prepared by the invention can be used to prepare a film with the flexibility same as that of the ZY-1 cured film, and the heat resistance of the film is obviously better than that of the film cured by ZY-1.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. A heat-resistant phenol curing agent for epoxy powder coating is characterized in that the curing agent is prepared by the following specific steps:
(1) preparation of intermediate product (a):
using bisphenol A type epoxy resin and amino silane as basic raw materials, and reacting for 3-4 hours at the temperature of 150-160 ℃ by using a quaternary ammonium salt catalyst to obtain an intermediate product (A), wherein the reaction molar ratio of the bisphenol A type epoxy resin to the amino silane is 1: 2-2.5;
(2) preparation of phenolic curing agent (B):
reacting the prepared intermediate product (A) with bisphenol A at the temperature of 110-120 ℃ for 10-12 hours under the catalysis of metallic sodium to prepare the phenolic curing agent (B), wherein the molar ratio of the intermediate product (A) to the bisphenol A is 1: 1.5-2.2.
2. A preparation method of a heat-resistant phenol curing agent for an epoxy powder coating is characterized by comprising the following steps:
(1) preparation of intermediate product (a):
using bisphenol A type epoxy resin and amino silane as basic raw materials, and reacting for 3-4 hours at the temperature of 150-160 ℃ by using a quaternary ammonium salt catalyst to obtain an intermediate product (A), wherein the reaction molar ratio of the bisphenol A type epoxy resin to the amino silane is 1: 2-2.5;
(2) preparation of phenolic curing agent (B):
reacting the prepared intermediate product (A) with bisphenol A at the temperature of 110-120 ℃ for 10-12 hours under the catalysis of metallic sodium to prepare the phenolic curing agent (B), wherein the molar ratio of the intermediate product (A) to the bisphenol A is 1: 1.5-2.2.
3. The method for preparing a heat-resistant phenol curing agent for an epoxy powder coating according to claim 2, wherein the bisphenol a type epoxy resin in the step (1) is one of epoxy resins E-55, E-51, E-44 and E-42.
4. The method for preparing a heat-resistant phenolic curing agent for epoxy powder coatings as claimed in claim 2, wherein the amino silane in step (1) is 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane or 3-aminopropylmethyldiethoxysilane.
5. The method of claim 2, wherein the quaternary ammonium salt catalyst in the step (1) is 1, 6-bis (dimethylamino) hexane, 1, 8-diazabicyclo [5.4.0] undecene-7 (DBU), benzyldimethylamine, tetramethylammonium chloride, tetraethylammonium chloride, or benzyltrimethylammonium chloride.
6. The method for preparing a heat-resistant phenol curing agent for epoxy powder paint as claimed in claim 2, wherein the amount of the catalyst used in the step (1) is 0.2wt% to 0.5 wt%.
7. The method for preparing a heat-resistant phenol curing agent for epoxy powder paints as claimed in claim 2, wherein the amount of the metallic sodium in the step (2) is 0.5 to 0.8 wt%.
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| CN112375210B (en) * | 2020-11-04 | 2022-11-25 | 黄山新佳精细材料有限公司 | Phenol curing agent for high-temperature-resistant and high-hardness epoxy resin powder coating and preparation method thereof |
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| JPH02227470A (en) * | 1989-02-28 | 1990-09-10 | Somar Corp | Epoxy resin powder coating composition |
| JP3708423B2 (en) * | 2000-10-20 | 2005-10-19 | 株式会社日鉱マテリアルズ | Phenolic curing agent for epoxy resin and epoxy resin composition using the same |
| CN106589319B (en) * | 2016-11-22 | 2018-10-12 | 天津翔盛新材料有限公司 | A kind of super flexible linear phenols curing agent of the special four-functional group of double antiseptic powder coating and synthetic method and application |
| CN106750187A (en) * | 2016-11-22 | 2017-05-31 | 天津翔盛新材料有限公司 | A kind of heavy corrosion protection epoxy powder high tenacity phenols curing agent and preparation method and application |
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