阅读说明：本技术 一种涂料用羧基改性含氟聚芳醚树脂及其制备方法 (Carboxyl modified fluorine-containing polyarylether resin for coating and preparation method thereof ) 是由 陈栋阳 张文梦 于 2019-12-12 设计创作，主要内容包括：本发明公开了一种涂料用羧基改性含氟聚芳醚树脂及其制备方法。本发明先利用四烯丙基联苯二酚,2,2’-双(4’-羟基苯基)丙烷和十氟联苯,进行缩聚反应来制备含氟聚芳醚树脂,再通过3-巯基-1-丙酸的烯-巯点击化学反应,制得所述涂料用羧基改性含氟聚芳醚树脂,其侧链为羧基封端的5个亚甲基和1个硫醚键组成的长线性结构,所得羧基改性含氟聚芳醚树脂在极性非质子溶剂中具有良好的溶解性,可以用溶液浇铸在马口铁上制得涂层,所制得的涂层具有高硬度、高附着力、耐高温、耐腐蚀性和疏水性等特点,在电子封装,精密仪器,航空航天,耐高温涂料和先进复合材料等领域具有广泛的用途。(The invention discloses a carboxyl modified fluorine-containing polyarylether resin for paint and a preparation method thereof. The invention firstly uses tetraallyl biphenyl diphenol, 2,2 '-bis (4' -hydroxyphenyl) propane and decafluorobiphenyl to carry out polycondensation reaction to prepare fluorine-containing polyarylether resin, and then uses alkene-thiol click chemical reaction of 3-mercapto-1-propionic acid to prepare the carboxyl modified fluorine-containing polyarylether resin for the paint, the side chain is a long linear structure consisting of 5 methylene groups and 1 thioether bond which are terminated by carboxyl, the obtained carboxyl modified fluorine-containing polyarylether resin has good solubility in polar aprotic solvent, can be cast on the tin plate by solution to prepare a coating, the prepared coating has the characteristics of high hardness, high adhesive force, high temperature resistance, corrosion resistance, hydrophobicity and the like, the composite material has wide application in the fields of electronic packaging, precise instruments, aerospace, high-temperature resistant coatings, advanced composite materials and the like.)

1. The carboxyl modified fluorine-containing polyarylether resin for the coating is characterized by having the following structural formula:

wherein m =10 to 200 and n =0 to 200.

2. The carboxyl modified fluorine-containing polyarylether resin for the coating as claimed in claim 1, which comprises the following steps:

(1) dissolving tetraallyl biphenyl diphenol, 2,2 '-bis (4' -hydroxyphenyl) propane and decafluorobiphenyl in a polar aprotic solvent, taking cesium fluoride as a catalyst, carrying out polymerization reaction under the protection of inert gas argon, slowly pouring reactants into deionized water after the reaction is finished, filtering, collecting precipitates, dissolving in a dichloromethane solvent, separating out and purifying in methanol, filtering, collecting the precipitates, and then carrying out vacuum drying to obtain the fluorine-containing polyarylether resin;

(2) dissolving the fluorine-containing polyarylether resin obtained in the step (1) and 3-mercapto-1-propionic acid in N-methyl pyrrolidone, reacting under the protection of argon by using azobisisobutyronitrile and crown ether as an initiator and a catalyst respectively, cooling to room temperature, slowly pouring into deionized water for precipitation, filtering, washing with deionized water, and drying to obtain the carboxyl modified fluorine-containing polyarylether resin.

3. The production method according to claim 2, characterized in that the molar amount of decafluorobiphenyl of step (1) is the sum of the molar amounts of tetraallyl biphenyl diphenol and 2,2 '-bis (4' -hydroxyphenyl) propane; the molar amount of cesium fluoride used is 2-10 times the molar amount of decafluorobiphenyl.

4. The process according to claim 2, wherein the polymerization temperature in the step (1) is 0 to 80 ℃ and the polymerization time is 10 to 60 hours.

5. The method according to claim 2, wherein the vacuum drying temperature in steps (1) and (2) is 60 to 120 ℃ and the vacuum drying time is 10 to 40 hours.

6. The method according to claim 2, wherein the polar aprotic solvent in step (1) is any one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide.

7. The method according to claim 2, wherein the molar amount of the 3-mercapto-1-propionic acid in the step (2) is 1 to 10 times the molar amount of the double bond in the fluorine-containing polyarylether resin.

8. The method according to claim 2, wherein the molar amount of azobisisobutyronitrile in the step (2) is 0.5 to 2 times the molar amount of double bonds in the fluorine-containing polyarylether resin.

9. The method according to claim 2, wherein the reaction temperature in the step (2) is 60 to 150 ℃ and the reaction time is 10 to 100 hours.

Technical Field

The invention relates to a carboxyl modified fluorine-containing polyarylether resin for paint and a preparation method thereof, belonging to the field of solvent type functional resin.

Background

The polyarylether is an engineering plastic with excellent performance, has the advantages of excellent thermal property, high mechanical strength, good chemical stability and the like, and has wide application space in the fields of electronic and electric appliances, transportation, electronic communication, precision instruments and aerospace. The polyarylene ether polymer can be used in various forms such as a film, a fiber, and a coating. The coating has the performances of high temperature resistance, abrasion resistance, corrosion resistance and the like when used as a coating.

The fluorine-containing polyarylether is prepared by introducing fluorine atoms into polyarylether molecular chains so as to improve or increase the performance of the original polyarylether material. The introduction of fluorine atoms reduces the rigidity of the polyarylether structure and improves the thermal property of the polymer. Because the C-F bond energy is lower, the surface free energy is reduced, and the material has good hydrophobic and oleophobic characteristics. Allied Signal et al synthesized the first generation of fluorine-containing polyarylether materials through decafluorobiphenyl and bisphenol monomers, which had good hydrophobic dielectric properties and thermal properties, and Cassidy et al reported a series of fluorine-containing polyarylether materials prepared from decafluorobiphenyl all showed low moisture absorption rate and good thermal stability. In addition, the fluorine-containing polymer also has super-strong weather resistance, dielectric property and stain resistance, which shows that the fluorine-containing polyarylether has wide prospect in the fields of electronic packaging, precision instruments, aerospace, high temperature resistant coating, advanced composite materials and the like.

However, the fluorine-containing polyarylether polymer is applied to the metal surface as a coating, and the problem of low adhesion exists, so that the improvement of the adhesion of the coating is the problem to be solved at present. The current bonding mechanism mainly comprises: mechanical theory, adsorption theory, chemical bond formation theory, electrostatic theory, weak boundary layer theory. Therefore, a way for forming a chemical bond between the coating and the metal substrate to effectively improve the adhesion of the coating is currently found.

Disclosure of Invention

The invention aims to provide a carboxyl modified fluorine-containing polyarylether resin for paint and a preparation method thereof, wherein the carboxyl modified fluorine-containing polyarylether resin is obtained by carrying out polycondensation reaction on tetraallyl diphenol, 2,2 '-bis (4' -hydroxyphenyl) propane and decafluorobiphenyl, and then grafting carboxyl through an addition reaction of sulfydryl; the resin has soft long side chains blocked by carboxyl and a rigid fluorine-containing aromatic main chain, so that the resin has better adhesion, toughness and higher hardness.

In order to achieve the purpose, the invention adopts the following technical scheme:

a carboxyl modified fluorine-containing polyarylether resin for paint has the following structural formula:

，

wherein m =10 to 200 and n =0 to 200.

The preparation method of the carboxyl modified fluorine-containing polyarylether resin for the coating comprises the following steps:

(1) dissolving tetraallyl biphenyl diphenol, 2,2 '-bis (4' -hydroxyphenyl) propane and decafluorobiphenyl in a polar aprotic solvent, and polymerizing for 10-60 hours at 0-80 ℃ under the protection of inert gas argon by taking cesium fluoride as a catalyst; slowly pouring reactants into deionized water to separate out after the reaction is finished, dissolving the dried precipitate in a dichloromethane solvent, separating out and purifying the precipitate in methanol, filtering and collecting the precipitate, and then performing vacuum drying at the temperature of 60-120 ℃ for 10-40 hours to prepare the fluorine-containing polyarylether resin; the reaction process is as follows:

。

(2) dissolving the fluorine-containing polyarylether resin obtained in the step (1) and 3-mercapto-1-propionic acid in N-methylpyrrolidone, reacting at 60-150 ℃ for 10-100 hours under the protection of argon gas by using azobisisobutyronitrile as an initiator and crown ether as a catalyst, then cooling to room temperature, slowly pouring into deionized water for precipitation, washing with deionized water for 2-10 times after filtration, and performing vacuum drying at 60-120 ℃ for 10-40 hours to obtain carboxyl modified fluorine-containing polyarylether resin; the reaction process is as follows:

。

further, the molar amount of the decafluorobiphenyl in the step (1) is the sum of the molar amounts of the tetraallyl biphenyl diphenol and the 2,2 '-bis (4' -hydroxyphenyl) propane; the molar amount of cesium fluoride used is 2-10 times the molar amount of decafluorobiphenyl.

Further, the polar aprotic solvent in step (1) is any one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide.

Further, the molar weight of the azobisisobutyronitrile in the step (2) is 0.5 to 2 times of the molar weight of the double bonds in the fluorine-containing polyarylether resin.

The preparation method of the carboxyl modified fluorine-containing polyarylether resin can be used for coating.

Compared with the prior art, the invention has the following beneficial effects:

(1) the raw materials adopted by the invention are common chemical raw materials, the operation is convenient, the industrialization is easy, the double bond functionalization is easy to carry out due to the rigid conjugated benzene ring of the diphenol, and the product is easy to separate and purify.

(2) The invention has the advantages of low-temperature polymerization, simple operation, few side reactions and high molecular weight

(3) The invention adopts the decafluorobiphenyl as a polymerization monomer, and can obviously improve the hydrophobicity of the product.

(4) The double bond of the fluorine-containing polyarylether resin obtained by the invention is at the tail end of the side chain, and the reaction activity is high.

(5) According to the invention, through addition reaction of alkene sulfydryl, a long linear side chain which is end-capped by carboxyl and has 5 methylene groups and 1 thioether bond is obtained, and a hydrogen bond is formed between the carboxyl and a metal substrate, so that the adhesion and toughness of the product are obviously improved.

(6) The coating prepared by adopting the carboxyl modified fluorine-containing polyarylether resin has the characteristics of high hardness, high adhesive force, high temperature resistance, corrosion resistance, hydrophobicity and the like.

Drawings

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a fluorine-containing polyarylether resin obtained in example 1;

FIG. 2 is an infrared spectrum of a fluorine-containing polyarylether resin obtained in example 1;

FIG. 3 is the NMR spectrum of a carboxyl group-modified fluorine-containing polyarylether resin obtained in example 4;

FIG. 4 is an infrared spectrum of a carboxyl-modified fluorine-containing polyarylether resin obtained in example 4.

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.