CN113861428B - Hydrogenated rosin modified fluorocarbon resin and preparation method thereof - Google Patents

Abstract

The invention discloses a hydrogenated rosin-modified fluorocarbon resin and a preparation method thereof, comprising: dissolving powdered hydrogenated rosin in a solvent to prepare a hydrogenated rosin solution with a mass concentration of 5%-85%; In the rosin solution under the condition of 0～60℃, slowly add the acylation reagent dropwise, and after the reflux reaction, separate and remove the excess acylation to obtain the acid chloride hydrogenated rosin solution; prepare the polyhydroxy fluorocarbon resin solution with the mass concentration of 10～80% , and then slowly dropwise added the acid chloride hydrogenated rosin solution to finish the reaction, washed with deionized water until neutral, distilled and purified to obtain hydrogenated rosin modified fluorocarbon resin. From the perspective of molecular structure design, the present invention uses hydrogenated rosin as a fluorocarbon resin modified material to synthesize a new type of modified fluorocarbon resin, and the introduction of hydrogenated rosin side groups further improves the hydrophobicity, antifouling and self-cleaning properties of the fluorocarbon resin , corrosion resistance and mechanical properties, further expanding the application of fluorocarbon coatings in the field of marine heavy corrosion protection.

Description

A kind of hydrogenated rosin modified fluorocarbon resin and preparation method thereof

technical field

The invention discloses and relates to the technical field of modified fluorocarbon resins, in particular to a hydrogenated rosin-modified fluorocarbon resin and a preparation method thereof.

Background technique

Fluorocarbon anti-corrosion coating is a kind of anti-corrosion coating with fluorocarbon resin as the main film-forming material. Because the carbon chain structure in the molecular structure of fluorocarbon resin is tightly wrapped by fluorine atoms, forming a helical three-dimensional arrangement conformation, which ensures the integrity and tightness of the structure to the greatest extent, and prevents many liquids and gases from affecting the paint film. Therefore, fluorocarbon anti-corrosion coatings have excellent waterproof and oleophobic effects, as well as excellent aging resistance and corrosion resistance, and are widely used in various Anti-corrosion of steel structure and concrete structure surface. However, in the face of various complex environmental factors such as heavy corrosion of the marine environment, mechanical impact of waves, exposure to sunlight, damp heat, salt erosion, etc., the adhesion, hardness, anti-fouling and self-cleaning properties of fluorocarbon anti-corrosion coatings are still slightly insufficient, and the service life of the material is still slightly insufficient. It is difficult to meet the actual requirements, and it is urgent to further improve its mechanical properties through effective methods, improve the comprehensive performance of fluorocarbon anti-corrosion coatings, and prolong the service life.

At present, the existing fluorocarbon coating modification methods mainly use physical blending methods, such as adding nanomaterials and functional materials such as graphene; or chemical modification methods, such as adding reactive active substances such as epoxy resin and polyurethane to improve fluorocarbon coatings. Mechanical properties and corrosion resistance of coatings. Although these methods can improve the hardness, wear resistance and corrosion resistance of fluorocarbon coatings to a certain extent, the improvement of the performance of fluorocarbon coatings is also limited due to the limitation of the amount of modified substances added. Fluorocarbon resin is the main film-forming substance for fluorocarbon anti-corrosion coatings, and its chemical structure determines the performance of fluorocarbon coatings. Therefore, from the perspective of molecular structure, designing and optimizing the chemical structure of fluorocarbon resins and synthesizing new fluorocarbon resins can be fundamentally To improve the comprehensive performance of fluorocarbon coatings, and further expand the application of fluorocarbon coatings in the field of marine heavy corrosion protection.

SUMMARY OF THE INVENTION

In view of this, the present disclosure provides a hydrogenated rosin-modified fluorocarbon resin and a preparation method thereof, so as to further improve the hydrophobicity, antifouling and self-cleaning properties, corrosion resistance and mechanical properties of the fluorocarbon resin, and further expand the application of fluorocarbon coatings in Application in the field of marine heavy corrosion protection.

In a first aspect, the present invention provides a method for preparing a hydrogenated rosin-modified fluorocarbon resin, comprising:

Dissolving the powdered hydrogenated rosin in a solvent to prepare a hydrogenated rosin solution with a mass concentration of 5%-85%;

Add an acid binding agent to the hydrogenated rosin solution, and after mixing evenly, slowly add the acylating agent dropwise at 0 to 60°C. After the dropwise addition, reflux the reaction for 1 to 6 hours to complete the reaction and separate and remove the excess acylation. chemical reagent to obtain acyl chloride hydrogenated rosin solution;

Prepare a polyhydroxy fluorocarbon resin solution with a mass concentration of 10-80%, add an acid binding agent, and mix evenly; then slowly add the acid chloride hydrogenated rosin solution dropwise to it, reflux for 2-48 hours, end the reaction, use deionized Washed with water until neutral, distilled and purified to obtain hydrogenated rosin modified fluorocarbon resin.

Preferably, the hydrogenated rosin is one of fully hydrogenated rosin, refined hydrogenated rosin or tetrahydro rosin.

Preferably, the solvent is one or more of toluene, benzene, ethyl acetate, butyl acetate, petroleum ether, dichloromethane, chloroform and carbon tetrachloride.

Preferably, the acid binding agent is triethylamine, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diisopropylethylamine, 4-dimethylformamide One or more of aminopyridines.

Preferably, the acylating reagent is one of thionyl chloride, oxalyl chloride, phosphorus trichloride, and phosphorus pentachloride.

In a second aspect, the present invention provides a hydrogenated rosin-modified fluorocarbon resin, which is prepared according to the preparation method of the fluorocarbon resin.

Preferably, the molecular structure of the fluorocarbon resin is a carbon chain as the main chain structure, and the side groups connected to the carbon atoms of the main chain are composed of fluorine atoms, hydroxyl groups, hydrogenated rosin ester groups, and/or chlorine atoms, hydrogen atoms, alkyl groups , alkoxy group, carboxyl group and one or more of ester group are formed together.

Preferably, in terms of mass percentage, fluorine atoms in the fluorocarbon resin account for 1% to 55% by mass; hydroxyl groups account for 0.5% to 15% by mass; hydrogenated rosin ester The mass percentage of the base in the whole is 1% to 35%.

The third aspect is the application of the fluorocarbon resin in the field of marine heavy corrosion protection.

The invention provides a hydrogenated rosin-modified fluorocarbon resin and a preparation method thereof. From the perspective of molecular structure design, hydrogenated rosin is used as a fluorocarbon resin modification material to synthesize a new type of modified fluorocarbon resin. The introduction of hydrogenated rosin group has obvious steric hindrance effect, better hydrophobicity, better heat resistance and anti-corrosion performance. It is used as the raw material of anti-corrosion coating and the coating film obtained by reacting with isocyanate curing agent is similar to ordinary fluorocarbon anti-corrosion coating. It has higher hardness, better adhesion to metal substrates, excellent corrosion resistance, and excellent artificial weathering resistance, which further expands the application range of fluorocarbon coatings as anti-corrosion coatings.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not intended to limit the disclosure of the present invention.

Detailed ways

Exemplary embodiments will be described in detail herein. The implementations described in the illustrative examples below are not intended to represent all implementations consistent with the present invention. Rather, they are merely examples of systems consistent with some aspects of the invention as recited in the appended claims.

In view of the problem that the current fluorocarbon coating modification method is limited by modified substances and affects the performance of the fluorocarbon coating, first, the present embodiment provides a preparation method of a hydrogenated rosin-modified fluorocarbon resin, including:

Dissolving the powdered hydrogenated rosin in a solvent to prepare a hydrogenated rosin solution with a mass concentration of 5%-85%;

Wherein the pulverized hydrogenated rosin can be made into pulverized hydrogenated rosin by grinding and pulverizing the bulk hydrogenated rosin in a grinding machine;

Add an acid binding agent to the hydrogenated rosin solution, and after mixing evenly, slowly add the acylating agent dropwise at 0 to 60°C. After the dropwise addition, reflux the reaction for 1 to 6 hours to complete the reaction and separate and remove the excess acylation. chemical reagent to obtain acyl chloride hydrogenated rosin solution;

Prepare a polyhydroxy fluorocarbon resin solution with a mass concentration of 10-80%, add an acid binding agent, and mix evenly; then slowly add the acid chloride hydrogenated rosin solution dropwise to it, reflux for 2-48 hours, end the reaction, use deionized Washed with water until neutral, distilled and purified to obtain hydrogenated rosin modified fluorocarbon resin.

The above hydrogenated rosin is fully hydrogenated rosin, refined hydrogenated rosin or tetrahydro rosin, preferably commercialized Eastman ForalAX-E fully hydrogenated rosin, Eastman Foral AX fully hydrogenated rosin, Japan Arakawa KE-604 hydrogenated rosin, Japan Arakawa KE- 100 hydrogenated rosin;

Above-mentioned solvent is one or more in toluene, benzene, ethyl acetate, butyl acetate, petroleum ether, dichloromethane, chloroform, carbon tetrachloride;

Above-mentioned acid binding agent is in triethylamine, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diisopropylethylamine, 4-dimethylaminopyridine. one or more;

The above-mentioned acylating reagent is one of thionyl chloride, oxalyl chloride, phosphorus trichloride and phosphorus pentachloride.

The hydrogenated rosin-modified fluorocarbon resin prepared according to the above-mentioned preparation method of the hydrogenated rosin-modified fluorocarbon resin.

The molecular structure of fluorocarbon resin is a carbon chain as the main chain structure, and the side groups connected to the carbon atoms of the main chain are composed of fluorine atoms, hydroxyl groups, hydrogenated rosin ester groups, and/or chlorine atoms, hydrogen atoms, alkyl groups, alkoxy groups, One or more of carboxyl group and ester group form together.

In terms of mass percentage, fluorine atoms in the fluorocarbon resin account for 1% to 55% of the overall mass; hydroxyl groups account for 0.5% to 15% of the overall mass; hydrogenated rosin ester groups account for the overall mass The percentage content is 1% to 35%.

The present invention will be further described below in conjunction with preferred specific embodiments to help understand the content of the present invention.

Example 1

Grind and pulverize 100g of Foral AX-E fully hydrogenated rosin in a grinder to make pulverized hydrogenated rosin for use; take 30g of pulverized Foral AX-E fully hydrogenated rosin and dissolve it in dichloromethane to prepare a mass concentration of 50% 7.3g of N,N-dimethylformamide was added to the above solution, and after mixing evenly, 13g of thionyl chloride was slowly added with a constant pressure dropping funnel at 23°C, and after the addition was completed, reflux reaction 2h, the reaction was terminated, and the excess thionyl chloride was removed by distillation and separation to obtain a hydrogenated rosin solution of acid chloride. Dissolve 1kg of hydroxyfluorocarbon resin with a hydroxyl value of 56 and a fluorine content of 20% in a dichloromethane solvent to prepare a solution with a mass concentration of 50%, add 10g of triethylamine, mix well, and then slowly dropwise add the above prepared solution. The obtained acyl chloride hydrogenated rosin solution was refluxed at room temperature for 8 hours to complete the reaction, washed with deionized water until neutral, and purified by distillation to obtain a hydrogenated rosin modified fluorocarbon resin containing hydrogenated rosin ester groups in the side chain, wherein the mass percentage of hydroxyl groups is 1.5%, the mass percentage of fluorine atoms is 19%, and the mass percentage of hydrogenated rosin ester group is 3%.

After experimental verification, referring to the chemical industry standard HG/T 3792-2014 "Cross-linked Fluorocarbon Resin Coatings", the coating film obtained by the reaction of the hydrogenated rosin-modified fluorocarbon resin prepared by the above method and the hexamethylene diisocyanate curing agent, Compared with the coating film made of unmodified fluorocarbon resin, the hardness is increased to 3H, the adhesion by tensile method is increased by 20%, there is no corrosion phenomenon after 1000h of neutral salt spray resistance test, and no foaming after 3000h of artificial weather resistance test. No falling off, no cracking, no chalking.

Example 2

100g of Japanese Arakawa KE-604 hydrogenated rosin was ground and pulverized in a grinding machine to make pulverized hydrogenated rosin for use; 50g of pulverized Japanese Arakawa KE-604 hydrogenated rosin was dissolved in toluene/acetic acid with a volume ratio of 1:1 A solution with a mass concentration of 40% is prepared in the butyl ester mixed solvent; 15g of pyridine and 0.5g of N,N-dimethylformamide are added to the above solution, and after mixing evenly, under the condition of 10 °C, use a constant pressure dropping funnel 25 g of oxalyl chloride was slowly added, and after the dropwise addition was completed, the reaction was refluxed for 4 hours to complete the reaction, and the excess oxalyl chloride was removed by distillation to obtain a hydrogenated rosin solution of acid chloride. Dissolve 1kg of hydroxyfluorocarbon resin with a hydroxyl value of 65 and a fluorine content of 30% in carbon tetrachloride solvent to prepare a solution with a mass concentration of 30%, and add 20g of triethylamine, 1g of N,N-dimethylethyl amide, mix well, then slowly dropwise add the hydrogenated acyl chloride rosin solution prepared above, reflux at room temperature for 12 hours, end the reaction, wash with deionized water until neutral, and distill and refine to obtain a hydrogenated rosin modified rosin containing a hydrogenated rosin ester group in the side chain. Fluorocarbon resin, wherein the mass percentage of hydroxyl groups is 1.6%, the mass percentage of fluorine atoms is 28%, and the mass percentage of hydrogenated rosin ester groups is 5%.

After experimental verification, referring to the chemical industry standard HG/T 3792-2014 "Cross-linked Fluorocarbon Resin Coatings", the coating film obtained by the reaction of the hydrogenated rosin-modified fluorocarbon resin prepared by the above method and the hexamethylene diisocyanate curing agent, Compared with the coating film made of unmodified fluorocarbon resin, the hardness is increased to 3H, the adhesion by tensile method is increased by 50%, there is no corrosion phenomenon after 1000h of neutral salt spray resistance test, and no bubbles after 3000h of artificial weather resistance test. No falling off, no cracking, no chalking.

Example 3

200g of domestic refined hydrogenated rosin is ground and pulverized in a grinding machine to make pulverized hydrogenated rosin for subsequent use; 160 g of pulverized domestically refined hydrogenated rosin is dissolved in a toluene/petroleum ether mixed solvent with a volume ratio of 2:1 to prepare A solution with a mass concentration of 60%; add 53g of N,N-triethylamine and 2g of N,N-diisopropylethylamine to the above solution, after mixing evenly, slowly add 73g of phosphorus trichloride at 0°C, After the addition is completed, the reaction is refluxed for 6 hours, the reaction is terminated, the excess phosphorus trichloride is removed by filtration and separation, and the hydrogenated rosin solution of acid chloride is obtained. Dissolve 1kg of hydroxyfluorocarbon resin with a hydroxyl value of 85 and a fluorine content of 35% in a dichloromethane/toluene solvent with a volume ratio of 1:3 to prepare a solution with a mass concentration of 60%, and add 55g of triethylamine, Mix evenly, then slowly add the above-obtained acyl chloride hydrogenated rosin solution dropwise, reflux at room temperature for 24 hours, end the reaction, wash with deionized water until neutral, and purify by distillation to obtain hydrogenated rosin modified fluorine containing hydrogenated rosin ester groups in the side chain. Carbon resin, wherein the mass percentage of hydroxyl groups is 1.5%, the mass percentage of fluorine atoms is 30%, and the mass percentage of hydrogenated rosin ester groups is 13%.

After experimental verification, referring to the chemical industry standard HG/T 3792-2014 "Cross-linked Fluorocarbon Resin Coatings", the coating film obtained by the reaction of the hydrogenated rosin-modified fluorocarbon resin prepared by the above method and the hexamethylene diisocyanate curing agent, Compared with the coating film made of unmodified fluorocarbon resin, the hardness is increased to 4H, the adhesion by tensile method is increased by 40%, there is no corrosion phenomenon after 1000h of neutral salt spray resistance test, and no foaming after 3000h of artificial weather resistance test. No falling off, no cracking, no chalking.

Other embodiments of the invention will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses or adaptations of the invention which follow the general principles of the invention and which include common knowledge or conventional techniques in the art not disclosed by the invention . The specification and examples are to be regarded as exemplary only, with the true scope and spirit of the invention being indicated by the claims.

Claims (9)

1. a preparation method of a hydrogenated rosin-modified fluorocarbon resin, is characterized in that, comprising: Dissolving the powdered hydrogenated rosin in a solvent to prepare a hydrogenated rosin solution with a mass concentration of 5%-85%; Add an acid binding agent to the hydrogenated rosin solution, and after mixing evenly, slowly add the acylating agent dropwise at 0 to 60°C. After the dropwise addition, reflux the reaction for 1 to 6 hours to complete the reaction and separate and remove the excess acylation. chemical reagent to obtain acyl chloride hydrogenated rosin solution; Prepare a polyhydroxy fluorocarbon resin solution with a mass concentration of 10-80%, add an acid binding agent, and mix evenly; then slowly add the acid chloride hydrogenated rosin solution dropwise to it, reflux for 2-48 hours, end the reaction, use deionized Washed with water until neutral, distilled and purified to obtain hydrogenated rosin modified fluorocarbon resin. 2 . The preparation method of a hydrogenated rosin-modified fluorocarbon resin according to claim 1 , wherein the hydrogenated rosin is one of fully hydrogenated rosin, refined hydrogenated rosin or tetrahydro rosin. 3 . 3. the preparation method of a kind of hydrogenated rosin modified fluorocarbon resin according to claim 1, is characterized in that, described solvent is toluene, benzene, ethyl acetate, butyl acetate, sherwood oil, dichloromethane, One or more of chloroform and carbon tetrachloride. 4. the preparation method of a kind of hydrogenated rosin modified fluorocarbon resin according to claim 1, is characterized in that, described acid binding agent is triethylamine, pyridine, N,N-dimethylformamide, N , One or more of N-dimethylacetamide, N,N-diisopropylethylamine and 4-dimethylaminopyridine. 5. the preparation method of a kind of hydrogenated rosin-modified fluorocarbon resin according to claim 1, is characterized in that, acylating reagent is in thionyl chloride, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride A sort of. 6. A hydrogenated rosin-modified fluorocarbon resin, characterized in that, the fluorocarbon resin is prepared by the method for preparing a fluorocarbon resin according to any one of claims 1-5. 7. a kind of hydrogenated rosin-modified fluorocarbon resin according to claim 6, is characterized in that, the molecular structure of described fluorocarbon resin takes carbon chain as main chain structure, and the side group connected with main chain carbon atom is composed of A fluorine atom, a hydroxyl group, a hydrogenated rosin ester group, and/or one or more of a chlorine atom, a hydrogen atom, an alkyl group, an alkoxy group, a carboxyl group, and an ester group form together. 8 . The fluorocarbon resin modified by hydrogenated rosin according to claim 6 , wherein, in the fluorocarbon resin, the mass percentage of fluorine atoms in the whole is 1%～ 55%; the mass percentage content of the hydroxyl group in the whole is 0.5%-15%; the mass percentage content of the hydrogenated rosin ester group in the whole is 1%-35%. 9 . The application of a hydrogenated rosin-modified fluorocarbon resin according to claim 6 , wherein the fluorocarbon resin is used in the field of marine heavy corrosion protection. 10 .