Special high polymer material emulsion as well as preparation method and application thereof

Abstract

The invention discloses a special high-molecular material emulsion and a preparation method and application thereof.The special high-molecular material is prepared from fluorine-containing arone monomers, bisphenol compounds and carboxylic acid functional monomers through nucleophilic polycondensation and post-functionalization, the surface of the high-molecular material contains a large number of carboxyl groups and hydroxyl groups, and the special high-molecular material emulsion has the advantages of being high in strength, good in mechanical property and the like. The coating has the characteristics of high temperature resistance, strong carbon fiber material adsorption and infiltration capability, long storage time, high coating hardness and pencil hardness, excellent salt spray resistance and the like, and can be widely applied to the fields of high-temperature-resistant and corrosion-resistant coatings, carbon fiber composite materials and the like; compared with a traditional sulfonation process, the method has more excellent environmental protection performance, belongs to the field of environment-friendly special polymer materials, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to a polymer material and a preparation method and application thereof, in particular to a carboxyl- and hydroxyl-modified polymer resin emulsion and a preparation method and application thereof. Background Art

[0002] Special polymer materials refer to a class of polymer compounds that exhibit excellent performance under specific environments or special needs. This type of material not only has the basic characteristics of traditional polymer materials such as light weight and high strength, but also has unique physical, chemical and mechanical properties, such as high temperature resistance, low temperature resistance, and high wear resistance. They mainly include polyimide (PI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), aramid (Kevlar), ultra-high molecular weight polyethylene, polytetrafluoroethylene (PTFE) and polysulfone (PSU). Among them, polyetheretherketone (PEEK) material can be used as a high-temperature resistant structural material and electrical insulation material due to its good chemical stability, wear resistance, high temperature resistance and chemical corrosion resistance. It can be composited with glass fiber or carbon fiber to prepare reinforcement materials, and is therefore widely used in aerospace, medical equipment, new energy vehicles, humanoid robots and other fields.

[0003] Traditional polyetheretherketone (PEEK) is widely used in engineering plastics due to its excellent performance, but its processing usually relies on high-temperature melt molding or solvent-based processes, which increases its application difficulty to a certain extent. PEEK emulsion has the characteristics of low VOC content, low equipment requirements and flexible processing, and is currently a hot research and development topic. Existing technologies mainly improve its hydrophilicity through sulfonation modification with concentrated sulfuric acid, but there are problems such as difficulty in controlling the sulfonation degree, complex process, excessive use of concentrated sulfuric acid, and severe pollution. Summary of the Invention

[0004] Objectives of the Invention: The first objective of the present invention is to provide a specialty polymer material emulsion that contains a large amount of carboxyl and hydroxyl groups on its surface, exhibits high film hardness (including pencil hardness), strong adhesion, strong adsorption and wetting ability for carbon fiber materials, long storage life, and excellent salt spray resistance. Another objective is to provide a method for preparing this emulsion. Finally, the present invention aims to provide applications of this emulsion in the preparation of corrosion-resistant and wear-resistant coatings or carbon fiber, glass fiber, and aramid fiber composite materials.

[0005] Technical solution: A special polymer material emulsion of the present invention is prepared by nucleophilic polycondensation and post-functionalization using fluorine-containing aromatic ketone monomers, bisphenol compounds, and carboxylic acid functional monomers as raw materials. The surface of the special polymer material contains carboxyl and hydroxyl groups.

[0006] The method for preparing the special polymer material emulsion of the present invention comprises the following steps:

[0007] (1) Polycondensation reaction: adding fluorinated aromatic ketone monomer, bisphenol compound, carboxylic acid functional monomer, and alkali metal carbonate to a solvent, heating and polymerizing in a light-proof and inert atmosphere to obtain a carboxylic acid-modified specialty polymer resin containing the solvent;

[0008] (2) Hydroxyl modification: sodium borohydride is added to a carboxylic acid-modified specialty polymer resin containing a solvent, heated for reaction, and the resulting prepolymer is poured into deionized water, crushed, washed, and dried to obtain a hydroxyl-carboxylic acid co-modified specialty polymer resin;

[0009] (3) Water-based treatment: Heat the special polymer resin modified with hydroxyl-carboxylic acid, add water, add alkali to adjust the pH, and shear emulsify.

[0010] Furthermore, in step (1), the fluorine-containing aromatic ketone monomer is 4,4-difluorobenzophenone; the bisphenol compound is one or more selected from the group consisting of hydroquinone, bisphenol A, 4,4-dihydroxydiphenyl ether, and 4,4-dihydroxydiphenyl sulfone; the carboxylic acid functional monomer is one or two selected from the group consisting of 2,5-dihydroxybenzoic acid and 3,5-dihydroxybenzoic acid; the alkali metal carbonate is a mixture of potassium carbonate and sodium carbonate; and the solvent is one or more selected from the group consisting of dimethyl sulfoxide, N-methylpyrrolidone, and sulfolane. The molar ratio of the fluorine-containing aromatic ketone monomer to the sum of the bisphenol compound and the carboxylic acid functional monomer is 1:(0.9-1.2), and the molar ratio of the carboxylic acid functional monomer to the bisphenol compound is (3-30):100; the mass ratio of potassium carbonate to sodium carbonate in the alkali metal carbonate is (2-30):1, and the molar ratio of the alkali metal carbonate to the fluorine-containing aromatic ketone monomer is (1-1.2):1. The conditions for heating polymerization are as follows: heating to 140-160°C, keeping warm for 1-3 hours, then heating to 180-200°C, prepolymerizing for 1-3 hours, then heating to 200-250°C, keeping warm for 2-4 hours. In step (2), sodium borohydride is 3-20% of the mass of the carboxylic acid-modified special polymer resin, the heating reaction is at 100-150°C, the reaction is carried out for 12-36 hours, and the resin is washed with ethanol and deionized water respectively. In step (3), the special polymer resin modified with hydroxyl-carboxylic acid is heated to 60-100°C, the base is one or more of ethylenediamine, triethylamine, and triethanolamine, the pH is adjusted to 7-8, and shear emulsification is carried out at 2000-5000 rpm / min for 20-60 minutes.

[0011] Furthermore, increasing the content of the carboxylic acid functional monomer can increase the hydrophilicity of the polymer material, making the prepared emulsion more stable; however, when the content of the carboxylic acid functional monomer is too high, it will affect the crystallinity and water resistance of the polymer material, causing the glass transition temperature and melting point of the material to decrease to a certain extent. Therefore, the content of the carboxylic acid functional monomer needs to be within a reasonable range. Therefore, the molar ratio of the fluorine-containing aromatic ketone monomer to the sum of the bisphenol compound and the carboxylic acid functional monomer is preferably 1:1 to 1.05, and the carboxylic acid functional monomer accounts for 4 to 10% of the amount of the bisphenol compound monomer. K2CO3 has higher reactivity than Na2CO3 and has better salt-forming effects with bisphenol compounds. When K2CO3 is used alone, its reaction speed is very fast, and a large molecular weight can be achieved in a short period of time, but its molecular weight distribution is relatively wide. Sodium salt has relatively low activity, and when Na2CO3 is used alone, the molecular weight of the polymer increases slowly. Therefore, the ratio of the two should be reasonably selected based on the reaction rate. Therefore, the preferred mass ratio of potassium carbonate to sodium carbonate is (10-20):1; the molar ratio of alkali metal carbonate to fluorinated aromatic ketone monomer is (1.02-1.1):1. As the amount of alkali metal increases, its molecular weight will continue to increase, but its molecular weight distribution will also become wider. This is because when the alkali metal content increases, the reaction speed increases, the molecular weight of the product obtained from the initial polymerization is relatively high, and it is easy to precipitate in the solvent, resulting in a wider molecular weight distribution.

[0012] Furthermore, in step (1), when the fluorine-containing aromatic ketone monomer is 4,4-difluorobenzophenone, the bisphenol compound is hydroquinone, and the carboxylic acid functional monomer is 3,5-dihydroxybenzoic acid, the synthesis route of the polycondensation reaction is as shown in the following formula (1):

[0013]

[0014] Here, x and y are both integers greater than or equal to 1.

[0015] In step (2), the synthetic route of the hydroxyl modification reaction is shown in the following formula (2):

[0016]

[0017] Here, x and y are both integers greater than or equal to 1.

[0018] In step (3), the base is triethylamine, and the reaction route of the aqueous treatment is shown in the following formula (3):

[0019]

[0020] Here, x and y are both integers greater than or equal to 1.

[0021] The above overall synthesis route is shown in the following formula (4):

[0022]

[0023] Here, x and y are both integers greater than or equal to 1.

[0024] In fact, polyetheretherketone (PEEK) can be produced by polycondensation of 4,4-difluorobenzophenone and hydroquinone. Traditional polyetheretherketone has high crystallinity, high strength, strong resistance to solvent penetration, and better corrosion resistance. However, its shrinkage rate is also high, and more precise control of molding conditions is required during the processing, which makes the processing more difficult. After adding some bisphenol A to the present invention, the crystallinity of the special polymer material can be reduced, the solubility of the material itself is increased, and the shrinkage rate during the molding process is reduced, and the dimensional stability during the molding process is better.

[0025] The special polymer material emulsion of claim 1 of the present invention is used in the preparation of anti-corrosion and wear-resistant coatings or carbon fiber, glass fiber, and aramid fiber composite materials.

[0026] Furthermore, a curing agent can be added when applying the special polymer material emulsion, and the amount of the curing agent is 0-10% of the mass of the special polymer material emulsion. The curing agent is a curing agent containing an isocyanate group or an amino resin. The specific curing agent is one or more of an adduct of toluene diisocyanate and trimethylolpropane (TDI-TMP), hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate dimer (TDI dimer), hydrophilic group-modified isocyanate, methyl etherified amino resin, butyl etherified amino resin, and mixed etherified amino resin.

[0027] Furthermore, the curing agent uses a hydrophilic group-modified isocyanate curing agent or amino resin, such as the commercially available Covestro DN, Asahi Kasei WT333, Asahi Kasei WL-72, and Cymel 325 amino resin. When the isocyanate type curing agent is selected, both can crosslink and cure at room temperature. However, when the amino resin type curing agent is selected, high-temperature crosslinking between 120 and 200 degrees Celsius is required for 5 to 60 minutes.

[0028] The present invention introduces carboxylic acid groups through copolymerization to achieve the preparation of a high-stability special polymer material emulsion. At the same time, the introduction of some hydroxyl groups can improve its physical and mechanical properties by adding an appropriate amount of curing agent. The polymer emulsion of the present invention has a large amount of carboxyl and hydroxyl groups on the surface, and has the characteristics of high pencil hardness, strong adhesion, strong adsorption and infiltration ability of carbon fiber materials, long storage time, and excellent salt spray resistance. It can be widely used in high-temperature resistant, corrosion-resistant coatings and carbon fiber composite materials. This direction is in line with the trend of high-performance and environmentally friendly polymer materials. It is expected to open up new application scenarios in the fields of medical care, electronics, environmentally friendly coatings, etc., while reducing the high cost threshold of traditional special polymer materials and having broad market application prospects. The present invention has a simple operation method, better environmental performance, and has broad application prospects.

[0029] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The present invention introduces carboxylic acid groups through copolymerization, which can realize the preparation of high-stability special polymer material emulsions, which is in line with the trend of green manufacturing, especially in the fields of medical care, food packaging, etc. (2) The prior art mainly improves the hydrophilicity of special polymer materials by sulfonation modification with concentrated sulfuric acid. This process has problems such as large amount of concentrated sulfuric acid used and serious pollution. The present invention can significantly reduce volatile organic compound (VOC) emissions and also reduce the difficulty of post-processing. (3) The special polymer material emulsion prepared by the present invention reduces the processing difficulty of traditional special polymer materials and is more suitable for thin layer application scenarios such as coatings and films. (4) The special polymer material emulsion prepared by the present invention can reduce processing energy consumption and equipment requirements, thereby reducing production costs and promoting the application of special polymer materials in more terminal markets. (5) The surface of the special polymer material emulsion prepared by the present invention also contains some hydroxyl groups. According to different usage scenarios, the physical and chemical properties of the material can be improved by adding an appropriate amount of curing agent, thereby meeting the usage requirements of different fields.

[0030] In summary, the special polymer material emulsion provided by the present invention can achieve the preparation of a high-stability special polymer material emulsion by introducing carboxylic acid groups through copolymerization. At the same time, the introduction of some hydroxyl groups can improve its physical and mechanical properties by adding an appropriate amount of curing agent. It has the characteristics of high adhesion, strong adsorption and wetting ability of carbon fiber materials, long storage time, high pencil hardness of the coating, and excellent salt spray resistance. It conforms to the trend of high performance and environmental protection of polymer materials, and is expected to open up new application scenarios in the fields of medical care, electronics, environmentally friendly coatings, etc., while reducing the high cost threshold of traditional special polymer materials, and has broad market application prospects. DETAILED DESCRIPTION

[0031] The technical solution of the present invention will be further described below in conjunction with embodiments.

[0032] The evaluation criteria for special polymer emulsions include the basic properties of special polymer emulsion coatings and the performance of composite materials after being compounded with carbon fiber materials.

[0033] 1. Basic properties of special polymer material emulsions: The sample for basic performance test of special polymer material emulsions should be tinplate that meets the national standard requirements. It must be degreased and sandblasted before use. The surface cleanliness should reach Sa2.5 level specified in the national standard GB / T8923.1-2011. The main test properties are as follows:

[0034] ①. Stability test: Place the prepared special polymer material emulsion in a 40℃ oven and check the coating stability after 90 days to see if there is any stratification.

[0035] ② Pencil hardness test: Refer to the national standard GB / T 6739 "Determination of paint film hardness by pencil method for paints and varnishes". Use pencils of different hardness (from soft to hard, such as 6B to 9H) to apply fixed pressure to the coating surface to scratch. The coating hardness is determined based on the highest pencil hardness level that does not scratch the coating.

[0036] ③. Contact angle test: Select the tinplate surface coated with special polymer material emulsion as the test sample. When preparing the sample, ensure that the sample surface is clean, flat and free of pollution.

[0037] The sample is fixed horizontally and a droplet (usually 2-5 μL) is added using a microsyringe, ensuring that the droplet size is moderate so that the contact angle can be clearly observed. Subsequently, a microscope is used to take a photo of the droplet in contact with the solid surface and the contact angle in the photo is measured using image processing software.

[0038] 2. Basic properties of special polymer material emulsion composite carbon fiber:

[0039] Special polymer material composite carbon fiber can be prepared by the following steps: dispersing carbon fiber cloth in special polymer material emulsion, and ensuring uniform distribution of fibers by ultrasonic treatment (20-60 minutes).

[0040] The carbon fiber impregnated with special polymer material emulsion is placed in a mold. After heating to the melting temperature, it is pressurized, maintained, cooled, and depressurized to form a laminate and cut into strips. The carbon fiber content must be between 50-60wt%. The following properties are mainly tested:

[0041] ①: Test tensile strength and flexural modulus according to ASTM D3039.

[0042] ②: Refer to STM D3518 standard to test its interlaminar shear strength.

[0043] Example 1

[0044] a) Polycondensation reaction: 218 g of 4,4'-difluorobenzophenone (1 mol), 69.3 g of hydroquinone (0.63 mol), 79.8 g of bisphenol A (0.35 mol), 6.16 g of 3,5-dihydroxybenzoic acid (0.04 mol), 133.9 g of K2CO3 (0.97 mol), 7.4 g of Na2CO3 (0.07 mol) and 1100 g of sulfolane were added to a three-necked flask equipped with a mechanical stirrer. In a light-proof and argon atmosphere, the temperature was raised to 160°C and kept warm for 1 hour. The temperature was then raised to 180°C for prepolymerization for 2 hours. Finally, the temperature was raised to 235°C and kept warm for 2 hours to carry out a polymerization reaction. After the reaction, a carboxylic acid-modified specialty polymer resin containing a solvent was obtained.

[0045] The synthetic route of the polycondensation reaction is shown in the following formula (1):

[0046]

[0047] Here, x and y are both integers greater than or equal to 1.

[0048] b) Hydroxyl Modification: The above-mentioned carboxylic acid-modified specialty polymer resin containing solvent and 26g of sodium borohydride were placed in a three-necked flask and reacted at 120°C for 20 hours. After the reaction, the resulting prepolymer was slowly poured into 3-5 times its mass of deionized water to remove excess heat from the reaction. After a white solid appeared in the water, it was separated by filtration. The resulting white solid was pulverized and then washed with ethanol and deionized water. After washing, it was dried in a vacuum oven at 40°C for 8 hours to obtain a white powder, which is a specialty polymer resin modified with both hydroxyl groups and carboxylic acid.

[0049] The synthetic route is shown in the following formula (2):

[0050]

[0051] Here, x and y are both integers greater than or equal to 1.

[0052] c) Water-based treatment: The hydroxy-carboxylic acid co-modified specialty polymer resin prepared in step b) was heated to 80°C, deionized water 3 times its mass was added, and high-speed shear emulsification was carried out at 3000 rpm / min for 30 minutes. Triethylamine was gradually added dropwise during the shearing process until the pH of the emulsion was between 7 and 8, thereby obtaining a milky white specialty polymer material emulsion.

[0053] The synthetic route is shown in the following formula (3):

[0054]

[0055] Here, x and y are both integers greater than or equal to 1.

[0056] The above overall synthesis route is shown in the following formula (4):

[0057]

[0058] Here, x and y are both integers greater than or equal to 1.

[0059] Example 2

[0060] The experimental process is the same as in Example 1, specifically as follows:

[0061] a) Polycondensation reaction: 218 g of 4,4'-difluorobenzophenone (1 mol), 66 g of hydroquinone (0.6 mol), 79.8 g of bisphenol A (0.35 mol), 9.24 g of 3,5-dihydroxybenzoic acid (0.06 mol), 135 g of K2CO3 (0.98 mol), 6.4 g of Na2CO3 (0.06 mol) and 1100 g of sulfolane were added to a three-necked flask equipped with a mechanical stirrer. In a light-proof and argon atmosphere, the temperature was raised to 150°C and kept warm for 1 hour. The temperature was then raised to 180°C for prepolymerization for 2 hours, and finally the temperature was raised to 230°C for 3 hours to carry out a polymerization reaction. After the reaction, a carboxylic acid-modified specialty polymer resin containing a solvent was obtained.

[0062] b) Hydroxyl Modification: The above-mentioned carboxylic acid-modified specialty polymer resin containing solvent and 25g of sodium borohydride were placed in a three-necked flask and reacted at 120°C for 24 hours. After the reaction, the resulting prepolymer was slowly poured into 3-5 times its mass of deionized water to remove excess heat from the reaction. Once a white solid appeared in the water, it was separated by filtration. The resulting white solid was pulverized and then washed with ethanol and deionized water. After washing, it was dried in a vacuum oven at 40°C for 8 hours to obtain a white powder, which is the specialty polymer resin modified with both hydroxyl groups and carboxylic acid.

[0063] c) Water-based treatment: The hydroxy-carboxylic acid co-modified specialty polymer resin prepared in step b) was heated to 80°C, deionized water 3 times its mass was added, and high-speed shear emulsification was carried out at 3000 rpm / min for 30 minutes. Triethylamine was gradually added dropwise during the shearing process until the pH of the emulsion was between 7 and 8, thereby obtaining a milky white specialty polymer material emulsion.

[0064] Example 3

[0065] The experimental process is the same as in Example 1, specifically as follows:

[0066] a) Polycondensation reaction: 218 g of 4,4'-difluorobenzophenone (1 mol), 44 g of hydroquinone (0.4 mol), 125.4 g of bisphenol A (0.55 mol), 10.78 g of 3,5-dihydroxybenzoic acid (0.07 mol), 138 g of K2CO3 (1 mol), 7.42 g of Na2CO3 (0.05 mol), 1000 g of sulfolane and 200 g of dimethyl sulfoxide were added to a three-necked flask equipped with a mechanical stirrer. The mixture was heated to 140°C in a light-proof and argon atmosphere and kept warm for 1.5 h. The temperature was then raised to 190°C for prepolymerization for 2 h. The temperature was finally raised to 225°C for 4 h to carry out a polymerization reaction. After the reaction, a carboxylic acid-modified specialty polymer resin containing a solvent was obtained.

[0067] b) Hydroxyl Modification: The above-mentioned carboxylic acid-modified specialty polymer resin containing solvent and 28g of sodium borohydride were placed in a three-necked flask and reacted at 130°C for 20 hours. After the reaction, the resulting prepolymer was slowly poured into 3-5 times its mass of deionized water to remove excess heat from the reaction. After a white solid appeared in the water, it was separated by filtration. The resulting white solid was pulverized and then washed with ethanol and deionized water. After washing, it was dried in a vacuum oven at 40°C for 10 hours to obtain a white powder, which is a specialty polymer resin modified with both hydroxyl groups and carboxylic acid.

[0068] c) Water-based treatment: The hydroxy-carboxylic acid co-modified specialty polymer resin prepared in step b) was heated to 90°C, deionized water three times its mass was added, and high-speed shear emulsification was carried out at 2000 rpm / min for 40 minutes. Triethylamine was gradually added dropwise during the shearing process until the pH of the emulsion was between 7 and 8, thereby obtaining a milky white specialty polymer material emulsion.

[0069] Example 4

[0070] The experimental process is the same as in Example 1, specifically as follows:

[0071] a) Polycondensation reaction: 218 g of 4,4'-difluorobenzophenone (1 mol), 88 g of hydroquinone (0.8 mol), 27.4 g of bisphenol A (0.12 mol), 15.4 g of 3,5-dihydroxybenzoic acid (0.1 mol), 131.1 g of K2CO3 (0.95 mol), 6.36 g of Na2CO3 (0.06 mol), 1000 g of sulfolane and 200 g of dimethyl sulfoxide were added to a three-necked flask equipped with a mechanical stirrer. The mixture was heated to 150°C in a light-proof and argon atmosphere, kept warm for 1 hour, then heated to 185°C for prepolymerization for 2 hours, and finally heated to 235°C for 3 hours to carry out a polymerization reaction. After the reaction, a carboxylic acid-modified specialty polymer resin containing a solvent was obtained.

[0072] b) Hydroxyl Modification: The above-mentioned carboxylic acid-modified specialty polymer resin containing solvent and 30g of sodium borohydride were placed in a three-necked flask and reacted at 125°C for 20 hours. After the reaction, the resulting prepolymer was slowly poured into 3-5 times its mass of deionized water to remove excess heat from the reaction. After a white solid appeared in the water, it was separated by filtration. The resulting white solid was pulverized and then washed with ethanol and deionized water. After washing, it was dried in a vacuum oven at 40°C for 8 hours to obtain a white powder, which is a specialty polymer resin modified with both hydroxyl groups and carboxylic acid.

[0073] c) Water-based treatment: The hydroxy-carboxylic acid co-modified specialty polymer resin prepared in step b) was heated to 85°C, deionized water 3 times its mass was added, and high-speed shear emulsification was carried out at 4000 rpm / min for 20 minutes. Triethylamine was gradually added dropwise during the shearing process until the pH of the emulsion was between 7 and 8, thereby obtaining a milky white specialty polymer material emulsion.

[0074] Comparative Example 1

[0075] The preparation process and relevant proportions are the same as in Example 1, except that the amount of carboxylic acid functional monomer added is less, as follows:

[0076] a) Polycondensation reaction: 218 g of 4,4'-difluorobenzophenone (1 mol), 69.3 g of hydroquinone (0.63 mol), 79.8 g of bisphenol A (0.35 mol), 3.1 g of 3,5-dihydroxybenzoic acid (0.02 mol), 133.9 g of K2CO3 (0.97 mol), 7.4 g of Na2CO3 (0.07 mol) and 1100 g of sulfolane were added to a three-necked flask equipped with a mechanical stirrer. In a light-proof and argon atmosphere, the temperature was raised to 160°C and kept warm for 1 hour, then raised to 180°C for prepolymerization for 2 hours, and finally raised to 235°C for 2 hours to carry out a polymerization reaction. After the reaction, a carboxylic acid-modified specialty polymer resin containing a solvent was obtained.

[0077] b) Hydroxyl Modification: The above-mentioned carboxylic acid-modified specialty polymer resin containing solvent and 26g of sodium borohydride were placed in a three-necked flask and reacted at 120°C for 20 hours. After the reaction, the resulting prepolymer was slowly poured into 3-5 times its mass of deionized water to remove excess heat from the reaction. After a white solid appeared in the water, it was separated by filtration. The resulting white solid was pulverized and then washed with ethanol and deionized water. After washing, it was dried in a vacuum oven at 40°C for 8 hours to obtain a white powder, which is a specialty polymer resin modified with both hydroxyl groups and carboxylic acid.

[0078] c) Water-based treatment: The hydroxy-carboxylic acid co-modified specialty polymer resin prepared in step b) was heated to 80°C, deionized water 3 times its mass was added, and high-speed shear emulsification was carried out at 3000 rpm / min for 30 minutes. Triethylamine was gradually added dropwise during the shearing process until the pH of the emulsion was between 7 and 8, thereby obtaining a milky white specialty polymer material emulsion.

[0079] Comparative Example 2

[0080] The preparation process and relevant proportions are the same as in Example 1, except that a larger amount of carboxylic acid functional monomer is added, as follows:

[0081] a) Polycondensation reaction: 218 g of 4,4'-difluorobenzophenone (1 mol), 69.3 g of hydroquinone (0.63 mol), 79.8 g of bisphenol A (0.35 mol), 23.1 g of 3,5-dihydroxybenzoic acid (0.15 mol), 133.9 g of K2CO3 (0.95 mol), 7.4 g of Na2CO3 (0.06 mol) and 1100 g of sulfolane were added to a three-necked flask equipped with a mechanical stirrer. In a light-proof and argon atmosphere, the temperature was raised to 160°C and kept warm for 1 hour. The temperature was then raised to 180°C for prepolymerization for 2 hours. Finally, the temperature was raised to 235°C and kept warm for 2 hours to carry out a polymerization reaction. After the reaction, a carboxylic acid-modified specialty polymer resin containing a solvent was obtained.

[0082] b) Hydroxyl Modification: The above-mentioned carboxylic acid-modified specialty polymer resin containing solvent and 26g of sodium borohydride were placed in a three-necked flask and reacted at 120°C for 20 hours. After the reaction, the resulting prepolymer was slowly poured into 3-5 times its mass of deionized water to remove excess heat from the reaction. After a white solid appeared in the water, it was separated by filtration. The resulting white solid was pulverized and then washed with ethanol and deionized water. After washing, it was dried in a vacuum oven at 40°C for 8 hours to obtain a white powder, which is a specialty polymer resin modified with both hydroxyl groups and carboxylic acid.

[0083] c) Water-based treatment: The hydroxy-carboxylic acid co-modified specialty polymer resin prepared in step b) was heated to 80°C, deionized water 3 times its mass was added, and high-speed shear emulsification was carried out at 3000 rpm / min for 30 minutes. Triethylamine was gradually added dropwise during the shearing process until the pH of the emulsion was between 7 and 8, thereby obtaining a milky white specialty polymer material emulsion.

[0084] Comparative Example 3

[0085] The preparation process and relevant proportions are the same as those in Example 1, except that no hydroxyl modification is performed, as follows:

[0086] a) Polycondensation reaction: 218 g of 4,4'-difluorobenzophenone (1 mol), 69.3 g of hydroquinone (0.63 mol), 79.8 g of bisphenol A (0.35 mol), 6.16 g of 3,5-dihydroxybenzoic acid (0.04 mol), 133.9 g of K2CO3 (0.97 mol), 7.4 g of Na2CO3 (0.07 mol) and 1100 g of sulfolane were added to a three-necked flask equipped with a mechanical stirrer. In a light-proof and argon atmosphere, the temperature was raised to 160°C and kept warm for 1 hour. The temperature was then raised to 180°C for prepolymerization for 2 hours. Finally, the temperature was raised to 235°C and kept warm for 2 hours to carry out a polymerization reaction. After the reaction, a carboxylic acid-modified specialty polymer resin containing a solvent was obtained.

[0087] b) Aqueous treatment: The carboxylic acid-modified specialty polymer resin containing a solvent prepared in step a) was heated to 90° C., deionized water 3 times its mass was added, and high-speed shearing emulsification was performed at 2000 rpm / min for 40 minutes. Triethylamine was gradually added dropwise during the shearing process until the pH of the emulsion was between 7 and 8, thereby obtaining a polymer material emulsion.

[0088] Example 5

[0089] 4% of the mass of hexamethylene diisocyanate (HDI) curing agent was added to the emulsion prepared in Example 1, 3% of the mass of DN curing agent (Covestro Polymers (China) Co., Ltd.) was added to the emulsion prepared in Example 2, 3% of the mass of WT333 curing agent (Asahi Kasei Fine Chemicals (Nantong) Co., Ltd.) was added to the emulsions prepared in Example 3 and Comparative Example 2, respectively, 5% of the mass of amino resin was added to the emulsion prepared in Example 4 as a curing agent (the curing agent needs to be cured at 180°C for 30 minutes.), and 5% of the mass of isophorone diisocyanate (IPDI) was added to the emulsion prepared in Comparative Example 3 as a curing agent, respectively, as Example 1-1, Example 2-1, Example 3-1, Example 4-1, Comparative Example 2-1 and Comparative Example 3-1.

[0090] The 13 water-based special polymer emulsions prepared in Examples 1 to 4, Comparative Examples 1 to 3, and Example 5 were placed in a 40° C. oven for 90 days to check the stability of the emulsions as coatings. At the same time, a degreased and sandblasted iron sheet with a surface cleanliness reaching Sa2.5 level specified in the national standard GB / T8923.1-2011 was used as a substrate. The 13 water-based special polymer emulsions in Examples 1 to 8, Comparative Examples 1 to 3, and Example 5 were applied to the surface using a two-wire rod. After coating, the emulsions were dried at 80° C. for 30 minutes to obtain a uniformly adhered emulsion coating, which was used for subsequent performance tests (pencil hardness and contact angle). The test results are shown in Table 1.

[0091] Table 1 Basic properties of emulsion used as coating

[0092]

[0093]

[0094] As can be seen from Table 1, the special polymer material emulsions prepared in Example 1, Example 2, Example 3, Example 4, Comparative Example 2 and Comparative Example 3 have good emulsion stability after being placed at 40°C for 90 days, without obvious stratification. The special polymer material emulsions in Example 1-1, Example 2-1, Example 3-1, Example 4-1, Comparative Example 2-1 and Comparative Example 3-1 after adding the curing agent will basically show stratification within 48 hours due to the addition of the curing agent; and in Comparative Example 1, due to the small amount of carboxylic acid functional monomer added, the emulsion stratification is serious; after the special polymer material emulsions in Examples 1 to 4 and Examples 1-1 to Example 4-1 are prepared into coatings on the surface of Mark Iron, the pencil hardness reaches more than 3H, and after adding the curing agent, the pencil hardness exceeds 5H, which may be because the hardness of the coating will be further improved after the resin is cross-linked and cured; in Comparative Example 2, due to the large amount of carboxylic acid functional monomer added, the emulsion stratification is serious; The pencil hardness dropped sharply. In Comparative Example 3, since no hydroxyl modification was performed, it was difficult for the curing agent to cross-link with the resin, and part of the curing agent also reacted with water, resulting in a downward trend in the pencil hardness of the coating. After the special polymer material emulsions in Examples 1 to 4 and Examples 1-1 to Example 4-1 were prepared into coatings on the surface of the Mark Iron, their water contact angles were all above 90°, which showed good hydrophilicity. Among them, in Comparative Examples 2 and Comparative Example 2-1, due to the addition of more carboxylic acid functional monomers, their water contact angles were lower than 70°, which showed good hydrophilicity. In comparison, the water contact angle of the PEEK resin in the prior art was approximately between 130 and 140°, and its hydrophilicity was poor. In summary, the amount of carboxylic acid functional monomer added should be between 4 and 10% of the amount of bisphenol compound. Too low an amount will lead to difficulty in emulsification of the emulsion and poor storage stability. Too high an amount will increase the hydrophilicity of the coating and reduce the pencil hardness.

[0095] The cut fiber cloths were respectively immersed in 13 kinds of water-based special polymer emulsions in Examples 1 to 4, Comparative Examples 1 to 3, and Example 5. After being fully soaked, they were taken out and dried. The operation was repeated to ensure that the resin sizing amount reached about 40%, and then heated and dried until the water was completely volatilized. The qualified pre-impregnated fiber cloths were evenly laid into a mold of appropriate size. After the mold was closed, they were placed in a hot press and heated to 270°C at a rate of 5°C / min. The temperature was kept at this temperature for 1 hour to ensure that the resin was completely melted. According to the size of the laminate to be produced, the pressure was maintained at 0.5 MPa for 2 hours, and then the pressure was maintained and the temperature was lowered until the temperature was below 40°C, and then the pressure was released and demolded.

[0096] The prepared fiber composite material was cut into strips 20 cm long and 12 mm wide (pressing thickness was 1 mm), and the tensile strength, flexural modulus and interlaminar shear strength of the strips were tested. The test results are shown in Table 2.

[0097] Table 2

[0098]

[0099] As can be seen from Table 2, the tensile strength, flexural modulus and interlaminar shear strength of the special polymer material emulsion-carbon fiber composite materials in Examples 1 to 4 and Examples 1-1 to 4-1 are relatively high, especially in Examples 1-1, 2-1, 3-1 and 4-1. This may be due to the addition of a curing agent for cross-linking, which has a high practical value. The tensile strength, flexural modulus and interlaminar shear strength of the special polymer material emulsion-carbon fiber composite materials prepared in Comparative Example 1, Comparative Example 2 and Comparative Example 2-1 are significantly lower than those in Examples 1 to 4 and 1-1 to 4-1. Comparative Example 1 may be due to the poor hydrophilicity of the emulsion, which cannot be evenly dispersed in water, making it impossible for the emulsion to be evenly wetted. Due to the carbon fiber material, Comparative Example 2 and Comparative Example 2-1 may be due to the addition of more carboxyl functional monomers, which makes the material's crystallinity lower, thereby greatly reducing the physical properties of the special polymer material emulsion-carbon fiber composite material; compared with the tensile strength, bending modulus and interlaminar shear strength of the special polymer material emulsion-carbon fiber composite material in Comparative Example 3 and Comparative Example 3-1, there is a certain degree of decline in the. This may be because Comparative Example 3 is not modified with hydroxyl groups, which makes it difficult for the curing agent to cross-link with the resin, and part of the curing agent also reacts with water to generate small molecule polymers; the present invention can adjust the hydrophilicity and physical properties of the emulsion according to different use requirements. At the same time, the operation method of the present invention is simple, low-cost, and suitable for industrial production.

Claims

1. A special polymer material emulsion, characterized in that: It is prepared using fluorinated aromatic ketone monomers, bisphenol compounds, and carboxylic acid functional monomers as raw materials through nucleophilic condensation and post-functionalization. The surface of the special polymer material contains carboxyl and hydroxyl groups.

2. The method for preparing the special polymer material emulsion according to claim 1, characterized in that: The following steps are involved: (1) Polycondensation reaction: adding fluorinated aromatic ketone monomer, bisphenol compound, carboxylic acid functional monomer, and alkali metal carbonate to a solvent, heating and polymerizing in a light-proof and inert atmosphere to obtain a carboxylic acid-modified specialty polymer resin containing the solvent; (2) Hydroxyl modification: sodium borohydride is added to a carboxylic acid-modified specialty polymer resin containing a solvent, heated for reaction, and the resulting prepolymer is poured into deionized water, crushed, washed, and dried to obtain a hydroxyl-carboxylic acid co-modified specialty polymer resin; (3) Water-based treatment: Heat the special polymer resin modified with hydroxyl-carboxylic acid, add water, add alkali to adjust the pH, and shear emulsify.

3. The preparation method according to claim 1, characterized in that: In step (1), the fluorine-containing aromatic ketone monomer is 4,4-difluorobenzophenone; the bisphenol compound is one or more of hydroquinone, bisphenol A, 4,4-dihydroxydiphenyl ether, and 4,4-dihydroxydiphenyl sulfone; the carboxylic acid functional monomer is one or two of 2,5-dihydroxybenzoic acid and 3,5-dihydroxybenzoic acid; the alkali metal carbonate is a mixture of potassium carbonate and sodium carbonate; and the solvent is one or more of dimethyl sulfoxide, N-methylpyrrolidone, and cyclopentane.

4. The preparation method according to claim 1, characterized in that: In step (1), the molar ratio of the fluorine-containing aromatic ketone monomer to the sum of the bisphenol compound and the carboxylic acid functional monomer is 1:(0.9-1.2), and the molar ratio of the carboxylic acid functional monomer to the bisphenol compound is (3-30):100; the mass ratio of potassium carbonate to sodium carbonate in the alkali metal carbonate is 2-30:1, and the molar ratio of the alkali metal carbonate to the fluorine-containing aromatic ketone monomer is (1-1.2):

1.

5. The preparation method according to claim 1, characterized in that: In step (1), the conditions for heating polymerization are: heating to 140-160° C., keeping warm for 1-3 hours, then heating to 180-200° C., prepolymerizing for 1-3 hours, then heating to 200-250° C., keeping warm for 2-4 hours.

6. The preparation method according to claim 1, characterized in that: In step (2), sodium borohydride accounts for 3-20% of the mass of the carboxylic acid-modified special polymer resin, the heating reaction is carried out at 100-150° C., the reaction is carried out for 12-36 hours, and the resin is washed with ethanol and deionized water respectively.

7. The preparation method according to claim 1, characterized in that: In step (3), the special polymer resin modified with hydroxyl-carboxylic acid is heated to 60-100° C., the base is one or more of ethylenediamine, triethylamine, and triethanolamine, the pH is adjusted to 7-8, and shear emulsification is carried out at 2000-5000 rpm / min for 20-60 minutes.

8. The preparation method according to claim 1, characterized in that: In step (1), when the fluorine-containing aromatic ketone monomer is 4,4-difluorobenzophenone, the bisphenol compound is hydroquinone, and the carboxylic acid functional monomer is 3,5-dihydroxybenzoic acid, the synthetic route of the polycondensation reaction is shown in the following formula (1): Wherein, x and y are both integers greater than 1.

9. The preparation method according to claim 8, characterized in that: In step (2), the synthetic route of the hydroxyl modification reaction is shown in the following formula (2): Here, x and y are both integers greater than or equal to 1.

10. The preparation method according to claim 9, characterized in that: In step (3), the base is triethylamine, and the reaction route of the aqueous treatment is shown in the following formula (3): Here, x and y are both integers greater than or equal to 1.

11. Use of the special polymer emulsion according to claim 1 in the preparation of anti-corrosion and wear-resistant coatings or carbon fiber, glass fiber, and aramid fiber composite materials.

12. The use according to claim 11, characterized in that When the special polymer material emulsion is used, a curing agent is added. The curing agent is a curing agent containing an isocyanate group or an amino resin. The amount of the curing agent is 0-10% of the mass of the special polymer material emulsion.

13. The use according to claim 12, characterized in that The curing agent is one or more of an adduct of toluene diisocyanate and trimethylolpropane (TDI-TMP), hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate dimer (TDI dimer), hydrophilic group-modified isocyanate, methyl etherified amino resin, butyl etherified amino resin, and mixed etherified amino resin.

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