HIGH-TEMPERATURE SELF-CROSSLINKING FLUORINE-CONTAINING POLYARYLETHERKETONE AND PREPARATION METHOD THEREOF, AND COATING MATERIAL AND PREPARATION METHOD THEREOF

Abstract

The present application relates to the technical field of polyaryletherketone, and discloses a preparation method for a coating material containing high-temperature self-crosslinking fluorine-containing polyaryletherketone. A molecular chain of the high-temperature self-crosslinking fluorine-containing polyaryletherketone contains two crosslinking groups of a styrene group and a thioether group, and its structural formula is:

##STR00001##

Herein, the value range of m is 1-40%, the value range of n is 60-99%, and R is a group that removes a phenolic hydroxyl group from hexafluorobisphenol A. In the high-temperature curing process after film coating, the crosslinking reaction occurs to form a crosslinked polymer coating layer, thereby a coating surface with good moisture and heat resistance, wear resistance, and low friction coefficient is formed.

Claims

1. A preparation method for a coating material containing high-temperature self-crosslinking fluorine-containing polyaryletherketone, wherein it is performed according to the following steps: S1, synthesis of high-temperature self-crosslinking fluorine-containing polyaryletherketone containing two crosslinking groups of styrene group and thioether group: adding raw materials 4,4-difluorobenzophenone, hexafluorobisphenol A, 4,4-dihydroxy p-phenylsulfide, anhydrous potassium carbonate, and N-methylpyrrolidone sequentially to a container equipped with a mechanical stirring device, a thermometer, a water separator, and a nitrogen gas fed, stirring and raising the temperature to 115-125 C., reacting for 2-3 h to remove water generated during the reaction, and then raising the temperature to 175-190 C., and continuously reacting for 2.5-3.5 h; and after a high-temperature polymerization reaction is completed, cooling a reaction system to a room temperature, adding 4-vinylbenzyl chloride and stirring at the room temperature for 20-25 h until the reaction is completed, pouring a reaction product into deionized water, crushing the product after being cooled, filtering after being washed with ethanol and deionized water, and then drying with blast air at 60 C. for 4-8 h, and vacuum-drying at 55-65 C. for 16-20 h; a structural formula of the high-temperature self-crosslinking fluorine-containing polyaryletherketone containing two crosslinking groups of the styrene group and the thioether group is: ##STR00008## wherein, the value range of m being 1-40%, the value range of n being 60-99%, and R being a group that removes a phenolic hydroxyl group from hexafluorobisphenol A; S2, synthesis of high-temperature self-crosslinking fluorine-containing polyaryletherketone containing styrene group: adding 4,4-difluorobenzophenone, hexafluorobisphenol A, anhydrous potassium carbonate, and N-methylpyrrolidone sequentially to a container equipped with a mechanical stirring device, a thermometer, a water separator, and a nitrogen gas fed, stirring and raising the temperature to 115-125 C., reacting for 2-3 h to remove water generated during the reaction, and then raising the temperature to 175-190 C., and continuously reacting for 2.5-3.5 h; and after a high-temperature polymerization reaction is completed, cooling a reaction system to a room temperature, adding 4-vinylbenzyl chloride and stirring at the room temperature for 20-25 h until the reaction is completed, pouring a reaction product into deionized water, crushing the product after being cooled, filtering after being washed with ethanol and deionized water, and then drying with blast air at 60 C. for 4-8 h, and vacuum-drying at 55-65 C. for 16-20 h; S3, synthesis of high-temperature self-crosslinking fluorine-containing polyaryletherketone containing thioether group: adding raw materials 4,4-difluorobenzophenone, hexafluorobisphenol A, 4,4-dihydroxy p-phenylsulfide, anhydrous potassium carbonate, and sulfolane sequentially to a container equipped with a mechanical stirring device, a thermometer, a water separator, and a nitrogen gas fed, stirring and raising the temperature to 115-125 C., reacting for 2-3 h to remove water generated during the reaction, and then raising the temperature to 175-190 C., and continuously reacting for 2.5-3.5 h; and after a high-temperature polymerization reaction is completed, cooling a reaction system, pouring a reaction product into deionized water, crushing the product after being cooled, filtering after being washed with ethanol and deionized water, and then drying with blast air at 60 C. for 4-8 h, and vacuum-drying at 55-65 C. for 16-20 h; and S4, preparation of coating material: dissolving high-temperature self-crosslinking fluorine-containing polyaryletherketone in a solvent, wherein the high-temperature self-crosslinking fluorine-containing polyaryletherketone comprising one or more of the high-temperature self-crosslinking fluorine-containing polyaryletherketone containing two crosslinking groups of the styrene group and the thioether group, the high-temperature self-crosslinking fluorine-containing polyaryletherketone containing the styrene group, and the high-temperature self-crosslinking fluorine-containing polyaryletherketone containing the thioether group, and the solid content range of the high-temperature self-crosslinking fluorine-containing polyaryletherketone being between 10-50 phr; performing the dissolution process within the range of 20-40 C., and after the high-temperature self-crosslinking fluorine-containing polyaryletherketone is completely dissolved, adding a diluent, a flatting agent, and a lubricant and stirring evenly.

2. The preparation method for the coating material containing the high-temperature self-crosslinking fluorine-containing polyaryletherketone as claimed in claim 1, wherein in the step S1, the molar ratio of the 4,4-difluorobenzophenone, hexafluorobisphenol A, 4,4-dihydroxy p-phenylsulfide, anhydrous potassium carbonate, and 4-vinylbenzyl chloride is 0.1803:0.159075-0.201495:0.010605-0.053025:0.252:0.013104-0.065522.

3. The preparation method for the coating material containing the high-temperature self-crosslinking fluorine-containing polyaryletherketone as claimed in claim 1, wherein in the step S2, the molar ratio of the 4,4-difluorobenzophenone, hexafluorobisphenol A, anhydrous potassium carbonate, and 4-vinylbenzyl chloride is 0.1803:0.159075-0.201495:0.252:

4. The preparation method for the coating material containing the high-temperature self-crosslinking fluorine-containing polyaryletherketone as claimed in claim 1, wherein in the step S3, the molar ratio of the 4,4-difluorobenzophenone, hexafluorobisphenol A, 4,4-dihydroxy p-phenylsulfide, and anhydrous potassium carbonate is 0.1803:0.159075-0.201495:010605-0.053025:0.252.

5. The preparation method for the coating material containing the high-temperature self-crosslinking fluorine-containing polyaryletherketone as claimed in claim 1, wherein in the step S4, calculated by the total mass of the coating material, the amount of the high-temperature self-crosslinking fluorine-containing polyaryletherketone is 10-60 phr, the amount of the solvent is 30-70 phr, the amount of the diluent is 10-40 phr; the amount of the flatting agent is 0.1-2.0 phr, and the amount of the lubricant is 1-10 phr.

6. The preparation method for the coating material containing the high-temperature self-crosslinking fluorine-containing polyaryletherketone as claimed in claim 1, wherein in the step S4, the solvent is a mixture of one or more of chloroform, 1,2-dichloroethane, tetrahydrofuran, cyclohexanone, N,N-dimethylformamide, N-methylpyrrolidone, and dimethylacetamide; the diluent is a mixture of one or more of toluene, xylene, hexane, cyclohexane, heptane, octane, and decane; the lubricant is a mixture of one or more of polyethylene wax, polyester wax, polyamide wax, polytetrafluoroethylene wax, and palm wax; and the flatting agent is a mixture of one or more of low-molecular-weight acrylic copolymer, polyether-modified polysiloxane, and silicone polymer.

7. The preparation method for the coating material containing the high-temperature self-crosslinking fluorine-containing polyaryletherketone as claimed in claim 1, wherein the low-molecular-weight acrylic copolymer is an acrylic acid-hydroxypropyl acrylate copolymer with a chain segment length of 500-3000; the polyether-modified polysiloxane is a mixture of one or more of polyether-grafted dimethyl polysiloxane with a chain segment length of 2000-5000, polyether-modified heptamethyltrisiloxane surfactant TRSE, polyether-modified octamethyltetrasiloxane surfactant TESE, S-7-type polyether-modified polysiloxane defoamer, S-8-type polyether-modified polysiloxane defoamer, and SiC-type polyether-modified polysiloxane defoamer; and the silicone polymer is a mixture of one or more of calcium carbonate-filled silicone sealant, modified silicone sealing material Caneca Ms polymer, and silicone-polyimide-synthesized halogen-free elastomer-type block copolymer SILTEM with a chain segment length of 2000-5000.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0050] The sole figure is a reaction formula diagram of a preparation process of high-temperature self-crosslinking fluorine-containing polyaryletherketone of the present application.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0051] Technical schemes of the present application are clearly and completely described below in combination with specific implementation modes. Apparently, embodiments described are only a part of the embodiments of the present application, not all of the embodiments.

[0052] Embodiment 1: this embodiment provides a synthesis method for high-temperature self-crosslinking fluorine-containing polyaryletherketone containing two crosslinking groups of a styrene group and a thioether group.

[0053] The reaction formula is shown in the sole figure. Raw materials 46.2849 g (0.21 mol) of 4,4-difluorobenzophenone, 61.8543 g (0.1803 mol) of hexafluorobisphenol A, 6.941 g (0.0318 mol) of crosslinking agent 4,4-dihydroxy p-phenylsulfide, 35.1808 g (0.252 mol) of anhydrous potassium carbonate, and 420 ml of reactive solvent NMP (N-methylpyrrolidone) are added sequentially to 1000 ml of a four-port flask equipped with a mechanical stirring device, a thermometer, a water separator, and a nitrogen gas fed, it is stirred and the temperature is raised to 120 C., it is reacted for 2 h to remove water generated during the reaction, and then the temperature is raised to 180 C., and it is continuously reacted for 3 h; and after a high-temperature polymerization reaction is completed, a reaction system is cooled to a room temperature, 3.2 g (0.021 mol) of 4-vinylbenzyl chloride is added and stirred at the room temperature for 24 h until the reaction is completed, a reaction product is poured into deionized water, the product is crushed after being cooled, it is filtered after being washed with ethanol and deionized water, and then it is dried with blast air at 60 C. for 6 h, and vacuum-dried at 60 C. for 18 h, to obtain high-temperature self-crosslinking fluorine-containing polyaryletherketone white polymer powder with the styrene group as an end group and the thioether group contained in the molecular chain, in which the molar fraction of the styrene group is 5%, and the molar fraction of the thioether group is 7.5%; and the yield is 95%.

[0054] Embodiment 2: this embodiment provides a synthesis method for high-temperature self-crosslinking fluorine-containing polyaryletherketone containing a styrene group.

[0055] 46.2849 g (0.21 mol) of 4,4-difluorobenzophenone, 72.7698 g (0.2121 mol) of hexafluorobisphenol A, 35.1808 g (0.252 mol) of anhydrous potassium carbonate, and 420 ml of reactive solvent NMP are added sequentially to 1000 ml of a four-port flask equipped with a mechanical stirring device, a thermometer, a water separator, and a nitrogen gas fed, it is stirred and the temperature is raised to 120 C., it is reacted for 2 h to remove water generated during the reaction, and then the temperature is raised to 180 C., and it is continuously reacted for 3 h; and after a high-temperature polymerization reaction is completed, a reaction system is cooled to a room temperature, 3.2 g (0.021 mol) of 4-vinylbenzyl chloride is added and stirred at the room temperature for 20-25 h until the reaction is completed, a reaction product is poured into deionized water, the product is crushed after being cooled, it is filtered after being washed with ethanol and deionized water, and then it is dried with blast air at 60 C. for 6 h, and vacuum-dried at 60 C. for 18 h, to obtain high-temperature self-crosslinking fluorine-containing polyaryletherketone white polymer powder containing the styrene group, in which the molar fraction of the styrene group is 5%, and the yield is 95%.

[0056] Embodiment 3: this embodiment provides a synthesis method for high-temperature self-crosslinking fluorine-containing polyaryletherketone containing a thioether group.

[0057] Raw materials 46.2849 g (0.21 mol) of 4,4-difluorobenzophenone, 61.8543 g (0.1803 mol) of hexafluorobisphenol A, 6.941 g (0.0318 mol) of crosslinking agent 4,4-dihydroxy p-phenylsulfide, 35.1808 g (0.252 mol) of anhydrous potassium carbonate, and 420 ml of reactive solvent sulfolane are added sequentially to 1000 ml of a four-port flask equipped with a mechanical stirring device, a thermometer, a water separator, and a nitrogen gas fed, it is stirred and the temperature is raised to 120 C., it is reacted for 2 h to remove water generated during the reaction, and then the temperature is raised to 180 C., and it is continuously reacted for 3 h; and after a high-temperature polymerization reaction is completed, a reaction system is cooled to a room temperature, a reaction product is poured into deionized water, the product is crushed after being cooled, it is filtered after being washed with ethanol and deionized water, and then it is dried with blast air at 60 C. for 6 h, and vacuum-dried at 60 C. for 18 h, to obtain high-temperature self-crosslinking fluorine-containing polyaryletherketone white polymer powder containing the thioether group, in which the molar fraction of the thioether group is 7.5%, and the yield is 95%.

[0058] Contrast example 1: this embodiment provides a preparation method for fluorine-containing polyaryletherketone without containing a crosslinking agent.

[0059] Raw materials 46.2849 g (0.21 mol) of 4,4-difluorobenzophenone, 72.7698 g (0.2121 mol) of hexafluorobisphenol A, 35.1808 g (0.0318 mol) of crosslinking agent 4,4-dihydroxy p-phenylsulfide, 35.1808 g (0.252 mol) of anhydrous potassium carbonate, and 420 ml of reactive solvent sulfolane are added sequentially to 1000 ml of a four-port flask equipped with a mechanical stirring device, a thermometer, a water separator, and a nitrogen gas fed, it is stirred and the temperature is raised to 120 C., it is reacted for 2 h to remove water generated during the reaction, and then the temperature is raised to 180 C., and it is continuously reacted for 3 h; and after a high-temperature polymerization reaction is completed, a reaction product is poured into deionized water, the product is crushed after being cooled, it is filtered after being washed with ethanol and deionized water, and then it is dried with blast air at 60 C. for 6 h, and vacuum-dried at 60 C. for 18 h, to obtain fluorine-containing polyaryletherketone white polymer powder without containing the crosslinking agent, and the yield is 95%.

[0060] The fluorine-containing polyaryletherketone prepared in the above Embodiments 1-3 and Contrast example 1 is respectively used to prepare a coating material according to the aforementioned preparation method for the coating material containing the high-temperature self-crosslinking fluorine-containing polyaryletherketone.

[0061] Specifically, in the aforementioned preparation method for the coating material containing the high-temperature self-crosslinking fluorine-containing polyaryletherketone, the method for preparing the coating material by using Embodiment 1 is that the high-temperature self-crosslinking fluorine-containing polyaryletherketone added in the step S4 is prepared only for Embodiment 1; the method for preparing the coating material by using Embodiment 2 is that the high-temperature self-crosslinking fluorine-containing polyaryletherketone added in the step S4 is prepared only for Embodiment 2; the method for preparing the coating material by using Embodiment 3 is that the high-temperature self-crosslinking fluorine-containing polyaryletherketone added in the step S4 is prepared only for Embodiment 3; and the method for preparing the coating material by using Contrast example 1 is that the fluorine-containing polyaryletherketone added in the step S4 is prepared only for Contrast example 1.

[0062] The amounts of the fluorine-containing polyaryletherketone added corresponding to the coating materials prepared in Embodiments 1-3 and Contrast example 1 are all 50 phr, the amount of the solvent N-methylpyrrolidone is 40 phr, the amount of the diluent hexane is 20 phr, and the amount of the flatting agent low-molecular-weight acrylic ester is 0.15 phr, product model: EPITEX 66, and seller: Wuhan ZeShanCheng Biomedical Technology Co., Ltd.; and the amount of the lubricant polyether-grafted dimethyl polysiloxane with the chain segment length of 2000-5000 is 3 phr, product model: SP-983, and seller: Guangzhou Xinguan Chemical Technology Co., Ltd. In addition, the low-molecular-weight acrylic ester may also adopt ACRYLATES COPOLYMER sold by Beijing HuameiHuli Biochemical Co., Ltd.; and the polyether-grafted dimethyl polysiloxane with the chain segment length of 2000-5000 may also adopt SR-202 sold by Guangdong Rebon High-tech Materials Co., Ltd. The performance comparison table of the coating materials prepared is shown in Table 3.

TABLE-US-00003 TABLE 3 Performance comparison table of coating materials prepared from fluorine- containing polyaryletherketone in Embodiments 1-3 and Contrast example 1 Contrast Embodi- Embodi- Embodi- Test item Test standard Comparison content Test condition example 1 ment 2 ment 3 ment 1 Moisture and heat GB/T Coating surface Original coating layer The paint film surface is flat and smooth resistance 28046.4-2011 condition 47 C./96% high The paint film is The paint film is not bubbled or fallen off moisture and heat, partially bubbled or after 72 h of treatment fallen off Scratch Original coating layer 2.672 3.458 3.743 4.084 resistance, N 47 C./96% high 2.071 3.246 3.512 4.041 moisture and heat, after 72 h of treatment Oil GB/T Coating surface Original coating layer The paint film surface is flat and smooth resistance 17948.1-2018 condition 160 C., after 72 h The paint film The paint film surface is flat and smooth of treatment surface is not flat Wear GB/T Scratch Original coating layer 2.672 3.458 3.743 4.084 resistance 4074.3-2008 resistance, N 160 C., after 72 h 1.876 3.196 3.625 4.063 of treatment Friction GB/T 0.108 0.109 0.109 0.108 coefficient 4074.3-2008

[0063] It may be seen from Table 3 that: in terms of the wear resistance, the wear resistance of Contrast example 1 without the styrene group and the thioether group is relatively low in both the original coating layer and after the high-temperature post-treatment, especially while only 1.876 N of a friction force is needed to damage the coating layer after the high-temperature treatment; the coating material prepared from the fluorine-containing polyaryletherketone containing the styrene group or the thioether group, under the conditions of both the original coating layer and after the high-temperature post-treatment, requires the friction force greater than 3.1 N to wear the coating layer, and it is apparent that the wear resistance is improved; and the wear resistance of Embodiment 1 is the best, and at least 4.063 N of the friction force is required to wear or damage the coating layer in both the original coating layer and after the high-temperature post-treatment, so the wear resistance is nearly doubled. In terms of the oil resistance, the coating surface of Contrast example 1 without containing the styrene group and the thioether group is not flat after the high-temperature treatment, it is indicated that in the high-temperature oil resistance experiment of the coating material, the paint layer is partially fallen off, and the oil resistance is relatively poor. For the coating material prepared from the fluorine-containing polyaryletherketone containing the styrene group or the thioether group, under the conditions of both the original coating layer and after the high-temperature post-treatment, the paint film surface is smooth and flat, and the paint film is not fallen off, it is apparent that the oil resistance is greatly improved. In terms of the moisture and heat resistance, the scratch resistance of Contrast example without containing the styrene group and the thioether group is relatively low in both the original coating layer and after the high-temperature post-treatment, especially after the high moisture and heat treatment, only 2.071 N of the friction force is needed to damage the coating layer; for the coating material prepared from the fluorine-containing polyaryletherketone containing the styrene group or the thioether group, under the conditions of both the original coating layer and after the high-temperature post-treatment, the friction forces required to wear the coating layer are all greater than 3.2 N, it is apparent that the moisture and heat resistance is improved; and the moisture and heat resistance of Embodiment 1 is the best, at least 4.041 N of the friction force is required to wear or damage the coating layer in both the original coating layer and after the high-temperature post-treatment, and the moisture and heat resistance is nearly doubled. There is no significant difference between the friction coefficients of the coating materials prepared in Embodiments 1-3 and Contrast example 1, and they are all around 0.108.

[0064] The high-temperature self-crosslinking fluorine-containing polyaryletherketone of the present application introduces the crosslinking groups of the styrene group and the thioether group into the molecular chain of the fluorine-containing polyaryletherketone, as to form the fluorine-containing polyaryletherketone with the styrene group as the end group and the thioether group contained in the middle of the molecular chain. Compared with the polyaryletherketone, the fluorine-containing polyaryletherketone of the present application may be used as a coating material matrix resin applied in the coating material because a fluorine substituent is introduced so that it may be dissolved in the conventional organic solvent; and under normal temperature conditions, its linear structure may be dissolved in the conventional organic solvent, and during post-coating heat treatment, a thioether bond and a vinyl group in the coating film may undergo self-crosslinking, the coating layer resin becomes a three-dimensional crosslinking network structure, so that the oil resistance and hydrolysis resistance at a high temperature and the moisture and heat resistance of the coating layer are significantly improved, thereby the long-term requirements of the special coating layer in the harsh working environments such as high temperature, high pressure, and high humidity are satisfied. The coating material prepared by the high-temperature self-crosslinking fluorine-containing polyaryletherketone of the present application may be stably used in the environments with the high temperature above 150 C., 2 atmospheric pressures, and the relative humidity of above 70%. The coating material or paint prepared by using the fluorine-containing polyaryletherketone of the present application also has the advantages of the fluorine-containing polyaryletherketone.

[0065] The above implementation modes are only preferred implementation modes of the present application, and may not be used to limit the scope of protection of the present application. Any non-substantive changes and replacements made by those skilled in the art on the basis of the present application all belong to the scope of protection claimed by the present application.