A PEEK resin polymer and its preparation method and application

Abstract

The invention relates to the field of polymer materials, and discloses a PEEK resin polymer and a preparation method and application thereof. The PEEK resin polymer contains repeating units shown in formulas I and II, wherein the molar content of the repeating units shown in formula I is 20-30%. The invention uses hexafluorobutanol, isophorone diisocyanate and diethanolamine as raw materials to synthesize fluorine-containing diols, uses 4,4'-bis(3-aminophenoxy)benzophenone and 4-chlorophthalic anhydride as raw materials to synthesize bischloroimide phenoxybenzophenone, then generates a terminal hydroxyl intermediate by reacting the fluorine-containing diol and the bischloroimide phenoxybenzophenone, and then introduces the terminal hydroxyl intermediate into the PEEK resin polymer structure, thereby enhancing the solubility thereof and improving the hydrophobicity and heat resistance thereof.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and specifically relates to a PEEK resin polymer and a preparation method and application thereof. Background Art

[0002] Polyetheretherketone is a semi-crystalline thermoplastic special engineering plastic with excellent comprehensive properties such as high temperature resistance, aging resistance, creep resistance, corrosion resistance, radiation resistance and good biocompatibility. It is widely used in civil fields such as aerospace, electronics and electrical, automotive parts, precision machinery, medical equipment and national defense and military fields. With the rapid development of various fields, the requirements for the high temperature modulus and strength of polyetheretherketone materials are gradually increasing.

[0003] Due to the strong rigidity and high regularity of the polyetheretherketone structure, the solubility of polyetheretherketone is poor and the melting temperature is high, resulting in poor processing performance and high processing cost of polyetheretherketone materials. In addition, the glass transition temperature of polyetheretherketone is only about 140°C, which causes its mechanical properties to be greatly attenuated at higher temperatures, limiting its application in high-temperature harsh environments. The existing technology uses a melt blending method to fill and modify polyetheretherketone with high heat-resistant fillers such as carbon nanotubes and graphite, but the addition of high heat-resistant fillers usually leads to a significant decrease in the mechanical strength and toughness of the material. In addition, due to the high melt viscosity and solvent resistance of polyetheretherketone, the introduced thermally conductive filler has the problem of poor interface compatibility. Summary of the invention

[0004] In order to solve the deficiencies mentioned in the above background technology, the purpose of the present invention is to provide a PEEK resin polymer and its preparation method and application, by reacting a fluorinated diol and bis(chloroimide)phenoxybenzophenone to generate a terminal hydroxyl intermediate, which is then introduced into the PEEK resin polymer structure to enhance its solubility while improving its hydrophobicity and heat resistance.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A PEEK resin polymer comprising repeating units shown in formula I and formula II:

[0007] (Formula I);

[0008] (Formula II);

[0009] Wherein, the molar content of the repeating unit shown in formula I is 20-30%.

[0010] Preferably, the preparation method of the PEEK resin polymer comprises the following steps:

[0011] A. Take hexafluorobutanol in a reactor, raise the temperature to 75-85°C, add isophorone diisocyanate and dibutyltin dilaurate to react for 2-3 hours, then cool to room temperature, add diethanolamine and continue to react for 10-20 minutes. After the reaction is completed, wash and dry to prepare a fluorinated diol;

[0012] B. Take 4,4'-bis(3-aminophenoxy)benzophenone, 4-chlorophthalic anhydride and toluene in a reactor, heat to 130-145°C, reflux for 3-5h, then heat to 165-175°C and continue to react for 1-2h. After the reaction is completed, the system solution is discharged in anhydrous ethanol, washed with toluene and filtered to dry, to prepare bischloroimidephenoxybenzophenone;

[0013] C. Put fluorinated diol and bis(chloroimide)phenoxybenzophenone into a reactor, add tetrahydrofuran solvent, stir and react for 5-7h, add triethylamine in batches during the reaction to remove hydrogen chloride produced by the reaction, and after the reaction is completed, filter, rotary evaporate and dry to obtain a terminal hydroxyl intermediate;

[0014] D. Take 4,4'-difluorobenzophenone, hydroquinone and terminal hydroxyl intermediate in a reactor, add alkali metal carbonate, cyclopentane and toluene solvent, heat to 145-155°C for reaction for 2-3h, then heat to 160-180°C for reaction for 0.5-1h, continue to heat to 195-220°C for reaction for 2-3h, after the reaction is completed, pour the generated product into deionized water, wash, filter and dry to prepare PEEK resin polymer.

[0015] Preferably, in step A, the molar ratio of hexafluorobutanol, isophorone diisocyanate and diethanolamine is 1-1.05:1:1-1.02.

[0016] Preferably, in step B, the molar ratio of 4,4'-bis(3-aminophenoxy)benzophenone to 4-chlorophthalic anhydride is 1:2-2.3.

[0017] Preferably, in step C, the molar ratio of the fluorinated diol to the bis(chloroimide)phenoxybenzophenone is 2-2.5:1.

[0018] Preferably, in step D, the total molar ratio of hydroquinone and the terminal hydroxyl intermediate to the molar ratio of 4,4'-difluorobenzophenone is 1-1.03:1.

[0019] Preferably, in step D, the alkali metal carbonate is a mixture of anhydrous potassium carbonate and anhydrous sodium carbonate in a molar ratio of 15 to 19:1.

[0020] As mentioned above, the application of PEEK resin polymer is used to prepare bullet casings, high temperature resistant electronic devices and aerospace structural parts.

[0021] Beneficial effects of the present invention:

[0022] The invention uses hexafluorobutanol, isophorone diisocyanate and diethanolamine as raw materials, and the hydroxyl group in the hexafluorobutanol structure reacts with the isocyanate group connected to the methylene group in the isophorone diisocyanate structure to prepare a fluorine-containing isocyanate substance, and then continues to react with diethanolamine. The activity of the secondary amine in the diethanolamine structure is more active than the hydroxyl group. The secondary amine in the diethanolamine reacts with the isocyanate group directly connected to the cyclohexane ring to generate a fluorine-containing diol by controlling the temperature. At the same time, the invention uses 4,4'-bis(3-aminophenoxy)benzophenone and 4-chlorophthalic anhydride as raw materials to synthesize bischloroimide phenoxybenzophenone, and then the prepared fluorine-containing diol and bischloroimide phenoxybenzophenone undergo a substitution reaction to prepare a terminal hydroxyl intermediate, and finally the terminal hydroxyl intermediate, 4,4'-difluorobenzophenone and hydroquinone are used as raw materials for copolymerization to obtain a PEEK resin polymer. The flexible chain segments in the PEEK resin polymer structure enhance its solubility, and the introduced fluorine-containing groups enhance its hydrophobicity, expanding its application in hydrophobic coatings, electronic devices, information materials and other fields. In addition, the introduced imide structure enhances its heat resistance, further expanding its application in bullet casings, high-temperature resistant electronic devices, aerospace structural parts and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 is an infrared spectrum of the fluorinated diol prepared in Example 1 of the present invention;

[0025] Figure 2 It is the infrared spectrum of bischloroimide phenoxybenzophenone prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1 A method for preparing a PEEK resin polymer comprises the following steps:

[0028] A. Take 9.10g of hexafluorobutanol in a reactor, heat it to 80°C, add 11.11g of isophorone diisocyanate and 0.005g of dibutyltin dilaurate to react for 3h, then cool to room temperature, add 5.26g of diethanolamine and continue to react for 20min. After the reaction is completed, wash and dry to prepare a fluorinated diol;

[0029] Infrared test image of fluorinated diol Figure 1 As shown, 3329cm -1 The characteristic absorption peak of -OH is 1242 cm -1 and 2028cm -1 The absorption peak of CF bond is 2268cm -1 The characteristic absorption peak of the isocyanate group disappeared, indicating that the fluorinated diol was successfully synthesized;

[0030] B. Take 9.91g of 4,4'-bis(3-aminophenoxy)benzophenone, 9.13g of 4-chlorophthalic anhydride and toluene in a reactor, heat to 140°C, reflux for 5h, then heat to 170°C and continue to react for 1h. After the reaction is completed, the system solution is discharged in anhydrous ethanol, washed with toluene and filtered to dry, to prepare bischloroimidephenoxybenzophenone;

[0031] The infrared test image of bis(chloroimide)phenoxybenzophenone is as follows: Figure 2 As shown, 3050cm -1 The absorption peak of the aromatic ring CH stretching vibration is 1720cm -1 The absorption peak of the carbonyl group of the imide ring is 1610 cm -1 The CN vibration absorption peak is at 1500cm -1 The absorption peak of the benzene ring skeleton is 1380cm -1 The characteristic absorption peak of the imide benzene ring is 1200cm -1 The position is the absorption peak of aromatic ether stretching vibration, indicating the successful synthesis of bis(chloroimide)phenoxybenzophenone;

[0032] C. 12.19 g of fluorinated diol and 7.26 g of bis(chloroimide)phenoxybenzophenone were placed in a reactor, 100 mL of tetrahydrofuran was added, and the mixture was stirred for 6 h. During the reaction, 2.12 g of triethylamine was added in batches to remove the hydrogen chloride produced by the reaction. After the reaction was completed, the mixture was filtered, rotary evaporated, and dried to obtain a terminal hydroxyl intermediate.

[0033] D. Take 6.55g 4,4'-difluorobenzophenone, 2.48g hydroquinone and 12.54g terminal hydroxyl intermediate in a reactor, add 3.94g anhydrous potassium carbonate, 0.16g anhydrous sodium carbonate, 34.8mL sulfolane and 10mL toluene solvent, heat to 150℃ for reaction for 3h, then heat to 170℃ for reaction for 1h, continue to heat to 200℃ for reaction for 2h, after the reaction is completed, pour the generated product into deionized water, wash, filter and dry to prepare PEEK resin polymer.

[0034] Example 2 A method for preparing a PEEK resin polymer comprises the following steps:

[0035] A. Take 9.10g of hexafluorobutanol in a reactor, heat it to 80°C, add 11.11g of isophorone diisocyanate and 0.005g of dibutyltin dilaurate to react for 3h, then cool to room temperature, add 5.26g of diethanolamine and continue to react for 20min. After the reaction is completed, wash and dry to prepare a fluorinated diol;

[0036] B. Take 9.91g of 4,4'-bis(3-aminophenoxy)benzophenone, 9.13g of 4-chlorophthalic anhydride and toluene in a reactor, heat to 140°C, reflux for 5h, then heat to 170°C and continue to react for 1h. After the reaction is completed, the system solution is discharged in anhydrous ethanol, washed with toluene and filtered to dry, to prepare bischloroimidephenoxybenzophenone;

[0037] C. 12.19 g of fluorinated diol and 7.26 g of bis(chloroimide)phenoxybenzophenone were placed in a reactor, 100 mL of tetrahydrofuran was added, and the mixture was stirred for 6 h. During the reaction, 2.12 g of triethylamine was added in batches to remove the hydrogen chloride produced by the reaction. After the reaction was completed, the mixture was filtered, rotary evaporated, and dried to obtain a terminal hydroxyl intermediate.

[0038] D. Take 6.55g 4,4'-difluorobenzophenone, 2.31g hydroquinone and 15.04g terminal hydroxyl intermediate in a reactor, add 3.94g anhydrous potassium carbonate, 0.16g anhydrous sodium carbonate, 34.8mL sulfolane and 10mL toluene solvent, heat to 150℃ for reaction for 3h, then heat to 170℃ for reaction for 1h, continue to heat to 200℃ for reaction for 2h, after the reaction is completed, pour the generated product into deionized water, wash, filter and dry to prepare PEEK resin polymer.

[0039] Example 3 A method for preparing a PEEK resin polymer comprises the following steps:

[0040] A. Take 9.10g of hexafluorobutanol in a reactor, heat it to 80°C, add 11.11g of isophorone diisocyanate and 0.005g of dibutyltin dilaurate to react for 3h, then cool to room temperature, add 5.26g of diethanolamine and continue to react for 20min. After the reaction is completed, wash and dry to prepare a fluorinated diol;

[0041] B. Take 9.91g of 4,4'-bis(3-aminophenoxy)benzophenone, 9.13g of 4-chlorophthalic anhydride and toluene in a reactor, heat to 140°C, reflux for 5h, then heat to 170°C and continue to react for 1h. After the reaction is completed, the system solution is discharged in anhydrous ethanol, washed with toluene and filtered to dry, to prepare bischloroimidephenoxybenzophenone;

[0042] C. 12.19 g of fluorinated diol and 7.26 g of bis(chloroimide)phenoxybenzophenone were placed in a reactor, 100 mL of tetrahydrofuran was added, and the mixture was stirred for 6 h. During the reaction, 2.12 g of triethylamine was added in batches to remove the hydrogen chloride produced by the reaction. After the reaction was completed, the mixture was filtered, rotary evaporated, and dried to obtain a terminal hydroxyl intermediate.

[0043] D. Take 6.55g 4,4'-difluorobenzophenone, 2.64g hydroquinone and 10.03g terminal hydroxyl intermediate in a reactor, add 3.94g anhydrous potassium carbonate, 0.16g anhydrous sodium carbonate, 34.8mL sulfolane and 10mL toluene solvent, heat to 150℃ for reaction for 3h, then heat to 170℃ for reaction for 1h, continue to heat to 200℃ for reaction for 2h, after the reaction is completed, pour the generated product into deionized water, wash, filter and dry to prepare PEEK resin polymer.

[0044] Comparative Example 1 A method for preparing a PEEK resin polymer comprises the following steps:

[0045] A. Take 9.91g of 4,4'-bis(3-aminophenoxy)benzophenone, 9.13g of 4-chlorophthalic anhydride and toluene in a reactor, heat to 140°C, reflux for 5h, then heat to 170°C and continue to react for 1h. After the reaction is completed, the system solution is discharged in anhydrous ethanol, washed with toluene and filtered to dry, to prepare bischloroimidephenoxybenzophenone;

[0046] B. Take 6.55g 4,4'-difluorobenzophenone, 2.48g hydroquinone and 5.44g dichloroimide phenoxybenzophenone in a reactor, add 3.94g anhydrous potassium carbonate, 0.16g anhydrous sodium carbonate, 34.8mL sulfolane and 10mL toluene solvent, heat to 150℃ and react for 3h, then heat to 170℃ and continue to react for 1h, continue to heat to 200℃ and react for 2h. After the reaction is completed, pour the generated product into deionized water, wash, filter and dry to prepare PEEK resin polymer.

[0047] Comparative Example 2 A method for preparing a PEEK resin polymer comprises the following steps:

[0048] Take 6.55g 4,4'-difluorobenzophenone, 2.48g hydroquinone and 0.93g 2,5-dihydroxytoluene in a reactor, add 3.94g anhydrous potassium carbonate, 0.16g anhydrous sodium carbonate, 34.8mL cyclopentane sulfone and 10mL toluene solvent, heat to 150°C for reaction for 3h, then heat to 170°C for reaction for 1h, continue to heat to 200°C for reaction for 2h, and after the reaction is completed, pour the generated product into deionized water, wash, filter and dry to prepare a PEEK resin polymer.

[0049] Performance Testing

[0050] The properties of the PEEK resin polymers prepared in Examples 1-3 and Comparative Examples 1-2 were tested:

[0051] (1) Solubility test: At room temperature, 0.01 g of the PEEK resin polymer prepared in Examples 1-3 was added to 1 mL of solvent respectively, and the solubility of the sample was tested. The test results are shown in Table 1.

[0052]

[0053] Note: + means dissolved, - means insoluble

[0054] It can be seen from the data results in Table 1 that the PEEK resin polymers prepared in Examples 1-3 of the present invention are soluble in most common organic solvents, and the solubility of the polymers is relatively strong. The reason is that the introduction of the trifluoromethyl group in the fluorinated diol enhances the flexibility of the molecular chain, and the introduction of the imide structure in the bischloroimide phenoxybenzophenone destroys the regularity of the polyetheretherketone structure, increases the free volume of the polymer main chain, and makes it easier for solvent molecules to penetrate, thereby improving the solubility of the PEEK resin polymer.

[0055] (2) Differential scanning calorimetry test: The glass transition temperature (Tg) of PEEK resin polymer was measured by differential scanning calorimeter. During the test, 8 mg of sample was weighed, the temperature range was set to 50~380℃, and the temperature was increased twice under nitrogen protection, with a heating rate of 10℃ / min; Thermogravimetric analysis test: The PEEK resin polymer sample was tested under nitrogen atmosphere by thermogravimetric analyzer, and the temperature was increased to 800℃ at a heating rate of 10℃ / min; Water contact angle test: The water contact angle of PEEK resin polymer was tested by contact angle meter, and the data results are shown in Table 2.

[0056]

[0057] From the data in Table 2, it can be seen that the glass transition temperature of the PEEK resin polymer prepared in Examples 1-3 of the present invention is greater than 170°C, the 5% thermal weight loss temperature and the 10% thermal weight loss temperature are greater than 550°C, and it has strong heat resistance. The reason is that the thermal stability of the PEEK resin polymer is determined by the polymer chain structure, the polarity of the imide structure introduced by the terminal hydroxyl intermediate is strong, and the intermolecular force between the molecular chains is strong, resulting in the PEEK resin polymer having a higher thermal decomposition temperature, and its water contact angle is greater than 120°, because fluorine has a strong electronegativity, and the introduction of fluorine atoms enhances the hydrophobicity of the PEEK resin polymer. Among them, no fluorinated diol is introduced in Comparative Example 1, and its measured hydrophobicity is lower than that of Examples 1-3, and no terminal hydroxyl intermediate is introduced in Comparative Example 2, and its measured water contact angle, glass transition temperature and thermal decomposition temperature are lower than those of Examples 1-3, indicating that the introduction of terminal hydroxyl intermediates can improve the hydrophobicity and heat resistance of PEEK resin polymers to a certain extent.

[0058] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0059] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A PEEK resin polymer, characterized in that: Containing repeating units shown in formula I and formula II: (Formula I); (Formula II); Wherein, the molar content of the repeating unit shown in formula I is 20-30%.

2. A method for preparing a PEEK resin polymer as claimed in claim 1, characterized in that: The following steps are involved: A. Take hexafluorobutanol in a reactor, raise the temperature to 75-85°C, add isophorone diisocyanate and dibutyltin dilaurate to react for 2-3 hours, then cool to room temperature, add diethanolamine and continue to react for 10-20 minutes. After the reaction is completed, wash and dry to prepare a fluorinated diol; B. Take 4,4'-bis(3-aminophenoxy)benzophenone, 4-chlorophthalic anhydride and toluene in a reactor, heat to 130-145°C, reflux for 3-5h, then heat to 165-175°C and continue to react for 1-2h. After the reaction is completed, the system solution is discharged in anhydrous ethanol, washed with toluene and filtered to dry, to prepare bischloroimidephenoxybenzophenone; C. Put fluorinated diol and bis(chloroimide)phenoxybenzophenone into a reactor, add tetrahydrofuran solvent, stir and react for 5-7h, add triethylamine in batches during the reaction to remove hydrogen chloride produced by the reaction, and after the reaction is completed, filter, rotary evaporate and dry to obtain a terminal hydroxyl intermediate; D. Take 4,4'-difluorobenzophenone, hydroquinone and terminal hydroxyl intermediate in a reactor, add alkali metal carbonate, cyclopentane and toluene solvent, heat to 145-155°C for reaction for 2-3h, then heat to 160-180°C for reaction for 0.5-1h, continue to heat to 195-220°C for reaction for 2-3h, after the reaction is completed, pour the generated product into deionized water, wash, filter and dry to prepare PEEK resin polymer.

3. The method for preparing a PEEK resin polymer according to claim 2, characterized in that: In the step A, the molar ratio of hexafluorobutanol, isophorone diisocyanate and diethanolamine is 1-1.05:1:1-1.

02.

4. The method for preparing a PEEK resin polymer according to claim 2, characterized in that: In the step B, the molar ratio of 4,4'-bis(3-aminophenoxy)benzophenone to 4-chlorophthalic anhydride is 1:2-2.

3.

5. The method for preparing a PEEK resin polymer according to claim 2, characterized in that: In the step C, the molar ratio of the fluorinated diol to the bis(chloroimide)phenoxybenzophenone is 2-2.5:

1.

6. The method for preparing a PEEK resin polymer according to claim 2, characterized in that: In the step D, the total molar ratio of hydroquinone and the terminal hydroxyl intermediate to the molar ratio of 4,4'-difluorobenzophenone is 1-1.03:

1.

7. The method for preparing a PEEK resin polymer according to claim 2, characterized in that: In the step D, the alkali metal carbonate is a mixture of anhydrous potassium carbonate and anhydrous sodium carbonate in a molar ratio of 15-19:

1.

8. An application of the PEEK resin polymer as claimed in claim 1, characterized in that: The PEEK resin polymer is used to prepare bullet casings, high-temperature resistant electronic devices and aerospace structural parts.

Images