Polyaryletherketone copolymer and preparation method thereof

Abstract

The invention discloses a polyaryletherketone copolymer and a preparation method thereof, the polyaryletherketone copolymer provided by the invention comprises a repeating unit in a formula I, a repeating unit in a formula II and a terminal unit, the repeating unit in the formula I comprises a 1, 4-naphthalene diphenol structure, and the molar ratio of the formula I to the formula II is 55: 45-95: 5. According to the polyaryletherketone copolymer, a 1, 4-naphthalene diphenol structure is introduced, so that the melting point is reduced while the high-temperature-resistant characteristic is maintained, the regulation and control of the melting point and the melt viscosity are realized at lower cost, and the polyaryletherketone copolymer is more suitable for industrial application such as carbon fiber impregnation and the like.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a polyaryletherketone copolymer and a preparation method thereof. Background Art

[0002] PEEK is an important high-performance engineering plastic with broad application prospects in aerospace, new energy vehicles, wind power and other fields. However, PEEK has a high melting point and melt viscosity, which makes it difficult to achieve a uniform effect when impregnated with continuous carbon fiber, making it impossible to prepare high-quality continuous carbon fiber reinforced prepreg unidirectional tape. This technical problem seriously restricts the application of PEEK as a substitute for traditional materials in the above fields.

[0003] In the prior art, PEEK materials are usually processed by traditional methods such as injection molding and extrusion molding, or by preparing continuous carbon fiber reinforced prepreg unidirectional tapes. These processing methods require high temperature and pressure conditions, and also rely on professional equipment and technology, which not only increases the difficulty of processing, but also significantly increases production costs. These problems pose a dual technical and economic challenge to manufacturers, and also affect the actual application effect of the product on the client side.

[0004] VICTREX-LMPAEK developed by British Victrex Manufacturing Company TM (low melting point PAEK) products, including VICTREXAE 250 unidirectional tape and VICTREX AM 200 wire, have improved processing performance to a certain extent, but these products use all-benzenediol structure raw material routes, such as 1,4-benzenediol, 1,2-benzenediol or 1,3-benzenediol, 4,4′-biphenylenediol, etc., resulting in high production costs. In addition, while maintaining high temperature resistance, these products also need to further optimize their performance indicators such as glass transition temperature (Tg). Summary of the invention

[0005] The purpose of the present invention is to provide a polyaryletherketone copolymer and a preparation method thereof, so as to solve the technical problems of high melting point and high viscosity of PEEK in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a polyaryletherketone copolymer, comprising: a repeating unit of formula I, a repeating unit of formula II and a terminal unit, wherein the molar ratio of the repeating unit of formula I to the repeating unit of formula II is 55:45 to 95:5;

[0008] The repeating unit of formula I comprises:

[0009]

[0010] The repeating unit of formula II is:

[0011]

[0012] Optionally, the repeating unit of formula I comprises a mixture of 50 to 90 mol% of a repeating unit of formula III and 10 to 50 mol% of a repeating unit of formula IV and an independent unit of formula V, wherein:

[0013] The repeating unit of formula III is:

[0014]

[0015] The repeating unit of formula IV is:

[0016]

[0017] The independent unit of formula V is a RnPEEK structural unit containing a 1,4-naphthalene diol structure.

[0018] Optionally, the repeating unit of formula I comprises a mixture of 65 to 90 mol % of the repeating unit of formula III and 10 to 35 mol % of the repeating unit of formula IV and the independent unit of formula V.

[0019] Optionally, the repeating unit of formula I comprises a mixture of 80 to 90 mol % of the repeating unit of formula III and 10 to 20 mol % of the repeating unit of formula IV and an independent unit of formula V.

[0020] Optionally, the repeating unit of formula I comprises 50 to 90 mol% of a repeating unit of formula III and 10 to 50 mol% of an independent unit of formula V, and the repeating unit of formula III is:

[0021]

[0022] The independent unit of formula V is a RnPEEK structural unit containing a 1,4-naphthalene diol structure.

[0023] Optionally, the molar ratio of the repeating unit of formula I to the repeating unit of formula II is 90:10 to 80:20.

[0024] Optionally, the terminal group of the copolymer is an -OH group or a -F group.

[0025] Optionally, the terminal groups of the copolymer include

[0026] The present invention also provides a method for preparing the polyaryletherketone copolymer as described above, comprising:

[0027] subjecting a mixture of 4,4'-difluorobenzophenone and a dihydroxy compound to a polycondensation reaction;

[0028] Adding a capping agent to the reaction system, wherein the capping agent is selected from at least one of phenol and 4-tert-butylphenol;

[0029] Wherein, the mixture of dihydroxy compounds includes 1,4-dihydroxynaphthalene, and at least one of 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl and 1,3-dihydroxybenzene;

[0030] The molar content of the 1,4-dihydroxynaphthalene is 10% to 50% of the total molar amount of the dihydroxy compound mixture.

[0031] Optionally, the polycondensation reaction is carried out under alkaline conditions, and the alkaline conditions are achieved by adding an alkaline compound, and the alkaline compound is selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide.

[0032] The polyaryletherketone copolymer provided by the present invention can effectively lower the melting point while maintaining a relatively high glass transition temperature by introducing 1,4-naphthalene diol structural units into the molecular structure, thereby reducing the processing temperature and improving the processing performance, making it easier to be impregnated with continuous carbon fibers, which is beneficial for preparing high-quality continuous carbon fiber reinforced prepreg unidirectional tapes.

[0033] By adopting a specific ratio of various structural units and using a capping agent for end-capping, the molecular weight distribution of the polymer can be further optimized, and its thermal stability and mechanical properties can be improved. At the same time, by carrying out the polycondensation reaction under alkaline conditions, the reaction rate and product yield can be increased and the production cost can be reduced. DETAILED DESCRIPTION

[0034] The present invention will be described in more detail below, wherein preferred embodiments of the present invention are shown, and it should be understood that those skilled in the art can modify the present invention described herein, and still achieve the beneficial effects of the present invention. Therefore, the following description should be understood as being widely known to those skilled in the art, and not as a limitation of the present invention.

[0035] The present invention is described in more detail by way of example in the following paragraphs. Advantages and features of the present invention will become more apparent from the following description.

[0036] The invention provides a polyaryletherketone copolymer, comprising: a repeating unit of formula I, a repeating unit of formula II and a terminal unit, wherein the molar ratio of the repeating unit of formula I to the repeating unit of formula II is 55:45 to 95:5.

[0037] The repeating unit of formula I comprises:

[0038]

[0039] The repeating unit of formula II is:

[0040]

[0041] The repeating unit of formula I comprises 50 to 90 mol% of the repeating unit of formula III and 10 to 50 mol% of a mixture of the repeating unit of formula IV and the independent unit of formula V, wherein:

[0042] The repeating unit of formula III is:

[0043]

[0044] The repeating unit of formula IV is:

[0045]

[0046] The independent unit of formula V is a RnPEEK structural unit containing a 1,4-naphthalene diol structure.

[0047] In a preferred embodiment, the repeating unit of formula I comprises a mixture of 65 to 90 mol% of repeating units of formula III and 10 to 35 mol% of repeating units of formula IV and independent units of formula V. In a more preferred embodiment, the repeating unit of formula I comprises a mixture of 80 to 90 mol% of repeating units of formula III and 10 to 20 mol% of repeating units of formula IV and independent units of formula V. This ratio can better balance the melting point and temperature resistance of the material.

[0048] In another specific embodiment, the copolymer may be a copolymer that does not include a repeating unit of formula IV.

[0049] That is, the repeating unit of formula I comprises 50 to 90 mol% of the repeating unit of formula III and 10 to 50 mol% of the independent unit of formula V, and the repeating unit of formula III is:

[0050]

[0051] The independent unit of formula V is a RnPEEK structural unit containing a 1,4-naphthalene diol structure.

[0052] It should be noted that Formula I provides no information as to whether the ether bond of the -O-Ph-O- moiety is arranged in a para, meta or ortho configuration, whereas Formulas III, IV and V specify this, as do all other configurations within the repeat unit.

[0053] Furthermore, the molar ratio of the repeating unit of formula I to the repeating unit of formula II is 60:40 to 90:10, preferably 70:30 to 90:10, and preferably 80:20 to 90:10.

[0054] In a more preferred embodiment, the molar ratio of the repeating unit of formula I to the repeating unit of formula II is 90:10 to 80:20.

[0055] Furthermore, the terminal group of the copolymer is an -OH group or a -F group.

[0056] Furthermore, the terminal groups of the copolymer include:

[0057]

[0058] In this embodiment, the terminal unit helps to improve the thermal stability of the copolymer.

[0059] The preparation method of the present invention is described in detail below:

[0060] S1: subjecting a mixture of 4,4'-difluorobenzophenone and a dihydroxy compound to a condensation reaction;

[0061] S2: adding a blocking agent to the reaction system, wherein the blocking agent is selected from at least one of phenol and 4-tert-butylphenol;

[0062] The mixture of dihydroxy compounds includes 1,4-dihydroxynaphthalene and at least one of 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl and 1,3-dihydroxybenzene; the molar content of 1,4-dihydroxynaphthalene is 10% to 50% of the total molar amount of the mixture of dihydroxy compounds.

[0063] The polycondensation reaction is carried out under alkaline conditions, and the alkaline conditions are achieved by adding an alkaline compound, and the alkaline compound is selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide. The specific reaction temperature, pressure and other conditions belong to the conventional means of those skilled in the art and will not be repeated here.

[0064] The present invention reduces the melting point of the material while maintaining good high temperature resistance by introducing a 1,4-naphthalene diol structure; adopts a low-cost 1,4-naphthalene diol structure raw material route to reduce production costs; by regulating the proportion of different structural units, the melting point and melt viscosity of the material can be flexibly adjusted; the processing performance of the material is improved to make it more suitable for industrial applications such as carbon fiber impregnation; the material has good thermal stability and mechanical properties and can be widely used in aerospace, new energy vehicles, wind power and other fields.

[0065] Embodiment 2

[0066] According to the polyaryletherketone copolymer and its preparation method provided in Example 1, this example provides performance characterization experiments, including a melting point (Tm) test experiment to verify the effect of lowering the melting point and a melt viscosity test to prove the improvement of processing performance.

[0067] Embodiment 3

[0068] According to a polyaryletherketone copolymer and a preparation method thereof provided in Example 1, this example provides a comparative experiment, in which the polyaryletherketone copolymer provided in Example 1 is compared with VICTREX-LMPAEK TM The performance of the products was compared to verify the effect of 1,4-naphthalenediol content on the performance, as well as the performance changes under different monomer ratios.

[0069] It can be seen from the above test results that the polyaryletherketone copolymer provided by the present invention achieves performance optimization by rationally designing the ratio of the repeating unit of formula I to the repeating unit of formula II (55:45 to 95:5) and introducing a specific ratio of 1,4-naphthalenediol structural units into the repeating unit of formula I.

[0070] In summary, the polyaryletherketone copolymer provided by the present invention comprises a repeating unit of formula I, a repeating unit of formula II and a terminal unit, and the molar ratio of the repeating unit of formula I to the repeating unit of formula II is 55:45 to 95:5. By introducing 1,4-naphthalene diol structural units and optimizing the proportion of each component, the copolymer achieves a lower melting point and regulation of melt viscosity while maintaining good high temperature resistance. The present invention adopts a low-cost 1,4-naphthalene diol structural raw material route, which not only reduces production costs, but also improves the processing properties of the material. The copolymer has excellent thermal stability and mechanical properties, is particularly suitable for industrial applications such as carbon fiber impregnation, and can be widely used in lightweight requirements in the fields of aerospace, new energy vehicles, wind power, etc.

[0071] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A polyaryletherketone copolymer, characterized in that: include: A repeating unit of formula I, a repeating unit of formula II and a terminal unit, wherein the molar ratio of the repeating unit of formula I to the repeating unit of formula II is 55:45 to 95:5; The repeating unit of formula I comprises: The repeating unit of formula II is:

2. The polyaryletherketone copolymer according to claim 1, characterized in that The repeating unit of formula I comprises 50 to 90 mol% of the repeating unit of formula III and 10 to 50 mol% of a mixture of the repeating unit of formula IV and the independent unit of formula V, wherein: The repeating unit of formula III is: The repeating unit of formula IV is: The independent unit of formula V is a RnPEEK structural unit containing a 1,4-naphthalene diol structure.

3. The polyaryletherketone copolymer according to claim 2, characterized in that The repeating unit of formula I comprises a mixture of 65 to 90 mol % of repeating units of formula III and 10 to 35 mol % of repeating units of formula IV and individual units of formula V.

4. The polyaryletherketone copolymer according to claim 3, characterized in that The repeating unit of formula I comprises a mixture of 80 to 90 mol % of the repeating unit of formula III and 10 to 20 mol % of the repeating unit of formula IV and the independent unit of formula V.

5. The polyaryletherketone copolymer according to claim 1, characterized in that The repeating unit of formula I comprises 50 to 90 mol% of a repeating unit of formula III and 10 to 50 mol% of an independent unit of formula V, wherein the repeating unit of formula III is: The independent unit of formula V is a RnPEEK structural unit containing a 1,4-naphthalene diol structure.

6. The polyaryletherketone copolymer according to claim 1, characterized in that The molar ratio of the repeating unit of formula I to the repeating unit of formula II is 90:10 to 80:

20.

7. The polyaryletherketone copolymer according to claim 1, characterized in that The terminal group of the copolymer is an -OH group or a -F group.

8. The polyaryletherketone copolymer according to claim 1, characterized in that The terminal groups of the copolymer include 9. A method for preparing the polyaryletherketone copolymer according to any one of claims 1 to 8, characterized in that: include: subjecting a mixture of 4,4'-difluorobenzophenone and a dihydroxy compound to a polycondensation reaction; Adding a capping agent to the reaction system, wherein the capping agent is selected from at least one of phenol and 4-tert-butylphenol; Wherein, the mixture of dihydroxy compounds includes 1,4-dihydroxynaphthalene, and at least one of 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl and 1,3-dihydroxybenzene; The molar content of the 1,4-dihydroxynaphthalene is 10% to 50% of the total molar amount of the dihydroxy compound mixture.

10. The method according to claim 9, characterized in that The polycondensation reaction is carried out under alkaline conditions, and the alkaline conditions are achieved by adding alkaline compounds, and the alkaline compound is selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide.

Images