Low-surface-energy polyaryletherketone resin as well as preparation method and application thereof

Abstract

The invention provides low-surface-energy polyaryletherketone resin and a preparation method and application thereof.The low-surface-energy polyaryletherketone resin is polyaryletherketone resin grafted with a siloxane side chain, and the mass ratio of the siloxane side chain to the polyaryletherketone resin is (5-20): 100; the polyaryletherketone resin with low surface energy contains a siloxane side chain; the value range of the polymerization degree of the polyaryletherketone is 30 to 600. According to the polyaryletherketone resin with low surface energy provided by the invention, a siloxane side chain is introduced to a main chain of the polyaryletherketone resin, so that the surface energy of the polyaryletherketone resin is reduced, and the polyaryletherketone resin has better self-lubricating performance, lower surface friction coefficient and better demolding performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer materials, in particular to a low-surface-energy polyaryletherketone resin and a preparation method and application thereof. BACKGROUND

[0002] Polyaryletherketone is a kind of crystalline polymer connected by phenylene ring through oxygen bridge (ether bond) and carbonyl (ketone). According to the connection order and proportion difference of ether bond, ketone group and benzene ring in the molecular chain, a plurality of polyaryletherketone polymers with different structures can be formed. Since the polyaryletherketone molecular structure contains rigid benzene ring, it has excellent high-temperature stability, mechanical properties, electrical insulation, radiation resistance and chemical resistance, etc. However, the polyaryletherketone itself contains polar groups, and the material has high surface energy, and the demolding property is also poor. In the demolding process, the workpiece is prone to deformation due to demolding difficulty. SUMMARY

[0003] The present application provides a low-surface-energy polyaryletherketone resin. By introducing siloxane side chains into the main chain of the polyaryletherketone resin, the surface energy of the polyaryletherketone resin is reduced, the self-lubricating property is better, the surface friction coefficient is reduced, and the demolding property is better.

[0004] A low-surface-energy polyaryletherketone resin, the low-surface-energy polyaryletherketone resin is a polyaryletherketone resin grafted with siloxane side chains, the mass ratio of the siloxane side chains to the polyaryletherketone resin is 5-20:100; the low-surface-energy polyaryletherketone resin contains a structural unit of the siloxane side chain, and the structural formula (I) is as follows:

[0005] Structural formula (I) The polyaryletherketone has a polymerization degree in the range of 30-600; in the structural formula (I), the structure of the substituent group R is , R1 is methyl or ethyl, R2 is -CH2- or -CH2CH2-, and m is less than 50.

[0006] The demolding property of the polyaryletherketone resin itself is poor. The siloxane side chains are grafted onto the main chain of the polyaryletherketone, the surface energy of the polyaryletherketone is reduced by using the siloxane side chains, the demolding property of the polyaryletherketone resin is enhanced, and the workpiece deformation problem caused by demolding difficulty in the demolding process is reduced.

[0007] Meanwhile, the low-surface-energy polyaryletherketone resin can be prepared into a workpiece for a field requiring a low friction coefficient, or made into a wear-resistant workpiece with high self-lubricating requirement, and the low-surface-energy polyaryletherketone resin can also be prepared into ultra-fine powder for electrostatic spraying or prepared into water-based non-stick coating in the form of dispersion liquid for non-stick coating industry.

[0008] If the content of the siloxane side chain on the polyaryletherketone resin is too high, the performance of the polyaryletherketone itself can be affected, and appropriate grafting can reduce the surface energy of the polyaryletherketone resin while maintaining the performance of the polyaryletherketone resin itself. The siloxane side chain on the polyaryletherketone resin is preferentially grafted at a position with less steric hindrance.

[0009] The following also provides several optional modes, but not as an additional limitation to the above overall scheme, just a further supplement or preferred, without technical or logical contradiction, each optional mode can be combined with the above overall scheme alone, but also between multiple optional modes.

[0010] Optionally, the polyaryletherketone resin has a degree of polymerization of 30 to 300. Further preferably, the polyaryletherketone resin has a degree of polymerization of 30 to 100.

[0011] Optionally, in the substituent R of structural formula (I), m is less than 30. Further preferably, in the substituent R of structural formula (I), m has a value range of 5 to 25.

[0012] Optionally, the polyaryletherketone resin is at least one of polyetherketone, polyetheretherketone, polyetherketoneketone, polyetheretherketoneketone, polyetherketoneetherketoneketone, and phenolphthalein type polyaryletherketone.

[0013] The main chain of the polyaryletherketone resin contains rigid benzene rings and carbonyl groups or ether bonds between the two benzene rings, and the siloxane side chain is connected at the carbonyl position.

[0014] The application also provides a preparation method of the low surface energy polyaryletherketone resin. (a) preparing a polyaryletherketone to obtain a polyaryletherketone resin solution, adding a monoamino siloxane to the polyaryletherketone resin solution, and reacting to obtain the low surface energy polyaryletherketone resin; (b) dissolving the polyaryletherketone resin and the monoamino siloxane in a diphenyl sulfone solvent, and reacting to obtain the low surface energy polyaryletherketone resin; (c) heating and blending the polyaryletherketone resin and the monoamino siloxane to react and melt extrude to obtain the low surface energy polyaryletherketone resin.

[0015] The structure of the monoamino siloxane is as follows:

[0016] In the structural formula, m has a value range of less than 50, further preferably, m has a value range of less than 30, and more preferably, m has a value range of 5 to 25, R1 is methyl or ethyl, and R2 is -CH2- or -CH2CH2-.

[0017] The carbonyl group in the polyaryletherketone reacts with the primary amine in the mono-amino siloxane via nucleophilic addition and dehydration to form a Schiff base structure (C=N-), and the siloxane is chemically grafted onto the main chain of the polyaryletherketone resin.

[0018] Optionally, in the method (a), the method (b), and the method (c), the mass ratio of the mono-amino siloxane to the polyaryletherketone resin is 5-20:100, and the average molar mass (molecular weight) of the mono-amino siloxane is 500-2000 g / mol.

[0019] The mass ratio of the mono-amino siloxane to the polyaryletherketone resin is 5-20:100. Further preferably, the mass ratio of the mono-amino siloxane to the polyaryletherketone resin is 10-20:100.

[0020] The molecular weight of the mono-amino siloxane is 500-2000 g / mol. Relative to mono-amino siloxanes with other molecular weights, this range of molecular weight ensures sufficient end-amino content for the grafting reaction, while providing a suitable molecular weight, hydrophobicity, and non-stick properties.

[0021] Optionally, in the method (a), after the mono-amino siloxane is added to the polyaryletherketone resin solution, the reaction is carried out at a temperature in the range of 250-350°C for a time of 5-60 min to obtain the low-surface-energy polyaryletherketone resin.

[0022] Optionally, in the method (b), the polyaryletherketone resin and the mono-amino siloxane are dissolved in a diphenyl sulfone solvent, and the reaction is carried out at a temperature in the range of 250-350°C for a time of 5-60 min to obtain the low-surface-energy polyaryletherketone resin.

[0023] Optionally, in the method (c), the polyaryletherketone resin and the mono-amino siloxane are heated and blended at a temperature of 300-420°C and melt-extruded to obtain the low-surface-energy polyaryletherketone resin.

[0024] In the method (a), the method (b), and the method (c), the molecular weight, melt viscosity, and melt flowability of the polyaryletherketone can be in a wide range. For example, for polyether ether ketone, the melt flow rate in the engineering plastics field is generally 5-100 cm 3 / 10 min (test conditions: 380°C, 5 kg); and the melt flow rate in the coating field is 80-150 cm 3 / 10 min (380°C, 5 kg). Relative to polymers with other melt flow rates, this flow parameter ensures that the polymer has sufficient flowability and film-forming property as a coating material, while still maintaining sufficient molecular weight and stable high polymer properties.

[0025] The methods (a), (b) and (c) are carried out at high temperature, which is beneficial to the grafting reaction. In the method (a), the mono-amino siloxane is directly added into the reaction solution after the synthesis of the polyaryletherketone resin, and in the method (b), the polyaryletherketone resin and the mono-amino siloxane are simultaneously dissolved in the diphenyl sulfone solvent.

[0026] After the reaction, the product obtained in the methods (a) and (b) is in liquid state, which is subjected to post-treatment, such as drying, to obtain the low surface energy polyaryletherketone resin in solid state, and in the method (c), the polyaryletherketone resin and the mono-amino siloxane are granulated in the twin-screw extruder to obtain the low surface energy polyaryletherketone resin in solid state.

[0027] The application also provides a low surface energy polyaryletherketone resin prepared by the above method.

[0028] The application also provides a polyaryletherketone product prepared by the low surface energy polyaryletherketone resin.

[0029] The low surface energy polyaryletherketone resin can be processed by injection molding, extrusion molding, compression molding and 3D printing, and for the processing technology involving demolding, the low surface energy polyaryletherketone resin provided by the application has the advantage of demolding, and the product size is more accurate.

[0030] The polyaryletherketone resin has wide application in industry, such as high-temperature hydraulic equipment sealing, chemical reaction kettle, pipeline flange, aircraft fuselage, wing, tail, implantable medical devices and the like, and the polyaryletherketone resin provided by the application has good demolding performance without loss of mechanical properties, and can be used in the existing polyaryletherketone resin scene.

[0031] The low surface energy polyaryletherketone resin provided by the application can reduce the surface energy of the polyaryletherketone resin by introducing appropriate length of siloxane side chain on the main chain of the polyaryletherketone resin, but does not affect the mechanical properties, high-temperature stability and other properties of the polyaryletherketone itself, and can be used as a self-lubricating workpiece to increase self-lubricating and wear-resistant properties, or as a non-stick coating raw material to provide non-stickiness, which has wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 Comparison of infrared spectra of PEEK resin and low surface energy PEEK resin prepared in Example 2; Figure 2 DSC graph of low surface energy PEEK resin prepared in Example 2; Figure 3G' and G" of the low surface energy PEEK resin prepared for Example 2 as a function of shear frequency. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by a person of ordinary skill in the art without any creative work fall within the scope of protection of the present application.

[0034] In order to better describe and illustrate the embodiments of the present application, one or more drawings can be referred to, but additional details or examples used to describe the drawings should not be considered as limiting the scope of any one of the inventions, the presently described embodiments or the preferred modes of the present application.

[0035] It should be noted that when a component is referred to as being "connected" with another component, it can be directly connected with the other component or there can be a middle component. When a component is referred to as being "disposed on" another component, it can be directly disposed on the other component or there can be a middle component.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein only for the purpose of describing the specific embodiments and is not intended to limit the present application.

[0037] Example 1 Low surface energy polyether ketone resin Take 100 g of polyether ketone powder (Gharda Company G-PAEK™ 1400P), mix 20 g of monoamine siloxane with a number average molecular weight of 1200 g / mol (0.017 mol), after uniform mixing, use a double screw extruder to granulate at 380°C, and the low surface energy polyether ketone resin is obtained.

[0038] Example 2 Low surface energy polyether ether ketone resin A 1 L four-necked flask was charged with 400 g of diphenyl sulfone, and heated to about 150°C. After the diphenyl sulfone was completely melted, 38.20 g (0.347 mol) of hydroquinone and 75.70 g (0.347 mol) of 4,4'-difluorobenzophenone were added, and stirred until uniform. Then, 37.14 g (0.35 mol) of sodium carbonate was added. The temperature was slowly increased to 300°C, and the reaction was continued for half an hour. Then, a resin solution containing 100 g (theoretical value) of polyether ether ketone was obtained. To the resin solution, 20 g (0.017 mol) of monoamino silicone having a number average molecular weight of 1200 g / mol was added, and the mixture was reacted at 300°C for 1 hour. The solution was poured into a flat-bottomed pan, and cooled. The product was pulverized and washed with ethanol until the diphenyl sulfone was completely removed. The product was dried, and a polyether ether ketone resin having low surface energy was obtained.

[0039] Example 3 Polyether ketone ketone resin having low surface energy A 1 L four-necked flask was charged with 400 g of diphenyl sulfone, and heated to about 150°C. After the diphenyl sulfone was completely melted, 38.20 g (0.347 mol) of hydroquinone and 75.70 g (0.347 mol) of 4,4'-difluorobenzophenone were added, and stirred until uniform. Then, 37.14 g (0.35 mol) of sodium carbonate was added. The temperature was slowly increased to 300°C, and the reaction was continued for half an hour. Then, a resin solution containing 100 g (theoretical value) of polyether ether ketone was obtained. To the resin solution, 20 g (0.017 mol) of monoamino silicone having a number average molecular weight of 1200 g / mol was added, and the mixture was reacted at 300°C for 1 hour. The solution was poured into a flat-bottomed pan, and cooled. The product was pulverized and washed with ethanol until the diphenyl sulfone was completely removed. The product was dried, and a polyether ether ketone resin having low surface energy was obtained.

[0040] Example 4 Polyether ether ketone ketone resin having low surface energy A 1 L four-necked flask was charged with 400 g of diphenyl sulfone, and heated to about 150°C. After the diphenyl sulfone was completely melted, 38.20 g (0.347 mol) of hydroquinone and 75.70 g (0.347 mol) of 4,4'-difluorobenzophenone were added, and stirred until uniform. Then, 37.14 g (0.35 mol) of sodium carbonate was added. The temperature was slowly increased to 300°C, and the reaction was continued for half an hour. Then, a resin solution containing 100 g (theoretical value) of polyether ether ketone was obtained. To the resin solution, 20 g (0.017 mol) of monoamino silicone having a number average molecular weight of 1200 g / mol was added, and the mixture was reacted at 300°C for 1 hour. The solution was poured into a flat-bottomed pan, and cooled. The product was pulverized and washed with ethanol until the diphenyl sulfone was completely removed. The product was dried, and a polyether ether ketone resin having low surface energy was obtained.

[0041] Example 5 Polyether ketone ether ketone ketone resin having low surface energy Take a 1L four-necked flask, and introduce argon. Add 350g of diphenyl sulfone, and heat to about 150℃. After completely melted, add 42.30g (0.197mol) of 4,4'-dihydroxybenzophenone and 63.67g (0.197mol) of 1,4-bis(4-fluorobenzoyl)benzene, and after stirring evenly, add 21.14g (0.200mol) of sodium carbonate. Slowly heat to 320℃, and continue to react for half an hour to obtain a resin solution containing 100g of polyether ketone ether ketone ketone. Add 20g (0.017mol) of monoamino silicone with a number average molecular weight of 1200g / mol, and react for 1 hour. Pour the solution into a flat-bottomed pan, and after cooling, crush and wash with ethanol several times until the diphenyl sulfone is completely removed. After drying, a low-surface-energy polyether ketone ether ketone ketone resin is obtained.

[0042] Example 6: Low-surface-energy phenolphthalein-type polyaryletherketone resin Take 100g of Zhejiang Park EPEKC phenolphthalein-type polyaryletherketone powder, and mix with 20g (0.017mol) of monoamino silicone with a number average molecular weight of 1200g / mol. After mixing evenly, use a twin-screw extruder to granulate at 300℃ to obtain a low-surface-energy phenolphthalein-type polyaryletherketone resin.

[0043] Examples 7-12 Table 1

[0044] In Examples 1-12, the monoamino silicone used is Yr21098 (number average molecular weight 1200) produced by Hubei Yaimaid Biological. The temperature in Table 1 is the temperature at which the monoamino silicone reacts with the polyaryletherketone resin.

[0045] The low-surface-energy polyaryletherketone resins prepared in Examples 1-12 were characterized for performance, and the results are shown in Table 2.

[0046] Table 2

[0047] In Table 2, the water contact angle was tested using the test method of GB / T22638.9-2016, and the tensile strength was tested using the test method of ISO527 standard.

[0048] The test method for thermal stability is as follows: The test was conducted using a Hacker rheometer. An isothermal time-scan test was selected. During the 150-minute isothermal test at the target temperature (30°C above the material's melting point), 150 sampling points were recorded with a spacing of 0.9 mm. The sample was heated for 2 minutes, scraped at the edge, and then isothermal for 2 minutes. The frequency was 1 Hz, and the viscosity change over time was monitored. If the parameters remained stable for a long period, it indicated that the material had good thermal stability. If significant drift occurred, it indicated that the thermal aging effect was significant. Table 2 shows the duration for which the sample viscosity remained stable.

[0049] In Table 2, the enthalpy change of melting at crystallization ΔHm is obtained using DSC testing (see attached figure). Figure 2 ΔHm can reflect the crystallinity of the material. The crystallinity of polyaryletherketone grafted with alkoxy side chains does not change significantly, and the physical properties of the material remain at the original level.

[0050] The infrared spectrum of the low surface energy PEEK prepared in Example 2 is shown in [reference needed]. Figure 1 As shown by the red line in the image, and Figure 1 Infrared spectrum of PEEK without grafted siloxane ( Figure 1 Compared to the black line in the image, it is 1046cm longer. -1 The infrared absorption peak at 2950 cm⁻¹ corresponds to the antisymmetric stretching vibration peak of the silicon-oxygen-silicon bond (Si-O-Si) in polysiloxane; -1 The absorption peaks at this location are more pronounced, originating from the aliphatic CH vibration peaks in siloxanes.

[0051] See Figure 2 As shown, the low surface energy polyetheretherketone resin of Example 2 was subjected to DSC testing. The DSC test was conducted in a nitrogen atmosphere, and the temperature control of the DSC included the following stages: 1. The temperature is increased from 25℃ to 380℃ at a rate of 20℃ / min; 2. Keep warm at 380℃ for 5 minutes; 3. Cooling from 380℃ to 25℃ at a rate of 40℃ / min; 4. The temperature is increased from 25℃ to 380℃ at a rate of 20℃ / min; 5. Keep warm at 380℃ for 5 minutes.

[0052] Figure 2 The data for each peak are summarized in Table 3.

[0053] Table 3

[0054] See Figure 2As shown, the onset temperature of the glass transition is 146.27℃, and the midpoint ISO is 150.76℃. The DSC curve of the polyether ether ketone grafted with siloxane does not change greatly compared with the polyether ether ketone without grafting siloxane, which proves that the physical properties of the material do not change greatly.

[0055] The low-surface-energy polyether ether ketone resin prepared in Example 2 was subjected to viscosity rheological test, and the results are shown in Table 2. Figure 3 As shown, with the increase of the frequency f, both G' and G'' monotonously increase, which indicates that the elasticity and viscosity of the material are enhanced at high frequency. The two curves have an intersection, and at the intersection point, G'=G'', which indicates that the material changes from "viscous behavior" to "elastic behavior".

[0056] The technical features of the above-described embodiments can be combined in any manner. In order to make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, however, as long as the combinations of the technical features do not contradict each other, they should be considered as falling within the scope of the present disclosure.

[0057] The above-described embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled persons in the art, some modifications and improvements can be made without departing from the concept of the present application, and these all fall within the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A polyaryletherketone resin having a low surface energy, characterized in that, The low-surface-energy polyaryletherketone resin is a polyaryletherketone resin grafted with siloxane side chains, and the mass ratio of the siloxane side chains to the polyaryletherketone resin is 5-20:100; the structural formula (I) of the structural unit containing the siloxane side chains in the low-surface-energy polyaryletherketone resin is shown as follows: The structural formula (I) is shown as follows: The degree of polymerization of the polyaryletherketone ranges from 30 to 600; in the structural formula (I), the structure of the substituent R is , R1 is a methyl or ethyl group, R2 is -CH2- or -CH2CH2-, and m is less than 50.

2. The low surface energy poly(arylene ether ketone) resin of claim 1, wherein, The degree of polymerization of the polyaryletherketone resin is 30-300.

3. The low surface energy poly(aryl ether ketone) resin of claim 1, wherein, In the substituent R of the structural formula (I), m is less than 30.

4. A process for the preparation of a low surface energy poly (arylene ether ketone) resin as claimed in any one of claims 1 to 3, characterised in that, Any one of the following methods is used: (a) preparing a polyaryletherketone to obtain a polyaryletherketone resin solution, adding a monoamino siloxane to the polyaryletherketone resin solution, and reacting to obtain the low-surface-energy polyaryletherketone resin; (b) dissolving the polyaryletherketone resin and the monoamino siloxane in a diphenyl sulfone solvent, and reacting to obtain the low-surface-energy polyaryletherketone resin; (c) heating and blending the polyaryletherketone resin and the monoamino siloxane for reaction and melt extrusion to obtain the low-surface-energy polyaryletherketone resin.

5. The method for preparing the low surface energy polyaryletherketone resin as described in claim 4, characterized in that, In the method (a), the method (b), and the method (c), the mass ratio of the monoamino siloxane to the polyaryletherketone resin is 5-20:100, and the average molar mass of the monoamino siloxane is 500-2000 g / mol.

6. The method for preparing the low surface energy polyaryletherketone resin as described in claim 4, characterized in that, In the method (a), after the monoamino siloxane is added to the polyaryletherketone resin solution, the reaction is carried out at a temperature in the range of 250-350°C for a time of 5-60 min to obtain the low-surface-energy polyaryletherketone resin.

7. The method for preparing the low surface energy polyaryletherketone resin as described in claim 4, characterized in that, In the method (b), the polyaryletherketone resin and the monoamino siloxane are dissolved in a diphenyl sulfone solvent, and the reaction is carried out at a temperature in the range of 250-350°C for a time of 5-60 min to obtain the low-surface-energy polyaryletherketone resin.

8. The method for preparing the low surface energy polyaryletherketone resin as described in claim 4, characterized in that, In the method (c), the polyaryletherketone resin and the monoamino siloxane are heated and blended for reaction at a temperature in the range of 300-420°C and melt extrusion to obtain the low-surface-energy polyaryletherketone resin.

9. A low surface energy polyaryletherketone resin, characterized in that, The low-surface-energy polyaryletherketone resin is prepared by using the preparation method according to any one of claims 4-8.

10. A polyaryletherketone article characterized in that, The low-surface-energy polyaryletherketone resin is prepared by using the low-surface-energy polyaryletherketone resin according to any one of claims 1-3.

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