Preparation method of polyaryletherketone resin containing alkyl structure, polyaryletherketone resin containing alkyl structure and application thereof

Abstract

The present application discloses a preparation method of a polyaryletherketone resin containing an alkyl structure, a polyaryletherketone resin containing an alkyl structure and an application thereof. The preparation method includes: reacting a mixture of a phenolic compound, a dihalobenzophenone compound, a catalyst, a water-carrying agent and a solvent under an inert atmosphere to obtain the polyaryletherketone resin containing an alkyl structure. The polyaryletherketone resin provided by the present application can be further modified to form a new structure having a nitrogen heterocycle or crosslinking, and these new structures have higher heat stability.

Description

Technical Field

[0001] The present application relates to a preparation method of a polyaryletherketone resin containing an alkyl structure, a polyaryletherketone resin containing an alkyl structure and applications thereof, and belongs to the technical field of polymer synthesis. Background Art

[0002] Polyaryletherketone resins are widely used special engineering plastics, mainly including polyetheretherketone, polyetherketoneetherketoneketone, etc. Due to the insufficient dimensional stability of semi-crystalline resins in a relatively large temperature range from the glass transition temperature to the melting point, a series of amorphous polyaryletherketone resins with excellent dimensional stability have been gradually developed to replace some applications in high-temperature fields. Since the polymer chain is mainly composed of carbonyl groups, aromatic rings and ether bonds, after introducing large distorted non-planar structural side groups, the chain rigidity increases and the glass transition temperature rises, resulting in a significant increase in the processing temperature. To solve the processing application problems brought about, polyaryletherketones containing alkyl structures have been synthesized. For example, bisphenol A is introduced into the main chain of polyaryletherketone, but the methyl group as a side group has a small steric hindrance and is affected by thermal motion, with a relatively low glass transition temperature of only 152-155°C. Bis(4-hydroxyphenyl)diisopropylmethane has a bis(isopropyl) side group structure and is more likely to move, with a glass transition temperature of 180-190°C, both not exceeding 200°C. Summary of the Invention

[0003] In the present application, an alkyl structure is introduced into the polymer main chain, and a dicarbonyl group is used to restrict the thermal motion of the alkyl chain. At the same time, the electron-withdrawing effect of the carbonyl group activates the para-halogen, so that a relatively high number-average molecular weight can be obtained while maintaining the processing performance of the polymer. The introduction of a flexible chain reduces the glass transition temperature of the polymer to a certain extent, and the reduction of the processing temperature enables some auxiliaries with relatively low thermal stability, such as polyethylene terephthalate, polyethylene furandicarboxylate, polyvinyl alcohol, etc., to be well dispersed in the molding of polyaryletherketone and will not degrade during the molding process.

[0004] In the present application, a polyaryletherketone resin with a relatively high molecular weight is prepared through a polycondensation reaction of a non-coplanar bisphenol and an activated bishalide compound containing an alkyl structure. The feature is the introduction of an alkyl group into the main chain, which takes into account both the rigidity and flexibility of the main chain, minimizing the reduction of the glass transition temperature of the polymer. This resin can further form a more stable polyarylether resin and find applications in special engineering plastics.

[0005] According to one aspect of the present application, a preparation method of a polyaryletherketone resin containing an alkyl structure is provided, and the preparation method includes:

[0006] Reacting a mixture of a phenolic compound, a bishalobenzophenone compound, a catalyst, a water-carrying agent and a solvent in an inert atmosphere to obtain the polyaryletherketone resin containing an alkyl structure.

[0007] Optionally, the phenolic compound is selected from at least one of phenolphthalein, bisphenol A, hexafluorobisphenol A, isatinone bisphenol, bisphenol fluorene, and phenolphthalinone.

[0008] Optionally, the dihalobenzophenone compound is selected from at least one of 1,4-bis(4-fluorophenyl)butane-1,4-dione, 1,3-bis(4-fluorophenyl)propane-1,3-dione, 1,4-bis(4-fluorophenyl)pentane-1,4-dione, 1,4-bis(4-fluorophenyl)hexane-1,4-dione, 1,4-bis(4-fluorophenyl)heptane-1,4-dione, and 1,4-bis(4-fluorophenyl)octane-1,4-dione.

[0009] Optionally, the molar ratio of the phenolic compound to the dihalobenzophenone compound is 1:1.

[0010] Optionally, the catalyst is selected from at least one of potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0011] Optionally, the molar ratio of the phenolic compound to the catalyst is 1:1 to 1:1.2.

[0012] Optionally, the water-carrying agent is selected from at least one of toluene, xylene, and n-hexane.

[0013] Optionally, the molar volume ratio of the phenolic compound to the water-carrying agent is 10 - 100 mol: 25 - 45 ml.

[0014] Optionally, the solvent is selected from at least one of N-methylpyrrolidone, sulfolane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0015] Optionally, the molar volume ratio of the phenolic compound to the solvent is 10 - 100 mol: 10 - 100 ml.

[0016] Optionally, the temperature of the reaction is 160 - 230 °C, and the reaction time is 2 - 8 h.

[0017] Optionally, the temperature of the reaction is selected from any value of 160 °C, 170 °C, 190 °C, 200 °C, 210 °C, 230 °C or the range value between any two of the above.

[0018] Optionally, the reaction time is selected from any value of 2 h, 3 h, 4 h, 5 h, 7 h, 8 h or the range value between any two of the above.

[0019] Optionally, the inert atmosphere is selected from at least one of a nitrogen atmosphere and an argon atmosphere.

[0020] According to another aspect of the present application, there is provided a polyaryletherketone resin containing an alkyl structure prepared by the above-mentioned preparation method, and the polyaryletherketone resin containing an alkyl structure is selected from one of the structures shown in Formula I, Formula II, Formula III, Formula IV, and Formula V;

[0021]

[0022] The value range of n is 0 to 100; the value range of m is 0 to 100; the value range of p is 0 to 100, the value range of q is 0 to 100, and the value range of e is 0 to 100.

[0023] Optionally, the glass transition temperature of the polyaryletherketone resin containing an alkyl structure is 150 to 220 °C.

[0024] According to still another aspect of the present application, there is provided an application of the polyaryletherketone resin containing an alkyl structure prepared by the above-mentioned preparation method and the polyaryletherketone resin containing an alkyl structure in special engineering plastics.

[0025] In the present application, starting from the molecular design of the polyaryletherketone resin, a polyaryletherketone material with high heat resistance is prepared through the polycondensation reaction of a bisphenol monomer with a side group structure and a diacyl bishalobenzene containing an alkyl chain. The relatively large side group increases the steric hindrance of the polymer side chain, hinders the stacking of the polymer main chain, and increases the molecular spatial volume; compared with dihalobenzophenone or bishalobenzil, the introduced alkyl chain increases the length of the repeating segment and increases the flexibility of the main chain. The diacyl containing an alkyl chain has two carbonyl groups, and can undergo cyclization reactions and intermolecular crosslinking reactions with o-phenylenediamine, substances with a 1,2-diamino structure, etc., to obtain special engineering plastics with higher stability.

[0026] The beneficial effects that can be produced by the present application include:

[0027] 1) The polyaryletherketone resin containing an alkyl structure provided by the present application has easily available raw materials and has a certain cost advantage.

[0028] 2) The polyaryletherketone resin provided by the present application can be further modified to form new structures with azacycles or crosslinks, and these new structures have higher heat stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is the DSC diagram in Example 5 of the present application.

[0030] Figure 2 It is the nuclear magnetic resonance hydrogen spectrum of Example 5 of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] The present application will be described in detail below in conjunction with embodiments, but the present application is not limited to these embodiments.

[0032] Unless otherwise specified, the raw materials in the embodiments of the present application are all purchased through commercial channels.

[0033] Example 1

[0034] 3.183 g of phenolphthalein, 2.743 g of 1,4-bis(4-fluorophenyl)butane-1,4-dione and 2.073 g of anhydrous potassium carbonate were added to a three-necked flask, and 12.5 g of sulfolane was added as a solvent to the three-necked flask. Under nitrogen protection, it was heated to 130 °C, and 25 ml of toluene was used to carry water for 4 hours. The temperature was raised to 200 °C and the reaction was carried out for 4 hours.

[0035] The product was poured into a mixed solution of alcohol and water for precipitation, crushed, repeatedly boiled and washed 10 times, and vacuum dried after filtration to obtain a yellow polymer powder. The value of n is 50.

[0036] The glass transition temperature was measured by differential scanning calorimetry and an instrument (DSC25, TA).

[0037] The glass transition temperature was 214 °C.

[0038]

[0039] Example 2

[0040] 2.284 g of bisphenol A, 3.072 g of 1,4-bis(4-chlorophenyl)butane-1,4-dione and 1.589 g of anhydrous potassium carbonate were added to a three-necked flask, 15 g of sulfolane was used as a solvent, and toluene was used to carry water. Under nitrogen protection, it was heated to 130 °C, and 10 ml of toluene was used to carry water for 2 hours. The temperature was raised to 180 °C and the reaction was carried out for 8 hours.

[0041] The product was poured into a mixed solution of alcohol and water for precipitation, crushed, repeatedly boiled and washed 10 times, and vacuum dried after filtration to obtain a yellow polymer powder. The value of n is 50, and the glass transition temperature is 170 °C.

[0042]

[0043] Example 3

[0044] 3.372 g of hexafluorobisphenol A, 2.743 g of 1,4-bis(4-fluorophenyl)butane-1,4-dione and 1.589 g of potassium carbonate were added to a three-necked flask with 14 g of N-methylpyrrolidone as a solvent. Under nitrogen protection, it was heated to 130 °C, and 5 ml of toluene was used to carry water for 1 hour. The temperature was raised to 170 °C and the reaction was carried out for 7 hours.

[0045] The product was poured into a mixed solution of alcohol and water for precipitation, crushed, repeatedly boiled and washed 10 times, filtered and then dried under vacuum to obtain a yellow polymer powder. The value of n is 50, and the glass transition temperature is 162 °C.

[0046]

[0047] Dissolve 0.5 g of the yellow polymer powder prepared in Example 3 in 10 ml of N-methylpyrrolidone, add 0.12 g of o-phenylenediamine, heat to 50 °C, and react for 18 h to obtain a light yellow precipitate of polyquinoxaline with a glass transition temperature of 183 °C.

[0048] Example 4

[0049] Add 3.372 g of hexafluorobisphenol A, 2.602 g of 1,3-bis(4-fluorophenyl)propane-1,3-dione, and 1.589 g of K2CO3 (15% in excess) to a three-necked flask. Add 14 g of N-methylpyrrolidone as a solvent to the three-necked flask, heat to 130 °C under nitrogen protection, and use 5 ml of toluene to carry water for 1 hour. Raise the temperature to 170 °C and react for 7 hours.

[0050]

[0051] The product was poured into a mixed solution of alcohol and water for precipitation, crushed, repeatedly boiled and washed 10 times, filtered and then dried under vacuum to obtain a yellow polymer powder. The value of n is 50, and the glass transition temperature is 162 °C.

[0052] Example 5

[0053] Add 3.934 g of isatin bisphenol, 2.743 g of 1,4-bis(4-fluorophenyl)butane-1,4-dione, and 1.589 g of potassium carbonate to a three-necked flask. Add 14 g of N-methylpyrrolidone as a solvent to the three-necked flask, heat to 130 °C under nitrogen protection, and use 5 ml of toluene to carry water for 1 hour. Raise the temperature to 170 °C and react for 7 hours.

[0054] The product was poured into a mixed solution of alcohol and water for precipitation, crushed, repeatedly boiled and washed 10 times, filtered and then dried under vacuum to obtain a yellow polymer powder. The value of n is 50, and the glass transition temperature is 162 °C.

[0055]

[0056] From Figure 1 it can be seen the glass transition temperature of the prepared polyaryletherketone. From Figure 2 it can be seen the structure of the prepared polyaryletherketone.

[0057] As described above, these are only several embodiments of the present application and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the relevant art can make some changes or modifications within the scope of the technical solution of the present application by using the disclosed technical content, which are equivalent to equivalent implementation cases and all fall within the scope of the technical solution.

Claims

1. A preparation method of a polyaryletherketone resin containing an alkyl structure, characterized in that, The preparation method includes: Under an inert atmosphere, reacting a mixture of a phenolic compound, a dihalobenzophenone compound, a catalyst, a water-carrying agent, and a solvent to obtain the polyaryletherketone resin with an alkyl structure; The phenolic compound is selected from at least one of phenolphthalein, bisphenol A, hexafluorobisphenol A, isatinone bisphenol, bisphenol fluorene, and phenolphthalin; The dihalobenzophenone compound is selected from at least one of 1,4-bis(4-fluorophenyl)butane-1,4-dione and 1,3-bis(4-fluorophenyl)propane-1,3-dione.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the phenolic compound to the dihalobenzophenone compound is 1:

1.

3. The preparation method according to claim 1, characterized in that, The catalyst is selected from at least one of potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate; The molar ratio of the phenolic compound to the catalyst is 1:1 to 1:

2.

4. The preparation method according to claim 1, characterized in that, The water-carrying agent is selected from at least one of toluene, xylene, and n-hexane; The molar volume ratio of the phenolic compound to the water-carrying agent is 10 - 100 mol: 25 - 45 ml.

5. The preparation method according to claim 1, characterized in that, The solvent is selected from at least one of N-methylpyrrolidone, sulfolane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide; The molar volume ratio of the phenolic compound to the solvent is 10 - 100 mol: 10 - 100 ml.

6. The preparation method according to claim 1, characterized in that, The temperature of the reaction is 160 - 230 °C, and the reaction time is 2 - 8 h; The inert atmosphere is selected from at least one of a nitrogen atmosphere and an argon atmosphere.

7. A polyaryletherketone resin containing an alkyl structure prepared by the preparation method according to any one of claims 1 to 6, characterized in that, The polyaryletherketone resin with an alkyl structure is selected from one of the structures shown in Formula I, Formula II, Formula III, Formula IV, and Formula V; The value range of n is 0 - 100; the value range of m is 0 - 100; the value range of p is 0 - 100, the value range of q is 0 - 100, and the value range of e is 0 - 100.

8. The polyaryletherketone resin containing an alkyl structure according to claim 7, characterized in that, The glass transition temperature of the polyaryletherketone resin with an alkyl structure is 150 - 220 °C.

9. Application of the polyaryletherketone resin containing an alkyl structure prepared by the preparation method according to any one of claims 1 to 6 in special engineering plastics.

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