Preparation method of polyaryletherketone resin with alkyl structure in main chain, polyaryletherketone resin with alkyl structure in main chain and application thereof

Abstract

The present application discloses a preparation method of a polyaryletherketone resin with an alkyl structure in the main chain, a polyaryletherketone resin with an alkyl structure in the main chain and applications thereof. The preparation method includes: reacting a mixture of a side-chain structure bisphenol monomer, a dialkyl chain diacyl dihalide compound, a solvent, a catalyst and a water-carrying agent to obtain the polyaryletherketone resin with an alkyl structure in the main chain. 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.

Description

Technical Field

[0001] The present application relates to a preparation method of a polyaryletherketone resin with an alkyl structure in the main chain, a polyaryletherketone resin with an alkyl structure in the main chain, and applications thereof, belonging 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, polyaryletherketone containing an alkyl structure has 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. Bisphenol A bis(4-phenoxyphenyl)phosphine oxide 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 to restrict the thermal motion of the alkyl chain with a dicarbonyl group. At the same time, the electron-withdrawing effect of the carbonyl group activates the para-halogen, enabling the obtaining of a relatively high number-average molecular weight 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. Meanwhile, the reduction of the processing temperature allows 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 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-planar bisphenol and an activated bis-halide compound containing an alkyl structure. The feature is the introduction of an alkyl group in 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 with an alkyl structure in the main chain is provided. The preparation method includes:

[0006] Reacting a mixture of a side-chain structure bisphenol monomer, a diacyl bis-halide compound containing an alkyl chain, a solvent, a catalyst, and a water-carrying agent to obtain the polyaryletherketone resin with an alkyl structure in the main chain.

[0007] Optionally, the side-group-structured bisphenol monomer is selected from at least one of isoindolinone bisphenol, hexafluorobisphenol A, phenolphthalein, bisphenol fluorene, bisphenol A, and phenolphthalin.

[0008] Optionally, the alkyl-chain-containing diacyl dihalide compound is selected from at least one of 1,4-bis(4-fluorophenyl)butane-1,4-dione, 4,4'-difluorobenzophenone, 1,4-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 side-group-structured bisphenol monomer to the alkyl-chain-containing diacyl dihalide compound is 1:1.

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

[0011] Optionally, the molar ratio of the side-group-structured bisphenol monomer 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 side-group-structured bisphenol monomer to the water-carrying agent is 10 to 100 mol: 25 to 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 dosage of the side-group-structured bisphenol monomer is 15% to 35% of the mass of the solvent.

[0016] Optionally, the temperature of the reaction is 160 to 230 °C, and the reaction time is 2 to 4 h.

[0017] According to another aspect of the present application, there is provided a polyaryletherketone resin having an alkyl structure in the main chain prepared by the above-mentioned preparation method, and the polyaryletherketone resin having an alkyl structure in the main chain is selected from one of the structures shown in Formula I, Formula II, and Formula III;

[0018]

[0019] In Formula I, the value range of m is 0 to 100, the value range of n is 01 to 100, and m and n are integers;

[0020] In formula II, m ranges from 0 to 100, n ranges from 0 to 100, and m and n are integers;

[0021] In formula III, m ranges from 0 to 100, n ranges from 0 to 100, and m and n are integers.

[0022] Specifically, the structures shown in formula I, formula II, and formula III are prepared through the following structural formula.

[0023]

[0024] Optionally, the glass transition temperature of the polyaryletherketone resin with an alkyl group-containing main chain is 160 - 220 °C.

[0025] According to another aspect of the present application, there is provided a polyaryletherketone resin with an alkyl group-containing main chain prepared by the above-mentioned preparation method, and the application of the above-mentioned polyaryletherketone resin with an alkyl group-containing main chain in special engineering plastics.

[0026] 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 dialkyl chain-containing diacyl dihalobenzene. 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 bis(halophenyl)glyoxal, the introduced alkyl chain increases the repeating segment length and the flexibility of the main chain. The dialkyl chain-containing diacyl group has two carbonyl groups, which can undergo cyclization reactions and intermolecular crosslinking reactions with o-phenylenediamine, substances with a 1,2-diamino structure, etc., to obtain a special engineering plastic with higher stability.

[0027] The beneficial effects that can be produced by the present application include:

[0028] 1) The polyaryletherketone resin with an alkyl group-containing main chain provided by the present application has easily available raw materials and has a certain cost advantage.

[0029] 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. Description of the Drawings

[0030] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the polyaryletherketone resin prepared in Example 1 of the present application. Detailed Embodiments

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

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

[0033]

[0034] Example 1

[0035] 11.8026 g of isoindolinone bisphenol, 1.6456 g of 1,4-bis(4-fluorophenyl)butane-1,4-dione, 5.2370 g of 4,4'-difluorobenzophenone and 4.7681 g of anhydrous potassium carbonate were added to a three-necked flask. 50.2 g of sulfolane was used as a solvent, and 45 ml of toluene was used as a water-carrying agent and added to the three-necked flask. Under nitrogen protection, it was heated to 130 °C, and toluene carried water for 4 hours. Then it was further heated to remove xylene and the generated water, and the temperature was raised to 200 °C and reacted for 4 hours.

[0036] The product was poured into a mixed solution of alcohol and water for precipitation, crushed, boiled and washed repeatedly 10 times, filtered and then dried in vacuo to obtain a yellow polymer powder. The value of m is 80, and the value of n is 20. It can be seen from Figure 1 the structure of the prepared polyaryletherketone.

[0037] The glass transition temperature was measured by differential scanning calorimetry and an instrument (DSC25, TA).

[0038] The glass transition temperature was 235 °C.

[0039]

[0040] Example 2

[0041] 5.9014 g of isoindolinone bisphenol, 4.7750 g of phenolphthalein, 8.2881 g of 1,4-bis(4-fluorophenyl)butane-1,4-dione and 5.2 g of anhydrous potassium carbonate were added to a three-necked flask. 40.8 g of sulfolane was used as a solvent, and 10 ml of toluene was used as a water-carrying agent and added to the three-necked flask. Toluene carried water, and under nitrogen protection, it was heated to 135 °C, and toluene carried water for 2 hours. Then the temperature was raised to 180 °C and reacted for 8 hours.

[0042] The product was poured into a mixed solution of alcohol and water for precipitation, crushed, boiled and washed repeatedly 10 times, filtered and then dried in vacuo to obtain a yellow polymer powder. The value of m is 50, and the value of n is 50. The glass transition temperature was 233 °C.

[0043]

[0044] Example 3

[0045] 3.362 g of hexafluorobisphenol A, 1.373 g of 1,4-bis(4-fluorophenyl)butane-1,4-dione, 1.3012 g of 1,4-bis(4-fluorophenyl)propane-1,3-dione and 1.589 g of potassium carbonate were added into a three-necked flask with 14 g of N-methylpyrrolidone as the solvent. Under nitrogen protection, the mixture was heated to 130 °C, and 5 ml of toluene was used to carry water for 1 hour. Then the temperature was raised to 170 °C and the reaction was carried out for 7 hours.

[0046] The product was poured into a mixed solution of alcohol and water for precipitation, crushed, boiled and washed repeatedly for 10 times, filtered and then dried in vacuo to obtain a yellow polymer powder. The value of m is 50 and the value of n is 50. The glass transition temperature is 162 °C.

[0047]

[0048] 0.5 g of the polymer powder prepared in Example 1 was dissolved in 10 ml of N-methylpyrrolidone, 0.12 g of o-phenylenediamine was added, and the mixture was heated to 50 °C and reacted for 18 h to obtain a light yellow precipitate of polyquinoxaline with a glass transition temperature of 263 °C.

[0049] The above 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 art, without departing from the technical solution of the present application, makes some changes or modifications using the disclosed technical content, which are equivalent to equivalent embodiments and all fall within the scope of the technical solution.

Claims

1. A preparation method of a polyaryletherketone resin with an alkyl structure in the main chain, characterized in that, The preparation method includes: Reacting a mixture of a side-chain structured bisphenol monomer, an alkyl-chain-containing diacyl dihalide compound, a solvent, a catalyst, and a water-carrying agent to obtain the polyaryletherketone resin with an alkyl structure in the main chain; The side-chain structured bisphenol monomer is selected from at least one of isatin bisphenol, hexafluorobisphenol A, phenolphthalein, bisphenol fluorene, bisphenol A, and phenolphthalin; The alkyl-chain-containing diacyl dihalide 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 side-chain structured bisphenol monomer to the alkyl-chain-containing diacyl dihalide 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 bicarbonate, and potassium bicarbonate; The molar ratio of the side-chain structured bisphenol monomer to the catalyst is 1:1 to 1:1.

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 side-chain structured bisphenol monomer 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 dosage of the side-chain structured bisphenol monomer is 15% - 35% of the mass of the solvent.

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 - 4 h.

7. A polyaryletherketone resin with an alkyl structure in the main chain prepared by the preparation method according to any one of claims 1 to 6, characterized in that, The polyaryletherketone resin with an alkyl structure in the main chain is selected from one of the structures shown in Formula II and Formula III; In Formula II, the value range of m is 0 - 100, the value range of n is 0 - 100, and m and n are integers; In Formula III, the value range of m is 0 - 100, the value range of n is 0 - 100, and m and n are integers.

8. The polyaryletherketone resin with an alkyl structure in the main chain according to claim 7, characterized in that, The glass transition temperature of the polyaryletherketone resin with an alkyl structure in the main chain is 160 - 220 °C.

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

Images