A polyaryletherketone containing triptycene structure and its preparation method and application as special engineering plastics

Abstract

The present application discloses a polyaryletherketone containing a triptycene structure, a preparation method thereof, and an application thereof as a special engineering plastic. The controllable preparation of end-capping, linear and hyperbranched structures is achieved, and the polyaryletherketone has a series of advantages such as simplicity, high efficiency, and low cost. The product thereof can be used as a dye in polymer recovery and film processing.

Description

Technical Field

[0001] The present application belongs to the technical field of polymer synthesis, and specifically relates to a polyaryletherketone containing a triptycene structure, a preparation method thereof, and an application thereof as a special engineering plastic. Background Art

[0002] Polyarylether resin (PAEK, PES) is a fully aromatic thermoplastic special engineering plastic. Since its development, it has been regarded as a key material for national defense and military industry, and is widely used in aerospace, automotive industry, electronic and electrical, and medical machinery. Phenolphthalein polyaryletherketone (PEK-C) is a typical amorphous polymer in PAEK. It has the advantages of high strength, high modulus, good dimensional stability, insulation, corrosion resistance, radiation resistance, self-flaming retardant, outstanding fatigue resistance, and outstanding tribological properties. Its glass transition temperature is 228-234℃. The use temperature of amorphous polymers is generally below Tg. In order to increase the use temperature of the material, the main practice in the industry is to increase the glass transition temperature of the material. The specific method is to increase the free volume and increase the rigidity of the main chain. Tributylene is a D 3h Symmetrical aromatic ring structure, skeleton has good symmetry and rigidity, prepared triptycene-based polymers such as polyaryletherketone, polyarylethersulfone, polyester, etc. have good solubility in halogenated hydrocarbons. Introducing it into polymers can greatly improve the heat resistance of materials. Since triptycene does not have nucleophilic conditions, making triptycene into bisphenol or dihalogen is a common method for introducing triptycene structure in this industry. Summary of the invention

[0003] The purpose of the present invention is to provide a simple and efficient method for preparing triptycene into halogenated benzoyltriptycene with nucleophilic activity, and successfully prepare the halogenated benzoyltriptycene into a polyaryletherketone resin containing triptycene.

[0004] The invention uses triptycene molecules with different numbers of halogenated benzophenone as raw materials, and uses them as end-capping agents, monomers and hyperbranched structures for the synthesis of polyaryletherketone resin.

[0005] According to one aspect of the present application, a polyaryletherketone containing a triptycene structure is provided, having a structure shown in Formula I;

[0006] The structure contains triptycene, and a benzoyl group is connected to the triptycene.

[0007]

[0008] Where n≥3;

[0009] Ar is a bisphenol monomer The aromatic ring skeleton remaining after removing the phenolic hydroxyl group;

[0010] The molecular weight of the polyaryletherketone containing triptycene structure is ≥5000Da, and the molecular weight distribution is ≤3.5.

[0011] According to another aspect of the present application, a method for preparing the above-mentioned polyaryletherketone containing a triptycene structure is provided, comprising at least the following steps:

[0012] The raw materials containing substituted triptycene and bisphenol compound are mixed with a water-carrying agent, carbonate and solvent, and heated for reaction to obtain the polyaryletherketone containing triptycene structure.

[0013] The substituted triptycene is selected from at least one of 2,6-bis(4-fluorobenzoyl)triptycene, 2,6-bis(4-chlorobenzoyl)triptycene, 2,6-bis(4-bromobenzoyl)triptycene and 2,6-bis(4-nitrobenzoyl)triptycene;

[0014] The bisphenol compound is at least one selected from bisphenol A, hexafluorobisphenol A, phenolphthalein, thymolphthalein, o-cresolphthalein, bisphenol fluorene, biphenol, and hydroquinone;

[0015] The water-carrying agent is selected from at least one of cyclohexane, n-heptane, benzene, toluene, xylene, and chlorobenzene;

[0016] The carbonate is selected from at least one of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, cerium carbonate, and calcium carbonate;

[0017] The solvent is selected from at least one of sulfolane, diphenyl sulfone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and N-cyclohexylpyrrolidone.

[0018] The relationship between the amounts of each substance is as follows: in terms of molar fraction, the molar ratio of the substituted triptycene, the bisphenol compound, and the carbonate is 1:0.90-1.20:0.95-3.0;

[0019] The mass of the solvent is 2 to 6 times the sum of the mass of the substituted triptycene and the bisphenol compound, preferably 3 to 4.5 times;

[0020] The mass of the water-carrying agent is 0.5 to 2 times the mass of the solvent.

[0021] The heating reaction process comprises: heating to boiling of the water-carrying agent under nitrogen protection, maintaining for 1 to 5 hours, removing the water-carrying agent, and then heating to 150 to 230° C., maintaining for 0.5 to 24 hours.

[0022] According to another aspect of the present application, a special engineering plastic is provided, comprising the above-mentioned polyaryletherketone containing a triptycene structure or the polyaryletherketone containing a triptycene structure prepared by the above-mentioned preparation method;

[0023] The glass transition temperature of the special engineering plastic is 250-320°C;

[0024] The linear expansion coefficient of the special engineering plastic is 50-60 μm / (m°C);

[0025] The tensile strength of the special engineering plastic is ≥85MPa, and the elongation at break is ≥4%.

[0026] The present invention provides a simple, effective and low-cost polyaryletherketone end-capping agent, monomer and hyperbranched structure, characterized in that the material is prepared by the following steps:

[0027] (1) Weigh the raw materials: 2,6-di(4-fluorobenzoyl)triptycene, bisphenol monomer, water-carrying agent, carbonate and solvent in molar portions, introduce nitrogen and stir to mix, gradually heat to the boiling point of the water-carrying agent for 1-5 hours, then heat to 150-230° C., react for 0.5-24 hours, and post-treat the obtained polymer to obtain a linear polyaryletherketone resin having a triptycene structure.

[0028] (2) Weigh the raw materials: 2-(4-fluorobenzoyl)triptycene, bisphenol monomer, difluorobenzophenone and / or difluorodiphenyl sulfone, water-carrying agent, carbonate and solvent in molar proportions, introduce nitrogen and stir to mix, gradually heat to the boiling point of the water-carrying agent for 1-5 hours, then heat to 150-230° C., react for 0.5-24 hours, and post-treat the obtained polymer to obtain a linear polyaryletherketone / sulfone resin having a triptycene terminal structure.

[0029] The beneficial effects of this application include:

[0030] 1. The present application can adjust the structure of the halogenated benzoyltriptycene and accurately control the position of the triptycene in the polymer backbone chain, so that the obtained products have various applications.

[0031] 2, 2, 6-bis (4-halobenzoyl) triptycene is used for the synthesis of linear poly (aryletherketone), which has a high glass transition temperature and good dimensional stability and is suitable for the manufacture of high temperature resistant precision parts. DETAILED DESCRIPTION

[0032] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0033] Example 1

[0034] 3.183g (10mmol) of phenolphthalein, 4.984g (10mmol) of 2,6-di(4-fluorobenzoyl)triptycene, 1.58g of potassium carbonate, 23.3g of cyclopentane (solid content 25%), and 12ml of toluene were added to a three-necked flask with mechanical stirring and a water separator, nitrogen was introduced, and the mixture was heated to 125-130°C to make toluene and the generated water azeotropic, react for 2h, and separate with a water separator. After distilling off the toluene, the mixture was heated to 180°C and continued to react for 3h. 0.7g of potassium carbonate was added and reacted for 1h. The system gradually became viscous, accompanied by a pole climbing phenomenon. The mixture was cooled, and 45ml of dimethylformamide was added to dilute the mixture, and the mixture was precipitated in ethanol / water. After mechanical crushing and washing, 6.997g of polyaryletherketone product was obtained, with a yield of 90.1%, and the product was beige brown.

[0035] The reaction process is as follows:

[0036]

[0037] Example 2

[0038] 3.183g (10mmol) of phenolphthalein, 0.4984g (1mmol) of 2,6-di(4-fluorobenzoyl)triptycene, 1.964g (9mmol) of 4,4-difluorobenzophenone, 1.58g of potassium carbonate, 23.3g of cyclopentane (solid content 25%), and 12ml of toluene were added to a three-necked flask with mechanical stirring and a water separator, nitrogen was introduced, and the mixture was heated to 125-130°C to make toluene and the generated water azeotropic, react for 2h, and separate with a water separator. After distilling off the toluene, the mixture was heated to 180°C and continued to react for 3h. 0.7g of potassium carbonate was added and reacted for 1h. The system gradually became viscous, accompanied by a pole climbing phenomenon. The mixture was cooled, 45ml of dimethylformamide was added to dilute the mixture, and the mixture was precipitated in ethanol / water. After mechanical crushing and washing, 4.697g of a polyaryletherketone product was obtained, which was white, and a polyaryletherketone copolymer with a triptycene structure was obtained.

[0039] Example 3

[0040] 4.305g (10mmol) of thymolphthalein, 0.4984g (1mmol) of 2,6-di(4-fluorobenzoyl)triptycene, 1.964g (9mmol) of 4,4-difluorobenzophenone, 0.79g of potassium carbonate, 0.70g of sodium carbonate, 23.3g of cyclopentane (solid content 25%), and 12ml of toluene were added to a three-necked flask with mechanical stirring and a water separator, nitrogen was introduced, and the mixture was heated to 120-135°C to make toluene and the generated water azeotropic, react for 4h, and separate with a water separator. After evaporating toluene, the mixture was heated to 190°C and reacted for 2h. The system gradually became viscous, accompanied by a pole climbing phenomenon. The mixture was cooled, 45ml of dimethylformamide was added to dilute the mixture, and the mixture was precipitated in ethanol / water. After mechanical crushing and washing, 5.602g of a polyaryletherketone product was obtained, which was white, and a polyaryletherketone copolymer with a triptycene structure was obtained.

[0041] Example 4

[0042] 3.183g (10mmol) of phenolphthalein, 0.4984g (1mmol) of 2,6-di(4-fluorobenzoyl)triptycene, 2.584g (9mmol) of 4,4-dichlorodiphenyl sulfone, 1.58g of potassium carbonate, 23.3g (solid content 25%) of N-methylpyrrolidone, and 18ml of xylene were added to a three-necked flask with mechanical stirring and a water separator, and nitrogen was introduced. The mixture was heated to 145-155°C to make xylene and the generated water azeotropic, and the reaction lasted for 4h, and the mixture was separated by a water separator. After the toluene was evaporated, the temperature was raised to 190°C, and the reaction continued for 24h. Then 0.7g of potassium carbonate was added and the reaction lasted for 1h. The system gradually became viscous, accompanied by a pole climbing phenomenon. The mixture was cooled, and 30ml of dimethylformamide was added to dilute the mixture, and the mixture was precipitated in ethanol / water. After mechanical crushing and water washing, 4.823 g of a white polyaryletherketone product was obtained, and a polyarylethersulfone copolymer with a triptycene structure was obtained.

[0043] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A polyaryletherketone containing a triptycene structure, characterized in that: Having the structure shown in Formula I; The structure contains triptycene, and the triptycene is connected to a benzoyl group; Where n≥3; Ar is a bisphenol monomer The aromatic ring skeleton remaining after removing the phenolic hydroxyl group; The molecular weight of the polyaryletherketone containing triptycene structure is ≥5000Da, and the molecular weight distribution is ≤3.

5.

2. A method for preparing the polyaryletherketone containing a triptycene structure according to claim 1, characterized in that: At least the following steps are included: The raw materials containing substituted triptycene and bisphenol compound are mixed with a water-carrying agent, carbonate and solvent, and heated for reaction to obtain the polyaryletherketone containing triptycene structure.

3. The preparation method according to claim 2, characterized in that: The substituted triptycene is selected from at least one of 2,6-bis(4-fluorobenzoyl)triptycene, 2,6-bis(4-chlorobenzoyl)triptycene, 2,6-bis(4-bromobenzoyl)triptycene and 2,6-bis(4-nitrobenzoyl)triptycene; The bisphenol compound is at least one selected from bisphenol A, hexafluorobisphenol A, phenolphthalein, thymolphthalein, o-cresolphthalein, bisphenol fluorene, biphenol, and hydroquinone; The water-carrying agent is selected from at least one of cyclohexane, n-heptane, benzene, toluene, xylene, and chlorobenzene; The carbonate is selected from at least one of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, cerium carbonate, and calcium carbonate; The solvent is selected from at least one of sulfolane, diphenyl sulfone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and N-cyclohexylpyrrolidone.

4. The preparation method according to claim 2, characterized in that: The relationship between the amounts of each substance is as follows: in terms of molar fraction, the molar ratio of the substituted triptycene, the bisphenol compound, and the carbonate is 1:0.90-1.20:0.95-3.0; The mass of the solvent is 2 to 6 times the sum of the mass of the substituted triptycene and the bisphenol compound; The mass of the water-carrying agent is 0.5 to 2 times the mass of the solvent.

5. The preparation method according to claim 2, characterized in that: The mass of the solvent is 3 to 4.5 times the sum of the masses of the substituted triptycene and the bisphenol compound.

6. The preparation method according to claim 2, characterized in that: The heating reaction process comprises: heating to boiling of the water-carrying agent under nitrogen protection, maintaining for 1 to 5 hours, removing the water-carrying agent, and then heating to 150 to 230° C., maintaining for 0.5 to 24 hours.

7. A special engineering plastic, characterized in that: A polyaryletherketone containing a triptycene structure as claimed in claim 1 or a polyaryletherketone containing a triptycene structure prepared by the preparation method according to any one of claims 2 to 6; The glass transition temperature of the special engineering plastic is 250-320°C; The linear expansion coefficient of the special engineering plastic is 50-60 μm / (m°C); The tensile strength of the special engineering plastic is ≥85MPa, and the elongation at break is ≥4%.

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