CN111548495A - Polyarylene sulfide sulfone containing phthalazinone structure and preparation method thereof - Google Patents

Abstract

The invention discloses a polyarylthiosulfone containing a phthalazinone structure and a preparation method thereof, wherein the preparation method comprises the steps of taking dihalogen diphenyl sulfone and equimolar bisphenol-like monomer containing the phthalazinone structure as raw materials, heating and dehydrating in a polar solvent or an aprotic polar solvent by taking alkali metal as a catalyst under the nitrogen atmosphere, removing moisture and an azeotropic dehydrating agent, polymerizing, cooling after the reaction is finished, diluting, precipitating in a precipitator, filtering and drying to obtain the polyarylthiosulfone. The polymer structure can be designed, and has excellent flexibility and ductility. Meanwhile, the polymer has better solubility, excellent thermal stability and good processability, so that the series of polymers are expected to be applied to the field of high molecular flame retardance.

Description

A kind of polyarylene sulfide sulfone containing naphthalene structure and preparation method thereof

technical field

The invention belongs to the field of polymer flame retardant, and in particular relates to a preparation method of a polyarylene sulfide sulfone containing a naphthalene structure.

Background technique

Polyarylethersulfone is a class of high-performance aromatic polymers. At present, the design, synthesis and modification of such compounds have shown good application prospects in the fields of separation membrane materials and fuel cells. Among them, naphthalenone-containing polyaryl ether sulfone is particularly concerned, because when the polymer molecule contains naphthalenone, its rigid structure increases the interaction between macromolecules and makes it have excellent heat resistance. sex and mechanical properties.

However, the prior art covers relatively few types of polymers, and the structures are relatively single. For the synthesis of some novel polymers, the present invention provides a new synthetic route and expands the application scope of the technology.

SUMMARY OF THE INVENTION

The invention provides a polyarylene sulfide sulfone containing a naphthalene structure and a preparation method thereof. The structure of the polymer can be designed, combined with the structural characteristics of the sulfide bond and the naphthalene, and has good properties at the same time. Flexibility, chemical stability and thermal stability.

For solving the above problems, the technical scheme of the present invention is:

A polyarylene sulfide sulfone containing a naphthalenone structure, the structure of the polyarylene sulfide sulfone is:

Wherein, m≥10, and m is an integer.

Based on the same inventive concept, the present invention also provides a method for preparing a polyarylene sulfide sulfone containing a naphthalenone structure, comprising: using dihalogendiphenyl sulfone and an equimolar amount of a naphthalenone structure-containing polyarylene sulfide sulfone The bisphenol-like monomer is used as the raw material. At the same time, the azeotropic dehydrating agent, the reaction medium and the catalyst are added to the three-necked flask. Dehydration, removing water and azeotropic dehydrating agent, polymerizing, after the reaction is completed, cooling, diluting, precipitating in a precipitating agent, filtering and drying to obtain the polyarylene sulfide sulfone.

Specifically, the structure of the dihalogen diphenyl sulfone is:

Wherein, X is F, Cl, Br.

Specifically, the structure of the bisphenol-like monomer containing the naphthalenone structure is:

Preferably, the polymerization reaction temperature of the polyarylene sulfide sulfone is 140-220° C., and the reaction time is 12-72 hours.

Preferably, the reaction medium is any one of dimethyl sulfoxide, diphenyl sulfone, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or a mixture thereof, the ratio of the reaction medium to the raw material is 3 mL/g to 6 mL/g.

Preferably, the azeotropic dehydrating agent is toluene, xylene or chlorobenzene, and the volume ratio of the azeotropic dehydrating agent to the raw material is 0.8:1 to 1.2:1.

Preferably, the precipitating agent is methanol, ethanol or acetone.

Preferably, the catalyst is selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium carbonate, and the molar ratio of the catalyst to any one of the reaction raw materials is 1:1 to 1.2:1, that is, with dihalodiphenyl Molar ratio of sulfone or bisphenol-like monomers containing naphthalenone structures.

Compared with the prior art, the present invention has the following advantages and positive effects due to the adoption of the above technical solutions:

The polyarylene sulfide sulfone molecular chain containing naphthalenone structural units of the present invention contains a large number of benzene rings, so that it has soluble properties, and the non-coplanar twisted structure of naphthalenone makes macromolecules interact with each other. is limited, thereby increasing the glass transition temperature of the polymer, and the presence of the sulfone group can also increase the glass transition temperature of the polymer and further improve its heat resistance grade. The polymer has a high thermal decomposition temperature, so it has good thermal stability and is expected to be used in the field of polymer flame retardant.

Description of drawings

Fig. 1 is the infrared spectrogram of the polyarylene sulfide sulfone containing the naphthalenone structure obtained in the embodiment of the present invention 1;

Fig. 2 is the TGA curve diagram of the polyarylene sulfide sulfone containing naphthalenone structure prepared in Example 1 of the present invention;

Fig. 3 is the DSC curve diagram of the polyarylene sulfide sulfone containing the naphthalenone structure prepared in Example 1 of the present invention.

Detailed ways

A kind of polyarylene sulfide sulfone containing naphthalenone structure proposed by the present invention and its preparation method will be described in further detail below with reference to the accompanying drawings and specific examples. The advantages and features of the present invention will become apparent from the following description and claims.

A method for preparing a polyarylene sulfide sulfone containing a naphthalenone structure, comprising: mixing dihalogendiphenyl sulfone with an equimolar bisphenol-like monomer containing a naphthalenone structure and a reaction medium, and reacting The mixing ratio of medium and reaction raw materials (dihalogen diphenyl sulfone and equimolar bisphenol-like monomer containing naphthalenone structure) is 3mL/g～6mL/g, and the reaction medium is dimethyl sulfoxide, Aprotic polar solvent or polar solvent of diphenylsulfone, sulfolane, N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide in sodium hydroxide or potassium hydroxide Or sodium bicarbonate or potassium carbonate is a catalyst, and the reaction medium mixed with the reaction raw materials, the catalyst and the azeotropic dehydrating agent are added to the three-necked flask, and the molar ratio of the catalyst to one of the two reaction raw materials is 1:1～1.2: 1. The volume ratio of the azeotropic dehydrating agent to the reaction raw materials is 0.8:1 to 1.2:1. The three-necked flask is connected to the condensing water separator, nitrogen is introduced, and a mechanical stirrer is installed; Moisture and azeotropic dehydrating agent, polymerization, after the reaction, cooling, dilution, precipitation in methanol, ethanol or acetone and other precipitating agents, filtration and drying to obtain the polyarylene sulfide sulfone, and the structure of the obtained polyarylene sulfide sulfone for:

Wherein, m≥10, and m is an integer.

Specifically, the structure of the dihalogen diphenyl sulfone is:

Among them, X is F, Cl, Br.

Specifically, the structure of the bisphenol-like monomer containing the naphthalenone structure is:

Preferably, the polymerization reaction temperature of the polyarylene sulfide sulfone is 140-220° C., and the reaction time is 12-72 hours.

Preferably, the azeotropic dehydrating agent is toluene, xylene or chlorobenzene.

Example 1

3.0 mmol difluorodiphenyl sulfone, 3.0 mmol 4-(4'-mercapto)phenyl-2,3-diazapine, 3.3 mmol potassium carbonate, 8 mL N,N-dimethylacetamide and 8 mL toluene Put it into a three-necked flask, connect the three-necked flask to a condensing water separator, introduce nitrogen, and install a mechanical stirrer. Under nitrogen atmosphere, be heated to 150 ℃, after azeotropic dehydration for 4 hours, remove moisture and toluene, be warmed up to 160～165 ℃, polymerize for 48 hours, after the reaction finishes, cool to 120 ℃, add 2mL N to the there-necked flask, N-dimethylacetamide, dilute the reaction solution, pour it into 300 mL of deionized water, wash and desalt, and bake at 100-120 ° C for 12 hours to obtain 1.306 g of polyarylene sulfide sulfone containing naphthalenone structure, Yield was 93%.

The infrared spectrum of Fig. 1 shows that the polyarylene sulfide sulfone obtained by the method of this example has the absorption peaks of polymer characteristic functional groups, 1700cm ^-1 C=O, 1160 and 1322cm ^-1 -SO ₂ -, 1080cm ^-1 -S –; Figure 2 shows that the decomposition temperature T _d5 of 5% of the polymer is 490 °C, Figure 3 shows that the obtained polymer has no glass transition temperature in the temperature range of 300 °C, so Figures 2 and 3 show that the obtained polymer The material has high thermal stability.

Example 2

3.0 mmol of dichlorodiphenyl sulfone, 3.0 mmol of 4-(4'-mercapto)phenyl-2,3-naphthyridine, 3.3 mmol of potassium carbonate, 8 mL of N,N-dimethylacetamide and 8 mL of toluene Put it into a three-necked flask, connect the three-necked flask to a condensing water separator, introduce nitrogen, and install a mechanical stirrer. Under nitrogen atmosphere, be heated to 150 ℃, after azeotropic dehydration for 4 hours, remove moisture and toluene, be warmed up to 160～165 ℃, polymerize for 48 hours, after the reaction finishes, cool to 120 ℃, add 2mL N to the there-necked flask, N-dimethylacetamide, dilute the reaction solution, pour it into 300 mL of deionized water, wash and desalt, and bake at 100-120 ° C for 12 hours to obtain 1.302 g of polyarylene sulfide sulfone containing naphthalenone structure, Yield was 92%.

The embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments. Even if various changes are made to the present invention, if these changes fall within the scope of the claims of the present invention and the technical equivalents thereof, they still fall within the protection scope of the present invention.

Claims (9)

1. a kind of polyarylene sulfide sulfone containing naphthalene structure, it is characterized in that, the structure of described polyarylene sulfide sulfone is:

Wherein, m≥10, and m is an integer. 2. a preparation method of the polyarylene sulfide sulfone containing naphthalenone structure, is characterized in that, comprising: with dihalogendiphenyl sulfone and equimolar containing the class bisphenol monomer of naphthalenone structure As raw materials, the raw materials are mixed into the three-necked flask, and at the same time, the azeotropic dehydrating agent, catalyst, and reaction medium are added to the three-necked flask. , cooled, diluted, precipitated in a precipitant, filtered and dried to obtain the polyarylene sulfide sulfone. 3. the preparation method of the polyarylene sulfide sulfone containing naphthalenone structure according to claim 2, is characterized in that, the structure of described dihalogen diphenyl sulfone is:

Wherein, X is F, Cl, Br. 4. the preparation method of the polyarylene sulfide sulfone containing naphthalenone structure according to claim 2, is characterized in that, the structure of the described bisphenol-like monomer containing naphthalenone structure is:

5. the preparation method of the polyarylene sulfide sulfone containing naphthalenone structure according to claim 2, is characterized in that, the polymerization reaction temperature of described polyarylene sulfide sulfone is 140-220 ℃, and the reaction time is 12 -72 hours. 6. the preparation method of the polyarylene sulfide sulfone containing naphthalenone structure according to claim 2, is characterized in that, described reaction medium is dimethyl sulfoxide, diphenyl sulfone, sulfolane, N-methyl sulfone pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, or a mixture thereof, and the ratio of the reaction medium to the raw material is 3 mL/g to 6 mL/g. 7. the preparation method of the polyarylene sulfide sulfone containing naphthalenone structure according to claim 2, is characterized in that, described azeotropic dehydrating agent is toluene, xylene or chlorobenzene, and described azeotropic dehydration The volume ratio of the agent to the raw material is 0.8:1 to 1.2:1. 8 . The preparation method of the polyarylene sulfide sulfone containing naphthalenone structure according to claim 2 , wherein the precipitating agent is water, methanol, ethanol or acetone. 9 . 9. the preparation method of the polyarylene sulfide sulfone containing naphthalenone structure according to claim 2, is characterized in that, described catalyzer is selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, The molar ratio of the catalyst to any one of the reaction raw materials is 1:1-1.2:1.

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