Amino-functionalized polyethersulfone as well as efficient preparation method and application thereof

Abstract

The invention relates to amino-functionalized polyethersulfone as well as an efficient preparation method and application thereof. The invention belongs to the field of preparation of functionalized polyethersulfone. The invention aims to solve the technical problems of high cost, tedious steps and low synthesis efficiency of the existing method for preparing amino-functionalized polyether sulfone. The amino-functionalized polyethersulfone polymer is synthesized and prepared by selecting a specific active monomer, so that the steps of protecting and deprotecting amino groups on the monomer are not needed in the polymerization process, and a conjugated structure in the specific dichloro monomer can stabilize the amino groups and obviously improve the polymerization reaction efficiency. The preparation method has the advantages of simple process, easily available raw materials and low cost. The method is applied to the fields of petrochemical engineering, fine chemical engineering and medical treatment.

Description

Technical Field

[0001] The present invention belongs to the field of the preparation of functionalized polyethersulfone, and particularly relates to an amino-functionalized polyethersulfone, an efficient preparation method thereof, and an application thereof. Background Art

[0002] Polyethersulfone is a thermoplastic polymer material with excellent comprehensive properties. Compared with polysulfone, polyethersulfone has higher heat resistance and rigidity, excellent creep resistance and dimensional stability at high temperatures, and excellent chemical resistance to inorganic drugs such as acids and bases, but has weak tolerance to polar solvents. Polyethersulfone has a wide range of applications in the fields of electronics and electrical appliances, machinery, automobiles, and medical devices.

[0003] Amino is a hydrophilic functional group with high reactivity. Introducing an amino group into the polymer backbone can, on the one hand, improve the hydrophilicity of the polymer; on the other hand, it can perform different functional modifications on the polymer and realize post-treatment steps such as grafting and crosslinking, so as to achieve different functional applications in many fields such as petrochemical industry, fine chemical industry, and medical production.

[0004] Traditional polyethersulfone materials without functionalized sites in the main chain have chemical reaction inertness, which restricts the functional modification of polyethersulfone on the one hand; on the other hand, it is difficult to perform crosslinking treatment, making it difficult for polyethersulfone materials to be applied in polar solvent systems. Currently, existing methods usually prepare amino-functionalized polymers by dehydration condensation of bisphenol monomers with amino groups through selection or synthesis. The selected amino-active monomers are mostly bisphenol monomers. However, due to the high reactivity of amino groups, most of the amino monomers crosslink during the polymerization process. Therefore, special reaction steps of protecting the amino monomers before the polymerization reaction and deprotecting after the polymerization reaction are often required, and the selected bisphenol monomers have a high cost. In addition, the reaction activity of the amino-modified bisphenol monomers is not high, resulting in a low synthesis efficiency of amino-functionalized polyethersulfone. There is an urgent need to develop a new method for efficiently synthesizing amino-functionalized polyethersulfone. Summary of the Invention

[0005] The purpose of the present invention is to solve the technical problems of the existing method for preparing amino-functionalized polyethersulfone, which has high cost, cumbersome steps, and low synthesis efficiency. Therefore, an amino-functionalized polyethersulfone, an efficient preparation method thereof, and an application thereof are provided.

[0006] The technical solution of the present invention is as follows:

[0007] One of the purposes of the present invention is to provide a structural general formula of an amino-functionalized polyethersulfone as shown in formula (1):

[0008]

[0009] Where 0 < x < 0.5, One or more of Formulas (2) to (15):

[0010]

[0011] Preferably, When there is one kind, the amino-functionalized polyethersulfone structure is one of Formulas (16) to (29):

[0012]

[0013]

[0014] where 0 < x < 0.5.

[0015] The second object of the present invention is to provide an efficient preparation method of the above-mentioned amino-functionalized polyethersulfone. The preparation method is carried out according to the following steps:

[0016] Under the protection of an inert atmosphere and the action of an alkali catalyst, one or more of the dichloro reaction monomers containing amino are subjected to a nucleophilic polycondensation reaction with a dihalodiphenylsulfone monomer and a bisphenol S monomer in a polar aprotic solvent to obtain an amino-functionalized polyethersulfone;

[0017] The structure of the dichloro reaction monomer containing amino is shown in Formulas (30) to (43):

[0018]

[0019]

[0020] Preferably, in the above preparation method of the present invention: the molar ratio of the dichloro reaction monomer containing amino, the dihalodiphenylsulfone monomer, the bisphenol S monomer to the alkali catalyst is y:(1 - y):1:(1.05 - 2.5), where 0 < y < 1.

[0021] Preferably, in the above preparation method of the present invention: the alkali catalyst is an alkali metal hydroxide and / or an alkali metal carbonate.

[0022] Preferably, in the above preparation method of the present invention: the polar aprotic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and sulfolane.

[0023] Preferably, in the above preparation method of the present invention: a water-carrying agent is further included during the reaction, and the water-carrying agent is toluene, xylene or cyclohexane.

[0024] Preferably, in the above preparation method of the present invention: the temperature of the nucleophilic polycondensation reaction is 210 - 270 °C, and the time is 4 - 7 h. More preferably, the temperature of the nucleophilic polycondensation reaction is 250 - 270 °C, and the time is 4 - 6 h.

[0025] The third object of the present invention is to provide an application of the above amino-functionalized polyethersulfone in the fields of petrochemical industry, fine chemical industry, and medical field.

[0026] The remarkable effects of the present invention compared with the prior art are as follows:

[0027] (1) The present invention selects specific active monomers to synthesize and prepare an amino-functionalized polyethersulfone polymer according to specific process steps, achieving the design purpose. The introduction of active amino groups provides active sites for subsequent other functionalization treatments and post-treatment steps such as grafting and crosslinking, broadening the application fields of polyethersulfone polymers.

[0028] (2) Currently, when synthesizing polyethersulfone polymers with amino functional groups, bisphenol monomers with amino groups are usually selected. Due to the high reactivity of amino groups, the amino groups need to be protected before polymerization, and the amino groups of the polymer need to be deprotected after polymerization. However, the present invention selects dichloro monomers with amino groups. Due to the special structure of the monomers, they can be directly used in the polymerization reaction without prior treatment steps. Moreover, the conjugated structure in the specific dichloro monomers can stabilize the amino groups, significantly improving the polymerization reaction efficiency.

[0029] (3) The preparation method provided by the present invention has simple process, easily available raw materials and low cost, and has broad application prospects. Description of the Drawings

[0030] Figure 1 It is the NMR spectrum of the amino-functionalized polyethersulfone prepared in Example 1. Detailed Embodiments

[0031] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0032] The experimental methods used in the following embodiments are all conventional methods unless otherwise specified. The materials, reagents, methods, and instruments used, unless otherwise specified, are all conventional materials, reagents, methods, and instruments in the art, and those skilled in the art can obtain them through commercial channels.

[0033] As used in the following embodiments, the terms "comprising", "including", "having", "containing" or any other variation thereof are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a listed element(s) is not necessarily limited to those element(s), but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0034] When an equivalent, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, it should be understood that all ranges formed by any pairing of any upper range limit or preferred value with any lower range limit or preferred value are specifically disclosed, regardless of whether the ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted as including the ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values and all integers and fractions within the range. In the specification and claims of this application, range limitations may be combined and / or interchanged, and if not otherwise stated, these ranges include all sub-ranges subsumed therein.

[0035] The indefinite articles "a" and "an" before an element or component of the present invention do not limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.

[0036] As used herein, "an embodiment" or "embodiments" of the present invention refer to specific features, structures, or characteristics that may be included in at least one implementation of the present invention. The phrase "in an embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment that is mutually exclusive with other embodiments.

[0037] The endpoints and any values in the ranges disclosed in the invention are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values may be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0038] Example 1

[0039] 25.027 g (0.1 mol) of bisphenol S monomer, 22.973 g (0.08 mol) of dichlorodiphenyl sulfone monomer, 3.28 g (0.02 mol) of 2-amino-4,6-dichloropyrimidine shown in formula (30), 10.7309 g (0.15 mol) of anhydrous potassium carbonate, and 100 mL of sulfolane were added to a 250 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator, and a condenser. Under nitrogen blowing, the mixture was heated to 260 °C and reacted for 4 h to obtain a red-brown viscous polymer solution. After adding 100 mL of N-methylpyrrolidone for dilution, potassium carbonate was removed by centrifugation. The resulting solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was crushed, washed, and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is as follows:

[0040]

[0041] Example 2

[0042] 25.027 g (0.1 mol) of bisphenol S monomer, 14.385 g (0.05 mol) of dichlorodiphenyl sulfone monomer, 8.199 g (0.05 mol) of 2-amino-4,6-dichloropyrimidine shown in formula (30), 10.7309 g (0.15 mol) of anhydrous potassium carbonate, and 100 mL of sulfolane were added to a 250 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator, and a condenser. Under nitrogen blowing, the mixture was heated to 250 °C and reacted for 6 h to obtain a red-brown viscous polymer solution. After adding 100 mL of N-methylpyrrolidone for dilution, potassium carbonate was removed by centrifugation. The resulting solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was crushed, washed, and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is as follows:

[0043]

[0044] Example 3

[0045] 25.027 g (0.1 mol) of bisphenol S monomer, 14.385 g (0.05 mol) of dichlorodiphenyl sulfone monomer, 8.199 g (0.05 mol) of 4-amino-2,6-dichloropyrimidine shown in formula (31), 10.7309 g (0.15 mol) of anhydrous sodium carbonate, and 100 mL of sulfolane were added to a 250 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator, and a condenser. Under nitrogen blowing, the mixture was heated to 260 °C and reacted for 6 h to obtain a red-brown viscous polymer solution. After adding 100 mL of N-methylpyrrolidone for dilution, potassium carbonate was removed by centrifugation. The resulting solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was crushed, washed, and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is as follows:

[0046]

[0047] Embodiment 4:

[0048] 25.027g (0.1mol) of bisphenol S monomer, 14.385g (0.05mol) of dichlorodiphenyl sulfone monomer, 8.199g (0.05mol) of 5-amino-4,6-dichloropyrimidine shown in formula (32) and 10.7309g (0.15mol) of anhydrous sodium carbonate, and 100mL of cyclopentane sulfone were added to a 250mL three-necked flask with a mechanical stirrer, a nitrogen inlet, a water separator, and a condenser. The mixture was heated to 250°C under nitrogen blowing conditions for 5h to obtain a reddish brown viscous polymer solution. 100mL of N-methylpyrrolidone was added for dilution and the solution was centrifuged to remove potassium carbonate. The obtained solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was crushed, washed, and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is shown below:

[0049]

[0050] Embodiment 5:

[0051] 25.027g (0.1mol) of bisphenol S monomer, 14.385g (0.05mol) of dichlorodiphenyl sulfone monomer, 8.199g (0.025mol) of 5-amino-4,6-dichloropyrimidine shown in formula (32), 8.199g (0.025mol) of 2-amino-4,6-dichloropyrimidine shown in formula (30) and 10.7309g (0.15mol) of anhydrous sodium carbonate, 100mL of cyclopentane sulfone were added to a 250mL three-necked flask containing a mechanical stirrer, a nitrogen inlet, a water separator and a condenser, and heated to 260°C under nitrogen blowing conditions for 6h to obtain a reddish brown viscous polymer solution, 100mL of N-methylpyrrolidone was added for dilution, and the solution was centrifuged to remove potassium carbonate, and the obtained solution was poured into a dilute hydrochloric acid solution for phase inversion, and the obtained solid was crushed, washed and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is shown below:

[0052]

[0053] The above are only preferred specific embodiments of the present invention, which are all different implementations based on the overall concept of the present invention, and the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. An amino-functionalized polyethersulfone, characterized in that Its general structural formula is shown in formula (1): Where 0<x<0.5, It is one or more of the formulas (2) to (15):

2. The polyethersulfone according to claim 1, characterized in that When is one, the amino-functionalized polyethersulfone structure is one of formulas (16) to (29): Where 0<x<0.

5.

3. The efficient preparation method of polyethersulfone according to claim 1 or 2, characterized in that: The method: Under the protection of an inert atmosphere and the action of a base catalyst, one or more dichloro reactive monomers containing an amino group are subjected to a nucleophilic polycondensation reaction with a dihalodiphenyl sulfone monomer and a bisphenol S monomer in a polar aprotic solvent to obtain an amino-functionalized polyether sulfone; The structures of the amino-containing dichloro reactive monomers are shown in formulas (30) to (43):

4. The method according to claim 3, characterized in that The molar ratio of the amino-containing dichloro reactive monomer, the dihalogen diphenyl sulfone monomer, the bisphenol S monomer and the base catalyst is y:(1-y):1:(1.05-2.5), wherein 0<y<1.

5. The method according to claim 3, characterized in that: The base catalyst is an alkali metal hydroxide and / or an alkali metal carbonate.

6. The method according to claim 3, characterized in that The polar aprotic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and cyclopentane.

7. The method according to claim 3, characterized in that The reaction process also includes a water-carrying agent.

8. The method according to claim 7, characterized in that The water-carrying agent is toluene, xylene or cyclohexane.

9. The method according to claim 3, characterized in that: The nucleophilic condensation reaction temperature is 210-270°C and the time is 4-7h.

10. Use of the polyethersulfone according to claim 1 or 2 in the fields of petrochemicals, fine chemicals and medicine.

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