Amino-functionalized polyether sulfone and efficient preparation method and application thereof

Abstract

An amino-functionalized polyether sulfone and its efficient preparation method and application. The present application belongs to the field of functionalized polyether sulfone preparation. The purpose of the present application is to solve the technical problems of high cost, complicated steps and low synthesis efficiency of the existing method for preparing amino-functionalized polyether sulfone. The amino-functionalized polyether sulfone polymer is synthesized by selecting a specific active monomer. The amino group on the monomer does not need to be protected and deprotected during the polymerization process. Moreover, the conjugated structure in the specific dichloromonomer can stabilize the amino group, significantly improving the polymerization reaction efficiency. The preparation method is simple, the raw materials are easy to obtain and the cost is low. It is applied to the fields of petroleum chemical industry, fine chemical industry and medical treatment.

Description

Technical Field

[0001] This invention belongs to the field of functionalized polyethersulfone preparation, specifically relating to an amino-functionalized polyethersulfone, its efficient preparation method, and its application. Background Technology

[0002] Polyethersulfone (PES) is a thermoplastic polymer with excellent overall performance. Compared to polysulfone (PS), PES has higher heat resistance and rigidity, excellent creep resistance and dimensional stability at high temperatures, and excellent resistance to inorganic chemicals such as acids and alkalis, but it has weak resistance to polar solvents. PES has wide applications in electronics, machinery, automotive, and medical devices.

[0003] Amino groups are highly reactive hydrophilic functional groups. Introducing amino groups into the polymer backbone can improve the hydrophilicity of the polymer. On the other hand, it can also enable different functional modifications to the polymer and achieve post-processing steps such as grafting and cross-linking, thereby realizing different functional applications in many fields such as petrochemicals, fine chemicals, and medical production.

[0004] Traditional polyethersulfone (PES) materials with no functionalization sites on the main chain are chemically inert, which limits their functionalization modification and makes them difficult to crosslink, hindering their application in polar solvent systems. Current methods typically prepare amino-functionalized polymers through the dehydration condensation of bisphenol monomers with amino groups, often using bisphenol monomers. However, the high reactivity of amino groups causes most of these monomers to crosslink during polymerization, requiring special steps for protecting the amino monomers before polymerization and deprotecting them afterward. Furthermore, the bisphenol monomers used are expensive. In addition, the low reactivity of amino-modified bisphenol monomers leads to low synthesis efficiency of amino-functionalized PES. Therefore, there is an urgent need to develop a new, efficient method for synthesizing amino-functionalized PES. Summary of the Invention

[0005] The purpose of this invention is to solve the technical problems of high cost, cumbersome steps, and low synthesis efficiency in existing methods for preparing amino-functionalized polyether sulfones. Instead, it provides an amino-functionalized polyether sulfone, its efficient preparation method, and its applications.

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

[0007] One of the objectives of this invention is to provide an amino-functionalized polyether sulfone with the general structural formula shown in formula (1):

[0008]

[0009] Where 0 < x < 0.5, It is one or more of the formulas (2) to (15):

[0010]

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

[0012]

[0013]

[0014] Where 0 < x < 0.5.

[0015] The second objective of this invention is to provide an efficient method for preparing the above-mentioned amino-functionalized polyether sulfone, wherein the preparation method is carried out according to the following steps:

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

[0017] The amino-containing dichloro reactive monomer has the structure shown in formulas (30) to (43):

[0018]

[0019]

[0020] Preferably, in the above preparation method of the present invention: the molar ratio of amino-containing dichloro reactive monomer, dihalodiphenyl sulfone monomer, bisphenol S monomer and base 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 alkaline 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, the reaction process further includes a dehydrating agent, wherein the dehydrating agent is toluene, xylene or cyclohexane.

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

[0025] The third objective of this invention is to provide an application of the above-mentioned amino-functionalized polyether sulfone in the fields of petrochemicals, fine chemicals, and medicine.

[0026] The significant advantages of this invention compared to existing technologies are:

[0027] (1) The present invention selects specific active monomers and synthesizes amino-functionalized polyethersulfone polymers according to specific process steps, thereby achieving the design purpose. The introduction of active amino groups provides active sites for subsequent functionalization and grafting crosslinking and other post-processing steps, thus broadening the application field of polyethersulfone polymers.

[0028] (2) Currently available methods for synthesizing polyethersulfone polymers with amino functional groups typically use bisphenol monomers containing amino groups. Due to the high reactivity of amino groups, the amino groups need to be protected before polymerization, and the polymer needs to undergo amino deprotection after polymerization. However, this invention uses dichloro monomers containing amino groups. Due to the special structure of the monomers, they can be used directly in the polymerization reaction without the need for pretreatment steps. Moreover, the conjugated structure in the specific dichloro monomers can stabilize the amino groups, significantly improving the polymerization efficiency.

[0029] (3) The preparation method provided by the present invention is simple, the raw materials are readily available and the cost is low, and it has broad application prospects. Attached Figure Description

[0030] Figure 1 The NMR spectrum of the amino-functionalized polyether sulfone prepared in Example 1 is shown. Detailed Implementation

[0031] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0033] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such a composition, step, method, article, or apparatus.

[0034] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range. In this specification and claims, range definitions may be combined and / or interchanged, unless otherwise stated, these ranges include all subranges contained therein.

[0035] The indefinite articles “a” and “an” preceding an element or component of this invention do not impose any limitation on the quantity (i.e., number of occurrences) of the element or component. Therefore, “an” or “a” 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] The term "an embodiment" or "embodiment" as used in this invention refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that excludes other embodiments.

[0037] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered 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 as 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. The mixture was heated to 260 °C for 4 h under nitrogen purging to obtain a reddish-brown viscous polymer solution. After dilution with 100 mL of N-methylpyrrolidone, the potassium carbonate was removed by centrifugation. The resulting solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was pulverized, washed, and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is shown below:

[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 (as 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. The mixture was heated to 250 °C for 6 h under nitrogen purging to obtain a reddish-brown viscous polymer solution. After dilution with 100 mL of N-methylpyrrolidone, the potassium carbonate was removed by centrifugation. The resulting solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was pulverized, washed, and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is shown below:

[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 (as 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. The mixture was heated to 260 °C for 6 h under nitrogen purging to obtain a reddish-brown viscous polymer solution. After dilution with 100 mL of N-methylpyrrolidone, potassium carbonate was removed by centrifugation. The resulting solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was pulverized, washed, and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is shown below:

[0046]

[0047] Example 4:

[0048] 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 5-amino-4,6-dichloropyrimidine as shown in formula (32), 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. The mixture was heated to 250 °C for 5 h under nitrogen purging to obtain a reddish-brown viscous polymer solution. After dilution with 100 mL of N-methylpyrrolidone, potassium carbonate was removed by centrifugation. The resulting solution was poured into a dilute hydrochloric acid solution for phase inversion. The obtained solid was pulverized, washed, and dried to obtain an amino-functionalized polyethersulfone polymer. The structure is shown below:

[0049]

[0050] Example 5:

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

[0052]

[0053] The above description is merely a preferred embodiment of the present invention. These specific embodiments are different implementations based on the overall concept of the present invention, and the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. An amino-functionalized polyethersulfone, characterized in that, Its general structural formula is shown in equation (1): ； Where 0 < x < 0.5, It is one or more of the formulas (2) to (15): , , , , , , , , , , , , and ; Amino-functionalized polyethersulfone is obtained by nucleophilic polycondensation of one or more amino-containing dichloro reactive monomers with dihalodiphenyl sulfone monomers and bisphenol S monomers in a polar aprotic solvent under the protection of an inert atmosphere and the action of an alkaline catalyst.

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

5.

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

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

5. The method according to claim 3, characterized in that, The alkaline 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 sulfolane.

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

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

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

10. The polyethersulfone according to claim 1 or 2 in petrochemical and fine chemical applications.

Images