Amino-functionalized polysulfone and its efficient preparation method and application

Abstract

An amino-functionalized polysulfone and its efficient preparation method and application. The present application belongs to the field of functionalized polysulfone 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 polysulfone. The amino-functionalized polysulfone 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 medical devices, aerospace, electronics and electrical appliances, food and daily necessities.

Description

Technical Field

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

[0002] Polysulfone is a thermoplastic resin containing sulfone (-SO2-) and aryl groups in its molecular backbone. It possesses excellent mechanical properties and thermal stability, high strength, high rigidity, hydrolysis resistance, good dimensional stability, and tolerance to common acids and alkalis. It is widely used in the production of medical devices, aerospace, electronics, food, and daily necessities. It is a high-performance engineering plastic with a wide range of applications.

[0003] However, the polysulfone materials with non-functionalized main chain prepared by the dehydration condensation of bisphenol A and dichlorodiphenyl sulfone have the following problems: (1) The polysulfone polymer with non-functionalized main chain has hydrophobic properties. When the polysulfone polymer is used in hemodialysis membranes, ultrafiltration membranes, and reverse osmosis bottom membranes, it will cause serious membrane fouling problems, which limits the application of polysulfone materials; (2) The main chain of traditional polysulfone polymers does not have sites for functionalization, which limits the functionalization modification of polysulfone and restricts its application in some special occasions.

[0004] Amino groups are highly reactive hydrophilic functional groups. Introducing amino groups into the polymer backbone can improve the polymer's hydrophilicity and allow for various functional modifications and post-processing steps such as grafting and cross-linking, thus enabling diverse functional applications in numerous fields such as petrochemicals, fine chemicals, and medical manufacturing. Current methods typically prepare amino-functionalized polymers by selecting or synthesizing bisphenol monomers with amino groups and then performing dehydration condensation. The selected amino monomers are mostly bisphenol monomers. However, due to the high reactivity of amino groups, most amino monomers undergo cross-linking during polymerization. Therefore, special reaction steps are often required to protect the amino monomers before polymerization and to deprotect them after polymerization, and the selected bisphenol monomers are relatively expensive. Furthermore, the low reactivity of amino-modified bisphenol monomers leads to low synthesis efficiency of amino-functionalized polysulfones. Therefore, there is an urgent need to develop a new method for the efficient synthesis of amino-functionalized polysulfones. 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 polysulfones. This invention provides an amino-functionalized polysulfone, 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 a general structural formula of amino-functionalized polysulfone as shown in formula (1):

[0008]

[0009] Where 0 < x < 1; It is one or more of the formulas (2) to (15):

[0010]

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

[0012]

[0013]

[0014]

[0015] Where 0 < x < 1.

[0016] The second objective of this invention is to provide an efficient method for preparing the above-mentioned amino-functionalized polysulfone, wherein the preparation method is carried out according to the following steps:

[0017] 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 monomers and bisphenol A monomers in a polar aprotic solvent to obtain amino-functionalized polysulfones.

[0018] The amino-containing dichloro reactive monomer has the structure shown in formulas (30) to (43):

[0019]

[0020] Preferably, in the above preparation method, the molar ratio of amino-containing dichloro reactive monomer, dihalodiphenyl sulfone monomer, bisphenol A monomer and base catalyst is y:(1-y):1:(1.05~2.5), where 0<y<1.

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

[0022] Preferably, in the above preparation method, 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, the reaction process also includes a dehydrating agent, which is toluene, xylene, or cyclohexane.

[0024] Preferably, in the above preparation method, the nucleophilic condensation reaction temperature is 180–230°C and the time is 1–7 h. More preferably, the nucleophilic condensation reaction temperature is 200–230°C and the time is 1–4 h.

[0025] The third objective of this invention is to provide an application of the above-mentioned amino-functionalized polysulfone in the fields of medical devices, aerospace, electronics, food and daily necessities.

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

[0027] (1) The present invention selects specific active monomers to synthesize and prepare amino-functionalized polysulfone polymers, achieving the design purpose. The synthesized amino-functionalized polymers significantly improve the hydrophilicity of polysulfone polymers by introducing side chain amino groups into the polymer backbone. At the same time, the introduction of active amino groups provides active sites for subsequent functionalization treatments or graft crosslinking and other post-treatment steps, thus broadening the application field of polysulfone polymers.

[0028] (2) By introducing a dichloro monomer with a specific structure into the polymerization process, the present invention not only eliminates the need for protection and deprotection steps on the amino group on the monomer during the polymerization process, but also the conjugated structure in the specific dichloro monomer can stabilize the amino group, thus 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 polysulfone 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 times) 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] In this invention, "an embodiment" or "embodiment" 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] 22.829 g (0.1 mol) of bisphenol A 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 N-methylpyrrolidone 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 220 °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 polysulfone polymer. The structure is shown in the figure.

[0040]

[0041] Example 2

[0042] 22.829 g (0.1 mol) of bisphenol A 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 N-methylpyrrolidone 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 230 °C for 2 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 polysulfone polymer. The structure is shown in the figure.

[0043]

[0044] Example 3

[0045] 22.829 g (0.1 mol) of bisphenol A 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 potassium carbonate, and 100 mL of N-methylpyrrolidone 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 180 °C for 7 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 polysulfone polymer. The structure is shown in the figure.

[0046]

[0047] Example 4:

[0048] 22.829 g (0.1 mol) of bisphenol A 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 potassium carbonate, and 100 mL of N-methylpyrrolidone 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 200 °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 polysulfone polymer. The structure is shown in the figure.

[0049]

[0050] Example 5:

[0051] 22.829 g (0.1 mol) of bisphenol A 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)), 10.7309 g (0.15 mol) of anhydrous potassium carbonate, and 100 mL of N-methylpyrrolidone were added to a 250 mL three-necked flask containing a mechanical stirrer, a nitrogen inlet, a water separator, and a condenser. The mixture was heated to 230 °C and reacted for 2.5 h under nitrogen purging to obtain a reddish-brown viscous polymer solution. After diluting 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 in the figure:

[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 polysulfone, characterized in that, Its general structural formula is shown in equation (1): ； Where 0 < x < 1, and x is the molar ratio; It is one or more of the formulas (2) to (15): , , , , , , , , , , , , and ; The polysulfone is prepared by: under the protection of an inert atmosphere and the action of an alkaline catalyst, one or more of the amino-containing dichloro reactive monomers are reacted with dihalodiphenyl sulfone monomers and bisphenol A monomers in a polar aprotic solvent to carry out nucleophilic polycondensation reaction to obtain amino-functionalized polysulfone.

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

3. The efficient preparation method of polysulfone 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 monomers and bisphenol A monomers in a polar aprotic solvent to obtain amino-functionalized polysulfones. The amino-containing dichloro reactive monomer has the structure 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 A monomer and 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 water-removing agent is toluene, xylene, or cyclohexane.

9. The method according to claim 3, characterized in that, The nucleophilic condensation reaction temperature is 180~230℃, and the time is 1~7h.

10. The application of the polysulfone according to claim 1 or 2 in the fields of medical device manufacturing, aerospace, electronics, food and daily necessities.

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