Synthesis method and application of poly (ether) sulfuryl block copolymer based on chain exchange reaction

Abstract

The invention relates to a synthesis method and application of a poly (ether) sulfuryl block copolymer based on chain exchange reaction, and belongs to the technical field of high polymer materials, the synthesis method comprises the following preparation steps: S1, taking an organic solvent, adding a poly (ether) sulfuryl material into the organic solvent, heating and stirring until the poly (ether) sulfuryl material is completely dissolved to obtain a mixed system; and S2, adding an amino-containing hydrophilic polymer material with reaction activity into the mixed system prepared in the step S1, and removing the solvent after reaction to obtain the poly (ether) sulfuryl block copolymer. The preparation process is easy to operate, the production period is short, the obtained material is stable in performance, and industrial production is easy.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction. Background Art

[0002] As a traditional special engineering plastic, poly(ether) sulfone-based materials are widely used in the fields of separation membrane, electronic appliances, vehicle engineering and food and medical equipment manufacturing due to their excellent mechanical properties, high mechanical strength and stable chemical properties. However, due to the fact that they contain more aromatic and methyl groups, the hydrophilicity of poly(ether) sulfone materials is poor, which reduces the pollution resistance and biocompatibility of their products, greatly limiting their development in the fields of separation membrane and biological and medical equipment manufacturing. Therefore, the improvement of the hydrophilic properties of poly(ether) sulfone-based materials can further increase the use value of poly(ether) sulfone-based materials. In order to improve the hydrophilicity of poly(ether) sulfone-based materials, the method of modifying poly(ether) sulfone into amphiphilic block copolymers with hydrophilic materials has been widely studied and can be applied to the fields of separation membrane and biological and medical equipment manufacturing.

[0003] At present, the mainstream route for synthesizing poly(ether) sulfone-based block copolymers is to add hydrophilic materials as end-capping agents during the Farnam process for synthesizing poly(ether) sulfone. For example, the route for synthesizing non-linear polysulfone-based block copolymers disclosed in patent CN117384385B, the inventor believes that the method in the patent is based on the monomer of poly(ether) sulfone, and has the problems of long synthesis cycle, complicated process and large consumption of organic solvent.

[0004] In view of the above-mentioned technical problems, the inventors believe that it is necessary to shorten the preparation cycle, simplify the process flow, reduce the consumption of organic solvents, and reduce the discharge of production waste liquid in order to solve the obstacles to the industrial synthesis of poly(ether)sulfone-based block copolymers. Summary of the invention

[0005] The purpose of the present invention is to provide a method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction. In the industrial synthesis of the poly(ether)sulfone-based block copolymer, the preparation cycle is shortened, the process flow is simplified, the consumption of organic solvents is reduced, and the discharge of production waste liquid is reduced. The implementation process is simple and easy, the cycle is short, the solvent consumption is small, and no alkaline catalyst is required. The hydrophilic chain segments in the synthesized product have multiple functional groups, such as hydroxyl groups, amino groups, etc.

[0006] On the one hand, the present invention provides a method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction, which adopts the following technical scheme:

[0007] The synthesis method of poly(ether)sulfone-based block copolymer based on chain exchange reaction comprises the following steps:

[0008] S1. Take an organic solvent and a poly(ether)sulfone material respectively and mix them. Heat and stir until completely dissolved to obtain a mixed system;

[0009] S2. Add a hydrophilic polymer material containing amino groups with reactive activity to the mixed system prepared in step S1. After the reaction, remove the solvent to obtain a poly(ether)sulfone-based block copolymer.

[0010] Preferably, the poly(ether)sulfone-based block copolymer in step S2 includes at least two different types of repeating units, which can be summarized as AB type, ABA type or ABC type;

[0011] Components A and C are hydrophilic polymer materials containing amino groups that can react with component B; the component B is a poly(ether)sulfone material with a molecular weight higher than 10,000 Da, and the component B accounts for 50-98% of the total amount of the poly(ether)sulfone-based block copolymer.

[0012] Preferably, the ratio of the organic solvent to the poly(ether)sulfone material in step S1 is (3-5):1.

[0013] Preferably, the mass ratio of the hydrophilic polymer material to the poly(ether)sulfone material in step S2 is 1:(2-6.25).

[0014] Preferably, the general formula of the poly(ether)sulfone material in step S1 includes:

[0015]

[0016] Any one or more of them.

[0017] Preferably, the hydrophilic polymer material containing amino groups in step S1 includes one or more of polyvinylamine, polyethyleneimine, hyperbranched polyethyleneimine, polyallylamine, polyacrylamide, and polyetheramine.

[0018] Preferably, the organic solvent in step S1 includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and sulfolane.

[0019] Preferably, the reaction temperature in step S1 is 90-150 °C respectively, and the reaction time is 0.5-1 h;

[0020] The reaction temperature in step S2 is 120-150 °C, and the reaction time is 1-2 h;

[0021] The molecular weight of the poly(ether)sulfone-based block copolymer is between 12,000 Da and 60,000 Da.

[0022] On the other hand, the application of a poly(ether)sulfone-based block copolymer prepared by the synthesis method of the above-mentioned poly(ether)sulfone-based block copolymer based on a chain exchange reaction in the fields of biology, medicine, and separation membranes.

[0023] In summary, the present invention includes the following beneficial technical effects:

[0024] 1. The present invention uses a poly(ether)sulfone material and a hydrophilic polymer material containing an amino group as reaction raw materials to simply and rapidly synthesize a novel poly(ether)sulfone-based block copolymer in one step; the preparation process is easy to operate, has a short production cycle, the obtained material has stable properties, and is easy for industrial production.

[0025] 2. The prepared novel poly(ether)sulfone-based block copolymer can be used to prepare functional devices or functional materials in the fields of biology, medicine, electronics, membrane separation, etc., and can be used as an additive to improve the functionality of materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a comparison chart of TGA and 1 H NMR of the block polymer PSf-b-PEI prepared in Example 1 with PSf and the block polymer PES-b-PEI prepared in Example 2 with PES. DETAILED DESCRIPTION OF THE INVENTION

[0027] The following further describes the present invention in detail with reference to examples.

[0028] The poly(ether)sulfone material is obtained through commercial channels. The poly(ether)sulfone material includes a polysulfone material and a polyethersulfone material, and its general formula includes:

[0029]

[0030] Any one or more of them.

[0031] EXAMPLES

[0032] Example 1

[0033] A synthesis method of a poly(ether)sulfone-based block copolymer based on a chain exchange reaction includes the following steps:

[0034] 1). Add 200 g of polysulfone (PSf) into a four-necked round-bottom flask equipped with a stirring paddle, use Schlenk operation to fully displace the air in the device, and then, under an inert gas atmosphere, add 800 mL of N,N-dimethylacetamide to the polysulfone (PSf), heat to 100 °C, and stir for 0.5 h. After that, the polysulfone (PSf) is completely dissolved to obtain a mixed system;

[0035] 2), Add 100 g of polyethyleneimine (PEI) to the mixed system prepared in step 1), heat it to 130 °C, after reacting for 2 h, sediment the reaction feed liquid in water to remove the unreacted polyethyleneimine (PEI) and solvent, obtain solid particles, and dry the solid particles in an oven to obtain polysulfone-block-polyethyleneimine block copolymer (PSf-b-PEI). The prepared polysulfone-block-polyethyleneimine block copolymer (PSf-b-PEI) can be applied in the fields of biology, medicine, electronics and membrane separation.

[0036] Refer to Figure 1 , Figure 1 Parts a and b in are the TGA of the block polymers PSf-b-PEI and PSf prepared in Example 1 and 1 The H NMR comparison chart. By thermogravimetric test, the content of the hydrophilic segment in the PSf-b-PEI block copolymer is 9%, the molecular weight of the material is 52 kDa by GPC test, and 1 The H NMR characterization proves the successful synthesis of this block copolymer.

[0037] Example 2

[0038] A method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction, comprising the following steps:

[0039] 1), Add 500 g of polyethersulfone (PES) to a four-necked round-bottom flask equipped with a stirring paddle, use Schlenk operation to fully displace the air in the device, and then, under an inert gas atmosphere, add 2.5 L of N-methyl-2-pyrrolidone to the polyethersulfone (PES), heat it to 90 °C, after stirring for 1 h, the polyethersulfone (PES) is completely dissolved to obtain a mixed system;

[0040] 2), Add 200 g of polyethyleneimine (PEI) to the mixed system prepared in step 1), heat it to 120 °C, after reacting for 2 h, sediment the reaction feed liquid in water to remove the unreacted polyethyleneimine (PEI) and solvent, obtain solid particles, and dry the solid particles in an oven to obtain polyethersulfone-block-polyethyleneimine block copolymer (PES-b-PEI). The prepared polyethersulfone-block-polyethyleneimine block copolymer (PES-b-PEI) can be applied in the fields of biology, medicine, electronics and membrane separation.

[0041] Refer to Figure 1 , Figure 1 Parts c and d in are the TGA of the block polymers PES-b-PEI and PES prepared in Example 2 and 1$^1$H NMR comparison chart. By thermogravimetric test, the content of hydrophilic segments in the block copolymer of PES-b-PEI and PES is 20%. By GPC test, the molecular weight of the material is 48 kDa. By 1 $^1$H NMR characterization proves the successful synthesis of this block copolymer.

[0042] Example 3

[0043] Synthesis method of poly(ether)sulfone-based block copolymer based on chain exchange reaction, comprising the following steps:

[0044] 1), Add 300 g of polysulfone (PSf) into a four-necked round-bottom flask equipped with a stirrer paddle, use Schlenk operation to fully displace the air in the device, and then under an inert gas atmosphere, add 1.5 L of dimethyl sulfoxide to the polysulfone (PSf), heat to 120 °C, and stir for 0.5 h. After that, the polysulfone (PSf) is completely dissolved to obtain a mixed system;

[0045] 2), Add 50 g of hyperbranched polyethyleneimine (HPEI) to the mixed system prepared in step 1), heat to 140 °C, and after reacting for 1 h, sediment the reaction liquid in water to remove the unreacted hyperbranched polyethyleneimine (HPEI) and the solvent to obtain solid particles, and place the solid particles in an oven to dry to obtain a polysulfone-block-hyperbranched polyethyleneimine block copolymer (PSf-b-HPEI). The prepared polysulfone-block-hyperbranched polyethyleneimine block copolymer (PSf-b-HPEI) can be applied in the fields of biology, medicine, electronics and membrane separation.

[0046] By GPC test, the molecular weight of the material is 55 kDa.

[0047] Example 4

[0048] Synthesis method of poly(ether)sulfone-based block copolymer based on chain exchange reaction, comprising the following steps:

[0049] 1), Add 300 g of polyethersulfone (PES) into a four-necked round-bottom flask equipped with a stirrer paddle, use Schlenk operation to fully displace the air in the device, and then under an inert gas atmosphere, add 1.5 L of dimethyl sulfoxide to the polyethersulfone (PES), heat to 150 °C, and stir for 0.5 h. After that, the polyethersulfone (PES) is completely dissolved to obtain a mixed system;

[0050] 2), Add 80 g of polyvinylamine (PEE) to the mixed system obtained in step 1), heat to 150 °C, after reacting for 2 h, settle the reaction material solution in water to remove the unreacted polyvinylamine (PEE) and solvent, obtain solid particles, and place the solid particles in an oven to dry to obtain polyethersulfone-block-polyvinylamine block copolymer (PES-b-PEE). The obtained polyethersulfone-block-polyvinylamine block copolymer (PES-b-PEE) can be applied in the fields of biology, medicine, electronics and membrane separation.

[0051] The molecular weight of the material was tested by GPC to be 51 kDa.

[0052] Example 5

[0053] A method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction, comprising the following steps:

[0054] 1), Add 500 g of polyethersulfone (PES) to a four-necked round-bottom flask equipped with a stirring paddle, use Schlenk operation to fully displace the air in the device, and then, under an inert gas atmosphere, add 1.5 L of N,N-dimethylacetamide to the polyethersulfone (PES), heat to 140 °C, after stirring for 0.5 h, the polyethersulfone (PES) is completely dissolved to obtain a mixed system;

[0055] 2), Add 80 g of polyetheramine (PEA) to the mixed system obtained in step 1), heat to 140 °C, after reacting for 1 h, settle the reaction material solution in water to remove the unreacted polyetheramine (PEA) and solvent, obtain solid particles, and place the solid particles in an oven to dry to obtain polyethersulfone-block-polyetheramine block copolymer (PES-b-PEA). The obtained polyethersulfone-block-polyetheramine block copolymer (PES-b-PEA) can be applied in the fields of biology, medicine, electronics and membrane separation.

[0056] The molecular weight of the material was tested by GPC to be 42 kDa.

[0057] Example 6

[0058] A method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction, comprising the following steps:

[0059] 1), Add 200 g of polysulfone (PSf) to a four-necked round-bottom flask equipped with a stirring paddle, use Schlenk operation to fully displace the air in the device, and then, under an inert gas atmosphere, add 1 L of N,N-dimethylformamide to the polysulfone (PSf), heat to 150 °C, after stirring for 0.5 h, the polysulfone (PSf) is completely dissolved to obtain a mixed system;

[0060] 2), Add 50 g of polyallylamine (PAA) to the mixed system prepared in step 1), heat to 150 °C, after reacting for 1 h, sediment the reaction material liquid in water to remove the unreacted polyallylamine (PAA) and solvent, obtain solid particles, and dry the solid particles in an oven to obtain a polyethersulfone-block-polyetheramine block copolymer (PSf-b-PAA). The prepared polyethersulfone-block-polyetheramine block copolymer (PSf-b-PAA) can be applied in the fields of biology, medicine, electronics and membrane separation.

[0061] The molecular weight of the material was tested by GPC to be 57 kDa

[0062] Performance test

[0063] Test example

[0064] Add 2 Kg of polyethersulfone (PES) to a reaction kettle equipped with a stirring paddle, use Schlenk operation to fully displace the air in the device, and then, under an inert gas atmosphere, add 7 L of N,N-dimethylacetamide to the system, heat to 140 °C, and stir for 1 h. After that, the polyethersulfone (PES) is completely dissolved to obtain a mixed system.

[0065] After the PES is completely dissolved, add 500 g of polyethyleneimine (PEI) to it, continue to react for 2 h, sediment the reaction material liquid in water to remove the unreacted polyethyleneimine (PEI) and solvent, and dry the obtained solid particles in an oven to obtain the required polyethersulfone-block-polyethyleneimine block copolymer (PES-b-PEI);

[0066] The content of the hydrophilic segment in the block copolymer was tested by thermogravimetry to be 18%;

[0067] Prepare a separation membrane from the polyethersulfone-block-polyethyleneimine block copolymer (PES-b-PEI) prepared in the test example by the non-solvent induced phase separation method, and at the same time set a control group to prepare a separation membrane from polyethersulfone by the non-solvent induced phase separation method. The mass ratio of each component is as follows:

[0068]

[0069] The water flux of the polyethersulfone separation membrane prepared in the control group is zero;

[0070] The pure water permeability coefficient of the PES-b-PEI block copolymer separation membrane prepared in the test example remains at 35 LMH·bar -1 , for MgCl 2 The retention rate is above 90%.

[0071] The above are all preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby. Therefore, all equivalent changes made according to the structure, shape and principle of the present invention shall be covered within the protection scope of the present invention.

Claims

1. A method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction, characterized in that: The following steps are involved: S1, taking an organic solvent and a poly(ether)sulfone material respectively, mixing them, heating and stirring until they are completely dissolved, to obtain a mixed system; S2, adding a reactive hydrophilic polymer material containing an amino group to the mixed system obtained in step S1, removing the solvent after the reaction, and obtaining a poly(ether)sulfone-based block copolymer.

2. The method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction according to claim 1, characterized in that: The poly(ether)sulfone-based block copolymer in step S2 comprises at least two different types of repeating units, which can be summarized as AB type, ABA type or ABC type; Components A and C are hydrophilic polymer materials containing amino groups capable of reacting with component B; the component B is a poly(ether)sulfone material with a molecular weight higher than 10,000 Da, and the component B accounts for 50-98% of the total amount of the poly(ether)sulfone block copolymer.

3. The method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction according to claim 1, characterized in that: The mass ratio of the organic solvent to the poly(ether)sulfone material in step S1 is (3-5):

1.

4. The method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction according to claim 1, characterized in that: The mass ratio of the hydrophilic polymer material to the poly(ether)sulfone material in step S2 is 1:(2-6.25).

5. The method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction according to claim 1, characterized in that: The general formula of the poly(ether)sulfone material in step S1 includes: Any one or more of these.

6. The method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction according to claim 1, characterized in that: The amino-containing hydrophilic polymer material in step S1 includes one or more of polyethylene amine, polyethylene imine, hyperbranched polyethylene imine, polyallylamine, polyacrylamide, and polyether amine.

7. The method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction according to claim 1, characterized in that: The organic solvent in step S1 includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and sulfolane.

8. The method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction according to claim 1, characterized in that: The reaction temperature in step S1 is 90-150°C and the reaction time is 0.5-1h; The reaction temperature in step S2 is 120-150°C and the reaction time is 1-2h; The molecular weight of the poly(ether)sulfone-based block copolymer is between 12,000 Da and 60,000 Da.

9. Application of a poly(ether)sulfone-based block copolymer obtained by the method for synthesizing a poly(ether)sulfone-based block copolymer based on a chain exchange reaction according to any one of claims 1 to 8 in the fields of biology, medicine, electronics and membrane separation.

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