CN106215727B - A kind of preparation method of polyaminoacid modified polyphenyl thioether perforated membrane - Google Patents

Abstract

The invention discloses a kind of preparation methods of polyaminoacid modified polyphenyl thioether perforated membrane.This method prepares PPS perforated membranes using TIPS, by nitrifying surface ammonification of the reduction method in PPS perforated membranes, cause the reaction of alpha amino acid N carboxyl inner-acid anhydrides by amino, is grafted to PPS porous film surfaces using different types of amino acid as characteristic group, obtains polyaminoacid MODIFIED PP S perforated membranes.This method is modified film surface, does not destroy the internal matrix structure and pore passage structure of film using the excellent physical and chemical performance of PPS perforated membranes, prepares a kind of perforated membrane with antipollution, biocompatibility.

Description

A kind of preparation method of polyamino acid modified polyphenylene sulfide porous membrane

technical field

The invention relates to the field of preparation of polymer membrane materials, in particular to a preparation method of a polyamino acid modified polyphenylene sulfide porous membrane.

Background technique

Polyphenylene sulfide (PPS) is a new type of thermoplastic resin with excellent high temperature resistance, solvent resistance, acid and alkali corrosion resistance, radiation resistance, flame retardancy and good mechanical and electrical properties. It is used in electronics, automobiles, machinery and It is widely used in the chemical industry and is known as the sixth largest engineering plastic. PPS material can be used at high temperature for a long time in acidic, alkaline and organic solvents, and its wear resistance and aging resistance are particularly strong. As a membrane material, PPS can realize the direct treatment of organic solvents. Because PPS has excellent creep resistance, good dimensional stability, and high elastic modulus, it can avoid the dissolution and shedding of the membrane material. In summary, PPS has the potential to be used as a membrane material.

However, due to the hydrophobicity of PPS, the surface of the porous PPS membrane prepared by the TIPS method is hydrophobic, especially for the separation of biologically active substances containing proteins, which tends to cause low flux, and the adhesion of proteins is easy to cause Membrane fouling, or even pore blockage, directly affects the service life of the membrane. Improving the hydrophilic property of the membrane can effectively improve the anti-fouling performance of the membrane; coating and grafting substances containing zwitterions on the surface of the membrane can effectively improve the anti-protein fouling performance of the membrane and improve the biocompatibility of the membrane.

Contents of the invention

Aiming at the deficiencies of the prior art, the technical problem to be solved by the present invention is to provide a method for preparing a polyamino acid modified polyphenylene sulfide porous membrane. In this method, TIPS is used to prepare PPS porous membrane, and the surface of PPS porous membrane is ammonized by nitration reduction method, and the α-amino acid-N-carboxyl internal acid anhydride reaction is initiated by amino group, and different kinds of amino acids are grafted into PPS porous membrane as characteristic groups. On the surface of the membrane, a polyamino acid modified PPS porous membrane is obtained.

The technical solution of the present invention to solve the technical problem is to provide a method for preparing a polyamino acid modified polyphenylene sulfide porous membrane, which is characterized in that it includes the following steps:

1) Put the PPS porous membrane prepared by the TIPS method into a nitric acid solution, and carry out nitration reaction at 30-80°C for 0.5-24h; after the reaction, wash the PPS porous membrane until there is no NO ₃ ^- on the surface, and obtain a nitrated PPS porous membrane;

2) Disperse 0.01-1g catalyst in 50-200ml reaction solvent for 10-60min, then put 1-50g nitrated PPS porous membrane into it, heat up to 60-120℃, add 2-10g reducing agent, react 1- After 10h, wash and dry to obtain ammoniated PPS porous membrane;

The catalyst is made by loading the active component on the carrier; the active component is Pd, Ag, Au, Ru, Cu, Ni or Fe; the carrier is activated carbon, carbon nanotube, graphene, layer graphite, SiC, ZrO ₂ , TiO ₂ , SiO ₂ , SnO ₂ , Al ₂ O ₃ , ZSM-5, SBA-15, MCM-41, aluminum phosphorus molecular sieve, montmorillonite, Y-type molecular sieve or β-type molecular sieve;

The reaction solvent is at least one of alcohol solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, organic amine solvents, hydrocarbon solvents or amide solvents;

The reducing agent is at least one of hydrazine hydrate, metal hydride, _Na2S , sodium thiosulfide or _H2 ;

3) Dissolve 0.02-1g of α-amino acid-N-carboxylidene anhydride in 50-200ml of aprotic solvent, then put 1-50g of ammoniated PPS porous membrane into it, react at 30-65°C for 1-48h, wash and put The product is soaked in NaOH solution, washed and dried to obtain a polyamino acid modified PPS porous membrane;

The α-amino acid-N-carboxyl anhydride is L-glutamic acid-γ-benzyl ester-N-carboxyl anhydride, L-glycine-N-carboxyl anhydride, alanine-N-carboxyl anhydride, valeric acid At least one of amino acid-N-carboxyl anhydride or isoleucine-N-carboxyl anhydride;

The aprotic solvent is at least one of ether solvents, ketone solvents, nitrile solvents, halogenated hydrocarbon solvents, hydrocarbon solvents, sulfone solvents or amide solvents.

Compared with the prior art, the beneficial effect of the present invention is that the method utilizes the excellent physical and chemical properties of the PPS porous membrane to modify the surface of the membrane without destroying the internal matrix structure and pore structure of the membrane, and prepares an anti-pollution, Biocompatible porous membrane. By grafting amino groups on the outer surface of PPS membrane pores, the transformation from hydrophobic membrane to hydrophilic membrane is realized, which greatly improves the pure water flux of the membrane; Ring-opening polymerization, obtained polyamino acid modified PPS porous membrane. The pore distribution of the membrane is narrow, mainly composed of nano-scale pore channels, and the water contact angle is between 40-80°, which can realize the selective separation of organic small molecular compounds or substances with biological activity. The membrane has good anti-pollution ability , improve the service life of the PPS porous membrane.

Detailed ways

Specific examples of the present invention are given below. The specific embodiments are only used to further describe the present invention in detail, and do not limit the protection scope of the claims of the present application.

The invention provides a method for preparing a polyamino acid modified polyphenylene sulfide porous membrane, which is characterized in that it comprises the following steps:

1) Put the PPS porous membrane prepared by the TIPS method into a nitric acid solution, and carry out nitration reaction at 30-80°C for 0.5-24h; after the reaction, wash the PPS porous membrane until there is no NO ₃ ^- on the surface, and obtain a nitrated PPS porous membrane;

The concentration of the nitric acid solution is 10-60%;

2) Disperse 0.01-1g catalyst in 50-200ml reaction solvent for 10-60min, then put 1-50g nitrated PPS porous membrane into it, heat up to 60-120℃, add 2-10g reducing agent, react 1- After 10h, wash and dry to obtain ammoniated PPS porous membrane;

The catalyst is made by loading the active component on the carrier; the active component is Pd, Ag, Au, Ru, Cu, Ni or Fe; the carrier is activated carbon, carbon nanotube, graphene, layer graphite, SiC, ZrO ₂ , TiO ₂ , SiO ₂ , SnO ₂ , Al ₂ O ₃ , ZSM-5, SBA-15, MCM-41, aluminum phosphorus molecular sieve, montmorillonite, Y-type molecular sieve or β-type molecular sieve;

The reaction solvent is at least one of alcohol solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents, organic amine solvents, hydrocarbon solvents or amide solvents; the alcohol solvent is propanol, At least one of isopropanol, butanol, isobutanol or benzyl alcohol; the halogenated hydrocarbon solvent is at least one of tetrachloromethane, 1,2-dichloroethane or tetrahydrofuran; the ether The class solvent is butyl ether; The ester class solvent is ethyl acetate, butyl acetate, ethyl benzoate, ethyl formate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or dipropyl carbonate At least one; the organic amine solvent is at least one of aniline, propylamine or butylamine; the hydrocarbon solvent is at least one of cyclohexane, benzene or toluene; the amide solvent N,N -at least one of dimethylformamide and N,N-diethylacetamide;

The reducing agent is at least one of hydrazine hydrate, metal hydride, Na ₂ S, sodium thiosulfide or H ₂ ; the metal hydride is NaAlH ₄ or NaBH ₄ ;

3) Dissolve 0.02-1g of α-amino acid-N-carboxylidene anhydride in 50-200ml of aprotic solvent, then put 1-50g of ammoniated PPS porous membrane into it, react at 30-65°C for 1-48h, wash and put The product is soaked in 0.1-2mol/L NaOH solution for 30min-24h, washed and dried to obtain a polyamino acid modified PPS porous membrane;

The α-amino acid-N-carboxyl anhydride is L-glutamic acid-γ-benzyl ester-N-carboxyl anhydride, L-glycine-N-carboxyl anhydride, alanine-N-carboxyl anhydride, valeric acid At least one of amino acid-N-carboxyl anhydride or isoleucine-N-carboxyl anhydride;

The aprotic solvent is at least one of ether solvents, ketone solvents, nitrile solvents, halogenated hydrocarbon solvents, hydrocarbon solvents, sulfone solvents or amide solvents; the ether solvent is tetrahydrofuran, ether or at least one of anisole; the ketone solvent is at least one of acetone, methyl ethyl ketone or acetophenone; the nitrile solvent is acetonitrile or butyronitrile; the halogenated hydrocarbon solvent is four At least one of chlorinated carbon, chloroform or 1,2-dichloroethane; the hydrocarbon solvent is at least one of benzene, toluene or cyclohexane; the sulfone solvent is dimethyl sulfoxide , at least one of sulfolane or diphenyl sulfone; the amide solvent is at least one of N,N-dimethylformamide, N-methylpyrrolidone or N,N-dimethylacetamide;

Example 1

(1) Put the PPS porous membrane prepared by the TIPS method into a nitric acid solution with a concentration of 33%, seal and soak it at 50°C for 4 hours, and wash the surface of the PPS porous membrane without NO ₃ ^- after the reaction, to obtain a nitrated PPS porous membrane;

(2) Disperse 0.06g of Pd/C catalyst in 30mL of isobutanol for 20min, then put 10g of nitrated PPS porous membrane into it, raise the temperature to 80°C, add 8mL of hydrazine hydrate, react for 4h, wash and dry to obtain ammoniated PPS porous membrane;

(3) Dissolve 0.02g of L-glutamic acid-γ-benzyl ester-N-carboxylidene anhydride in 50ml of anhydrous tetrahydrofuran, then put 10g of ammoniated PPS porous membrane into it, react at 40°C for 4h, wash and put The product was soaked in 2mol/L NaOH solution for 2h, washed and dried to obtain a polyamino acid modified PPS porous membrane.

The pore size distribution of the membrane measured by mercury intrusion porosimetry is 0.1-1 micron, the water contact angle is 75°, the average water flux of the membrane is 121L/m ² h, the water flux of the membrane remains basically unchanged after 48 days of use, and no organic matter pollution is found.

Example 2

(1) Put the PPS porous membrane prepared by the TIPS method into a nitric acid solution with a concentration of 33%, seal and soak it at 50°C for 4 hours, and wash the surface of the PPS porous membrane without NO ₃ ^- after the reaction, to obtain a nitrated PPS porous membrane;

(2) Disperse 0.06g Ni/SiO ₂ catalyst in 30mL CCl ₄ for 20min, then put 10g nitrated PPS porous membrane into it, raise the temperature to 75°C, add 8gH ₂ , react for 4h, wash and dry to obtain ammoniated PPS Porous membrane;

(3) Dissolve 0.02g of isoleucine-N-carboxylidene anhydride in 50ml of anhydrous methyl ethyl ketone, then put 10g of ammoniated PPS porous membrane into it, react at 40°C for 4h, wash and dry to obtain polyamino acid modified Permanent PPS porous membrane.

The pore size distribution of the membrane measured by mercury intrusion porosimetry is 0.1-1.2 microns, the water contact angle is 71°, and the average water flux of the membrane is 125L/m ² h. After the membrane was used for 48 days, the water flux remained basically unchanged, and no organic matter pollution was found.

Example 3

(1) Put the PPS porous membrane prepared by the TIPS method into a nitric acid solution with a concentration of 33%, seal and soak it at 50°C for 4 hours, and wash the surface of the PPS porous membrane without NO ₃ ^- after the reaction, to obtain a nitrated PPS porous membrane;

(2) Disperse 0.06g of Ru/SBA-15 catalyst in 30mL of tetrahydrofuran for 20min, then put 10g of nitrated PPS porous membrane into it, raise the temperature to 60°C, add 12g of sodium thiosulfide, react for 4h, wash and dry to obtain Ammonia PPS porous membrane;

(3) Dissolve 0.05g of L-glycine-N-carboxyl internal acid anhydride in 100ml of anhydrous acetonitrile, then put 10g of ammoniated PPS porous membrane into it, react at 40°C for 4h, wash and dry to obtain polyamino acid modified PPS porous membrane.

The pore size distribution of the membrane measured by mercury intrusion porosimetry is 0.1-1.35 microns, the water contact angle is 63°, and the average water flux of the membrane is 138L/m ² h. After the membrane was used for 48 days, the water flux remained basically unchanged, and no organic matter pollution was found.

Example 4

(1) Put the PPS porous membrane prepared by the TIPS method into a nitric acid solution with a concentration of 33%, seal and soak it at 50°C for 4 hours, and wash the surface of the PPS porous membrane without NO ₃ ^- after the reaction, to obtain a nitrated PPS porous membrane;

(2) Disperse 0.06g Fe/ZMS-5 catalyst in 30mL dimethyl carbonate for 20min, then put 10g nitrated PPS porous membrane into it, raise the temperature to 80°C, add 8g NaAlH ₄ , react for 4h, wash and dry, Obtain ammoniated PPS porous membrane;

(3) Dissolve 0.05g of alanine-N-carboxyl internal acid anhydride in 60ml of anhydrous carbon tetrachloride, then put 10g of ammoniated PPS porous membrane into it, react at 40°C for 4h, wash and dry to obtain polyamino acid Modified PPS porous membrane.

The pore size distribution of the membrane measured by mercury intrusion porosimetry is 0.1-1.4 microns, the water contact angle is 68°, and the average water flux of the membrane is 147L/m ² h. After the membrane was used for 48 days, the water flux remained basically unchanged, and no organic matter pollution was found.

Example 5

(1) Put the PPS porous membrane prepared by the TIPS method into a nitric acid solution with a concentration of 33%, seal and soak it at 50°C for 4 hours, and wash the surface of the PPS porous membrane without NO ₃ ^- after the reaction, to obtain a nitrated PPS porous membrane;

(2) Disperse 0.06g Cu/SiC catalyst in 30mL N,N-dimethylformamide for 20min, then put 10g nitrated PPS porous membrane into it, raise the temperature to 80℃, add 8g NaBH ₄ , and react for 4h, Washing and drying to obtain ammoniated PPS porous membrane;

(3) Dissolve 0.1g of valine-N-carboxylidene anhydride in 100ml of anhydrous dimethyl sulfoxide, then put 10g of ammoniated PPS porous membrane into it, react at 40°C for 4h, wash and dry to obtain poly Amino acid modified PPS porous membrane.

The pore size distribution of the membrane measured by mercury intrusion porosimetry is 0.1-1.4 microns, the water contact angle is 72°, and the average water flux of the membrane is 135L/m ² h. After the membrane was used for 48 days, the water flux remained basically unchanged, and no organic matter pollution was found.

What is not mentioned in the present invention is applicable to the prior art.

Claims (6)

1. a kind of preparation method of polyaminoacid modified polyphenyl thioether perforated membrane, it is characterised in that include the following steps：

1) PPS perforated membranes prepared by TIPS methods are put into salpeter solution, nitration reaction 0.5- is carried out under the conditions of 30-80 DEG C 24h；Washing PPS perforated membranes to surface does not have NO after reaction₃ ^-, obtain nitrification PPS perforated membranes；

2) 0.01-1g catalyst is placed in 50-200ml reaction dissolvents and disperses 10-60min, then 1-50g nitrifications PPS is porous Film is put into wherein, is warming up to 60-120 DEG C, and 2-10g reducing agents are added, and after reacting 1-10h, washs drying, it is more to obtain ammonification PPS Pore membrane；

The catalyst be active component is loaded on carrier made of；The active component is Pd, Ag, Au, Ru, Cu, Ni Or Fe；The carrier is activated carbon, carbon nanotube, graphene, lamellar graphite, SiC, ZrO₂、TiO₂、SiO₂、SnO₂、Al₂O₃、 ZSM-5, SBA-15, MCM-41, phosphate aluminium molecular sieve, montmorillonite, Y type molecular sieve or beta molecular sieve；

The reaction dissolvent is that alcohols solvent, halogenated hydrocarbon solvent, ether solvent, esters solvent, organic amine solvent, hydro carbons are molten At least one of agent or amide solvent；

The reducing agent is hydrazine hydrate, metal hydride, Na₂S, thio vulcanized sodium or H₂At least one of；

3) 0.02-1g a-amino acid-N- carboxyl inner-acid anhydrides are dissolved in 50-200ml aprotic solvent, then by 1-50g ammonifications PPS perforated membranes are put into wherein, and product is put into NaOH solution after cleaning and impregnates by 30-65 DEG C of reaction 1-48h, after washing is dry, Obtain polyaminoacid MODIFIED PP S perforated membranes；

A-amino acid-N- carboxyl the inner-acid anhydrides are Pidolidone-γ-benzyl ester-N- carboxyls inner-acid anhydride, L- glycine-N- carboxyls In inner-acid anhydride, alanine-N- carboxyls inner-acid anhydride, valine-N- carboxyls inner-acid anhydride or isoleucine-N- carboxyl inner-acid anhydrides at least It is a kind of；

The aprotic solvent is ether solvent, ketones solvent, nitrile solvents, halogenated hydrocarbon solvent, hydrocarbon solvent, sulfone class solvent Or at least one of amide solvent.

2. the preparation method of polyaminoacid modified polyphenyl thioether perforated membrane according to claim 1, it is characterised in that described A concentration of 10-60% of salpeter solution in step 1).

3. the preparation method of polyaminoacid modified polyphenyl thioether perforated membrane according to claim 1, it is characterised in that step 2) metal hydride described in is NaAlH₄Or NaBH₄。

4. the preparation method of polyaminoacid modified polyphenyl thioether perforated membrane according to claim 1, it is characterised in that step 2) alcohols solvent described in is at least one of propyl alcohol, isopropanol, butanol, isobutanol or benzyl alcohol；The halogenated hydrocarbon is molten Agent is tetrachloromethane or 1,2- dichloroethanes；The ether solvent is butyl ether；The esters solvent is ethyl acetate, acetic acid fourth At least one in ester, ethyl benzoate, Ethyl formate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or dipropyl carbonate Kind；The organic amine solvent is at least one of aniline, propylamine or butylamine；The hydrocarbon solvent is hexamethylene, benzene or first At least one of benzene；The amide solvent is N,N-dimethylformamide or N, N- diethyl acetamides.

5. the preparation method of polyaminoacid modified polyphenyl thioether perforated membrane according to claim 1, it is characterised in that described The time that product impregnates in NaOH solution in step 3) is 30min-24h, and the concentration of NaOH solution is 0.1-2mol/L.

6. the preparation method of polyaminoacid modified polyphenyl thioether perforated membrane according to claim 1, it is characterised in that described Step 3) the ether solvent is at least one of tetrahydrofuran, ether or methyl phenyl ethers anisole；The ketones solvent is acetone, butanone Or at least one of acetophenone；The nitrile solvents are acetonitrile or butyronitrile；The halogenated hydrocarbon solvent is carbon tetrachloride, chloroform Or at least one of 1,2- dichloroethanes；The hydrocarbon solvent is at least one of benzene, toluene or hexamethylene；The sulfone class Solvent is at least one of dimethyl sulfoxide (DMSO), sulfolane or diphenyl sulphone (DPS)；The amide solvent is n,N-Dimethylformamide, At least one of N-Methyl pyrrolidone or DMAC N,N' dimethyl acetamide.