CN110746593A

CN110746593A - Multi-sulfonic polymer and application thereof in water treatment

Info

Publication number: CN110746593A
Application number: CN201810815939.1A
Authority: CN
Inventors: 陈桥; 陈广明; 邵芳可
Original assignee: Toray Pioneer Materials Research And Development (china) Co Ltd
Current assignee: Toray Pioneer Materials Research And Development (china) Co Ltd; Toray Advanced Materials Research Laboratories China Co Ltd
Priority date: 2018-07-24
Filing date: 2018-07-24
Publication date: 2020-02-04

Abstract

The invention discloses a multi-sulfonic acid group polymer, which contains sulfonic acid groups with high density and concentrated distribution, so that the polymer can effectively remove organic substances containing hydroxyl and phenolic hydroxyl in water through the action of hydrogen bonds; meanwhile, the structure at the end group contains amino or imino, so that the pollution resistance of the membrane can be improved. The invention provides a functional layer material for a beneficial water treatment composite membrane, which can remove phenols and polyalcohol compounds in water simultaneously and improve the pollution resistance of the membrane.

Description

Multi-sulfonic polymer and application thereof in water treatment

Technical Field

The invention relates to a polysulfonic polymer, in particular to a polysulfonic polymer and application thereof as a water treatment composite membrane.

Background

The polymer material containing sulfonic acid group has wide application prospect in membrane water treatment including reverse osmosis, nanofiltration, ultrafiltration, microfiltration and the like, and proton exchange membrane fuel cell field. As an independent film material, it is required to satisfy various requirements such as extremely high chemical stability, physical stability and thermal stability in order to meet practical use. However, as the number of sulfonic acid groups increases, the chemical and electrochemical durability of the film material as a single film material is reduced, and thus the application range is limited.

As a proton exchange membrane for a fuel cell, as mentioned in the prior arts [ CN103814062A ] and [ CN103635507B ], although the increase in the number of sulfonic acid groups can significantly improve the proton conductivity thereof, the hot water resistance and physical durability brought thereby are not small and varied, so that the content of sulfonic acid groups is limited, and in order to improve the durability of the material, microscopic phase-separated conformation is achieved by designing the chemical structure of blocks to achieve a sulfonic acid group-containing segment and a sulfonic acid group-free segment that ensures mechanical durability.

As a water treatment membrane material, the membrane can be divided into a hydrophilic membrane and a hydrophobic membrane according to the hydrophilic and hydrophobic properties of the membrane. Homogeneous membranes with single properties often cannot completely meet the requirements in practical application, which prompts people to research composite membranes, such as CN107983164A, CN108114616A and the like, so that the composite membranes have the excellent performances of various membranes. The hydrophobic membrane material comprises polyvinylidene fluoride, polypropylene, polytetrafluoroethylene and the like, and can be used as a bottom membrane or a base membrane due to good hydrophobicity and chemical corrosion resistance. But the hydrophobic membrane generates adsorption pollution due to strong hydrophobicity, so that two main separation indexes of membrane flux and rejection rate are reduced, and the service life of the membrane is shortened. Therefore, the composite film can be effectively relieved by compounding with a hydrophilic film, and the application possibility of the composite film in water phase systems such as biochemical pharmacy, food and beverage, water body purification and the like is expanded. Since the mechanical properties of the composite membrane are mainly provided by the base membrane, the requirements for stability of the functional hydrophilic membrane or coating layer as a part of the composite membrane can be slightly reduced compared with the single membrane material, thereby providing a new application direction for the hydrophilic polymer with multi-sulfonic groups.

Although the phenolic compounds are important chemical raw materials, the phenolic compounds also belong to organic pollutants with strong toxicity. The method is widely used in petrochemical, printing and dyeing, pesticide and other industries, and surface water is extremely easy to be polluted due to the existence of phenolic substances in industrial sewage. The polyol compound is widely used for producing industrial products such as alkyd resin, varnish, polyester resin, explosive and the like and is an important intermediate for synthesizing drying oil, adhesive, plasticizer and surfactant, and the attention on water treatment is relatively low due to low toxicity of the polyol compound.

Disclosure of Invention

The invention provides a polysulfonic polymer which can be used as a functional layer of a composite membrane for water treatment. The sulfonic group of the multi-sulfonic group polymer with high density and concentrated distribution can generate hydrogen bond action with organic substances containing hydroxyl and phenolic hydroxyl in water, so that the multi-sulfonic group polymer can be effectively removed; and the amine group or the imine group is contained, so that the pollution resistance of the film can be improved. The invention aims to provide a functional layer material for a water treatment composite membrane, which is beneficial for removing phenols and polyalcohol compounds in water simultaneously and improving the anti-pollution capability of the membrane.

The object of the invention can be achieved by the following measures:

a polysulfonate-based polymer having a structure represented by the following general formula (N1):

in the general formula (N1), N1, N2, N3 and N4 are independently integers of 0-2, and the sum of the integers is more than or equal to 4; m is an integer of 1 or more; each Y1, Y2 is independently a keto group, a sulfone group, a direct bond, -PO (R1) -, - (CF)₂)_f-or-C (CF)₃)₂-any one of (a) and (b), wherein R1 is an organic group, and f is an integer of 1 to 5; m1 to M4 are any of hydrogen, metal cations, ammonium cations, or hydrocarbon groups having 1 to 20 carbon atoms; each X1 is independently O or S; q1 is an organic group containing an amine group or an imine group; q2 is any one of an organic group containing an amine group or an imine group, an organic group containing a halogen, -OH or-SH.

In the present invention, the polysulfonic acid-based polymer has a repeating unit containing one or more sulfonic acid groups, that is, in the above formula (N1), m is an integer of 1 or more. From the viewpoint of chemical stability, physical durability, and the like, m is preferably an integer of 4 or more. The repeating units may be formed by condensation of dihalides and diphenol compounds.

Since the polymer is removed by hydrogen bonding between the sulfonic acid group and the organic substance containing a hydroxyl group or a phenolic hydroxyl group when it is used in the field of water treatment, the number of sulfonic acid groups per repeating unit is 4 or more, that is, the sum of n1, n2, n3 and n4 is 4 or more. In the repeating unit, the position of the sulfonic acid group is not particularly specified, that is, the polysulfonic acid-based polymer can be synthesized from a sulfonic acid group-containing dihalide compound and a sulfonic acid group-containing dihydric phenol aromatic compound, can be synthesized from a sulfonic acid group-containing dihalide compound and a sulfonic acid group-free dihydric phenol aromatic compound, or can be synthesized from a sulfonic acid group-free dihalide compound and a sulfonic acid group-containing dihydric phenol aromatic compound.

However, from the viewpoint of effectively removing organic substances containing hydroxyl groups and phenolic hydroxyl groups from the polymer, it is preferable that the sulfonic acid groups are uniformly dispersed in each repeating unit, that is, each benzene ring contains 1 or 2 sulfonic acid groups (that is, n1, n2, n3, and n4 are independently an integer of 1 or 2), and the sum of the number of sulfonic acid groups in the repeating units is 4 to 8. More preferably, at least one benzene ring in each repeating unit is substituted with 2 sulfonic acid groups, i.e., the sum of the number of sulfonic acid groups in the repeating unit is 5 to 8 (the sum of n1 to n4 is 5 to 8). That is, the main chain part of the polymer is synthesized from the sulfonic acid group-containing dihalide compound and the sulfonic acid group-containing dihydric phenol aromatic compound.

In the above formula (N1), each of Y1 and Y2 is independently a ketone group, a sulfone group, a direct bond, -PO (R1) - (wherein R1 is an organic group), -CF₂)_f- (wherein f is an integer of 1 to 5) or-C (CF)₃)₂-any of the above. Among them, a ketone group (-CO-) and a sulfone group (-SO) are preferable from the viewpoints of chemical stability and cost₂-) or a direct bond. From the viewpoint of physical durability, Y1 is more preferably a ketone group or a direct bond; y2 is preferably a keto group or a sulfone group, most preferably a keto group. Specific examples of the organic group of R1 include any of a hydroxyl group, a carboxyl group, an amino group, a halogen, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silyl group, an ester group, an oxyalkyl group, an oxyaryl group, and derivatives thereof. From the viewpoint of structural stability, R1 is preferably any of C1 to C10 alkyl groups, C3 to C10 cycloalkyl groups, aryl groups, sulfonic acid group-containing aryl groups, C1 to C10 oxyalkyl groups, oxyaryl groups, sulfonic acid group-containing oxyaryl groups, or derivatives thereof. From the viewpoint of ease of obtaining a monomer raw material for synthesizing the polysulfonic acid group of the present invention, R1 is more preferably an aryl group, a sulfonic acid group-containing aryl group or a derivative thereofMost preferably a sulfonic acid group-containing phenyl group.

In the above formula (N1), each X1 is O or S, and is preferably O from the viewpoint of cost and physical durability.

In the above formula (N1), M1 to M4 are independently any of hydrogen, a metal cation, an ammonium cation, or a hydrocarbon group having 1 to 20 carbon atoms. Among them, examples of the metal cation include any of sodium, potassium, aluminum, magnesium, calcium, copper, nickel, cobalt, lead, zinc, tin, antimony, bismuth, silver, platinum, ruthenium, rhodium, palladium, osmium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, vanadium, titanium, indium, thallium, germanium, selenium, or tellurium ions. However, M1 to M4 are preferably hydrogen from the viewpoint of effectively removing organic substances containing a hydroxyl group and a phenolic hydroxyl group.

In the formula (N1), Q1 is an organic group containing an amine group or an imine group. When Q1 is an organic group containing an amine group, for example, the structure shown by the following formula (T1) can be given. When Q1 is an organic group containing an imino group, for example, it has a structure represented by the following formula (T2).

Wherein Z1 is any one of an ether group, a direct bond, an alkylene group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silane group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group or a derivative thereof, and Z3 is any one of an aldehyde group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silane group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group or a derivative thereof. From the viewpoint of structural stability, Z1 is preferably a direct bond, a C1 to C10 alkylene group, a C3 to C10 cycloalkyl group, a C1 to C10 oxyalkyl group, or a derivative thereof. From the viewpoint of ease of obtaining the compound, Z1 is more preferably a direct bond, a C1 to C5 alkylene group, or a derivative thereof. From the viewpoint of structural stability, Z3 is preferably any one of an aldehyde group, a C1 to C10 alkyl group, a C3 to C10 cycloalkyl group, a C1 to C10 oxyalkyl group, or a derivative thereof, and more preferably any one of an aldehyde group, a C3 to C10 cycloalkyl group, or a derivative thereof.

Z2 and Z4 are each independently any one of hydrogen, hydroxyl, amine, aldehyde, carboxyl or cyano. Since the polysulfonic acid-based polymer of the present invention is a functional layer as a water treatment membrane, Z2 and Z4 are more preferably a hydroxyl group or a carboxyl group, respectively, in order to increase the action between them and the base membrane, i.e., from the viewpoint of introduction of reactive sites.

In the present invention, X2 and X3 are preferably O from the viewpoint of cost and physical durability.

In the formula (N1), Q2 represents any of an organic group containing an amino group or an imino group, an organic group containing a halogen, -OH or-SH. From the viewpoint of ease of reaction control, Q2 is preferably any of an organic group containing an amine group or an imine group, or-OH or-SH. As described above, the polysulfonate-based polymer of the present invention is used as a functional layer of a water treatment membrane, and Q2 is preferably an organic group containing an amine group or an imine group from the viewpoint of improving the stain resistance of base films and increasing the action between the base films. When Q2 is an organic group containing an amine group, Q2 may have a structure represented by the following formula (T3), for example. When Q2 is an organic group containing an imino group, Q2 has a structure represented by the following formula T4, for example.

Wherein Z5 is any one of an ether group, a direct bond, an alkylene group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silane group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group or a derivative thereof, and Z7 is any one of an aldehyde group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silane group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group or a derivative thereof. From the viewpoint of structural stability, Z5 is preferably a direct bond, a C1 to C10 alkylene group, a C3 to C10 cycloalkyl group, a C1 to C10 oxyalkyl group, or a derivative thereof. From the viewpoint of ease of obtaining the compound, Z5 is more preferably a direct bond, a C1 to C5 alkylene group, or a derivative thereof. From the viewpoint of structural stability, Z7 is preferably any one of an aldehyde group, a C1 to C10 alkyl group, a C3 to C10 cycloalkyl group, a C1 to C10 oxyalkyl group, or a derivative thereof, and more preferably any one of an aldehyde group, a C3 to C10 cycloalkyl group, or a derivative thereof.

Z6 and Z8 are each independently any one of hydrogen, hydroxyl group, amine group, aldehyde group, carboxyl group or cyano group, and since the polysulfonate-based polymer of the present invention is a functional layer as a water treatment membrane, Z6 and Z8 are more preferably hydroxyl group or carboxyl group in order to increase its action between base membranes, i.e., from the viewpoint of introduction of reactive sites.

From the viewpoint of cost and physical durability, X4 and X6 are preferably O, and X5 and X7 are each independently O or S, preferably O.

In the above formula (N1), Q2 is preferably an organic group having a Q1 structure, that is, Z1 is the same as Z5, Z2 is the same as Z6, Z3 is the same as Z7, Z4 is the same as Z8, X2 is the same as X4, and X3 is the same as X6, from the viewpoint of easiness of reaction control.

A and B are structures capable of bonding a main chain and a compound containing amino and imino groups, and the specific structure is a divalent group having a structure shown in the following formula (T5).

Y3 is a keto group, a sulfone group, a direct bond, -PO (R2) - (wherein R2 is an organic group), -CF₂)_f1- (wherein f1 is an integer of 1 to 5) or-C (CF)₃)₂-any of the above. From the viewpoint of chemical stability and cost, Y3 is preferably a ketone group, a sulfone group or a direct bond. Specific examples of the organic group of R2 include a hydroxyl group, a carboxyl group, an amino group, a halogen, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silyl group, an ester group, an oxyalkyl group, an oxyaryl group, and derivatives thereof. From the viewpoint of structural stability, R2 is preferably a C1-C10 alkyl group, a C3-C10 cycloalkyl group, an aryl group, or a sulfonic acid group-containing aryl groupAny one of C1-C10 oxyalkyl, oxyaryl containing sulfonic group, or derivative thereof. From the viewpoint of ease of obtaining the compound, R2 is more preferably any of an aryl group, a sulfonic acid group-containing aryl group, or a derivative thereof, and most preferably a sulfonic acid group-containing phenyl group. From the viewpoint of physical durability, Y3 is preferably a ketone group or a sulfone group, and most preferably a ketone group.

M5 and M6 are independently any of hydrogen, metal cations, ammonium cations, or hydrocarbon groups having 1 to 20 carbon atoms, wherein the metal cations can be exemplified by any of sodium, potassium, aluminum, magnesium, calcium, copper, nickel, cobalt, lead, zinc, tin, antimony, bismuth, silver, platinum, ruthenium, rhodium, palladium, osmium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, vanadium, titanium, indium, thallium, germanium, selenium, or tellurium ions. However, M5 and M6 are preferably hydrogen from the viewpoint of effectively removing organic substances containing a hydroxyl group and a phenolic hydroxyl group.

n5 and n6 are independently integers of 1 or 2.

From the viewpoint of reaction control, a and B preferably have the same partial structure as that of the main chain constituent unit, that is, Y3 is the same as Y2, n5 is the same as n3, n6 is the same as n4, M5 is the same as M3, and M6 is the same as M4.

The following describes a method for synthesizing the polysulfonic acid-based polymer of the present invention. But the invention is not limited thereto. In the present invention, the preparation of the polysulfonic acid-based polymer comprises two steps:

synthesizing a main chain part of a polymer with at least one end being capped by halide through a nucleophilic substitution reaction of a dihalide compound with a structure shown as a general formula T6 and a dihydric phenol aromatic compound with a structure shown as a general formula T7;

and (II) introducing an organic group containing an amine group or an organic group containing an imine group into at least one end of the segment from a compound having a structure represented by the general formula T8 or a compound having a structure represented by the general formula T9.

The polymer backbone portion in the step (one) may be obtained by a monomer mixing reaction in the presence of a basic compound. The polymerization can be carried out at a temperature in the range from 0 to 350 ℃ and preferably from 50 to 250 ℃. When the temperature is lower than 0 ℃, the reaction tends to be insufficient, and when the temperature is higher than 350 ℃, the polymer tends to be degraded. The reaction can be carried out without solvent, but is preferably carried out in a solvent. Useful solvents include, but are not limited to, aprotic polar solvents such as N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphorous triamide, and the like, and solvents that can serve as stable solvents in aromatic nucleophilic substitution reactions can be used. These organic solvents may be used alone or in combination of two or more.

The basic compound includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., and a basic compound which can make the aromatic diol into an active phenoxy compound structure can be used. In order to increase the nucleophilicity of the phenoxide, crown ether such as 18-crown-6 may be suitably added. The sodium ion or potassium ion of the sulfonic acid group can improve the solubility in an organic solvent by coordinating with these crown ethers, and therefore, it is preferable to use such crown ethers.

In aromatic nucleophilic substitution reactions, water is a by-product in some cases. In this case, toluene or the like may be present in the reaction system, and regardless of the polymerization solvent, it may move to the outside of the system as an azeotrope with water. Water absorbents such as molecular sieves and the like may also be used in the method of moving water to the outside of the system.

The entrainer used to remove the water of reaction or water introduced during the reaction is generally any inactive compound that does not substantially hinder polymerization, can co-distill with water, and can boil between about 25 ℃ to about 250 ℃. Typical entrainers include benzene, toluene, xylene, chlorobenzene, dichloromethane, dichlorobenzene, trichlorobenzene, cyclohexanone, and the like. Naturally, it is advantageous to select an entrainer with a boiling point lower than that of the bipolar solvent used. An entrainer is generally used, but is not necessarily required when high reaction temperatures are used, for example temperatures of 200 ℃ or more, especially when an inert gas is continuously sprayed onto the reaction mixture. It is generally desirable to carry out the reaction under an inert atmosphere in the absence of oxygen.

When the aromatic nucleophilic substitution reaction is carried out in a solvent, the monomer is preferably fed so that the concentration of the polymer to be produced is 5 to 50% by weight. At a concentration of less than 5% by weight, the degree of polymerization tends to be difficult to increase. On the other hand, when the concentration is more than 50% by weight, the viscosity of the reaction system tends to be too high, and it is difficult to conduct the post-treatment of the reaction product.

The terminal structure of the polymer main chain obtained in the step (one) can be confirmed by 1H-NMR of a nuclear magnetic resonance spectroscopic solution.

The main chain part of the polymer having at least one terminal halide end-capped in the step (two) obtained in the step (one) can be obtained by mixing and reacting a monomer having an amine group or an imine group in the presence of a basic compound. The main chain portion of the polymer having at least one terminal halide end obtained in the step (one) may or may not be subjected to a purification treatment. The reaction conditions of the step (II) are the same as those of the step (I).

The reaction may be carried out at a temperature in the range of 0 to 350 c, preferably 50 to 250 c. When the temperature is lower than 0 ℃, the reaction tends to be insufficient, and when the temperature is higher than 350 ℃, the polymer tends to be degraded. The reaction can be carried out without solvent, but is preferably carried out in a solvent. Useful solvents include, but are not limited to, aprotic polar solvents such as N, N-dimethylacetamide, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphorous triamide, and the like, and solvents that can serve as stable solvents in aromatic nucleophilic substitution reactions can be used. These organic solvents may be used alone or in combination of two or more.

The basic compound includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., and a basic compound which can make the aromatic diol into an active phenoxy compound structure can be used.

In the same step (one), water is a by-product in some cases in the aromatic nucleophilic substitution reaction. In this case, toluene or the like may be present in the reaction system, and regardless of the polymerization solvent, it may move to the outside of the system as an azeotrope with water. Water absorbents such as molecular sieves and the like may also be used in the method of moving water to the outside of the system.

When the aromatic nucleophilic substitution reaction is carried out in a solvent, the monomer is preferably fed so that the concentration of the polymer to be produced is 5 to 50% by weight. When the concentration is less than 5% by weight, the degree of polymerization tends to be difficult to increase. On the other hand, when the concentration is more than 50% by weight, the viscosity of the reaction system tends to be too high, and it is difficult to conduct the post-treatment of the reaction product.

After the reaction is completed, the residue is cleaned, and the solvent can be removed from the reaction solution by evaporation, followed by obtaining the desired polymer. Alternatively, the polymer can be obtained by adding the reaction solution to a solvent in which the solubility of the polymer is low and the solubility of the by-product inorganic salt is high, thereby removing the inorganic salt, precipitating the polymer as a solid, and filtering the filtrate. The recovered polymer is optionally washed with water, alcohol or other solvent and dried.

In the above preparation method, the specific structure of the dihalide compound represented by the general formula T6 is as follows:

wherein Y2' is a keto group, a sulfone group, a direct bond, -PO (R3) - (wherein R3 is an organic group), -CF₂)_f2- (wherein f2 is an integer of 1 to 5) or-C (CF)₃)₂Any one of W is F, Cl, Br or I, M3 'and M4' are any one of hydrogen, metal cations, ammonium cations or hydrocarbon groups with 1 to 20 carbon atoms independently, and n31 and n41 are integers of 0 to 2 independently.

Here, W may be fluorine, chlorine, bromine or iodine, but from the viewpoint of reactivity, among them, fluorine or chlorine is preferable, and fluorine is most preferable. Examples of the electron-withdrawing group Y2' include a ketone group, a sulfone group, a direct bond, -PO (R3) - (wherein R3 is an organic group), -CF₂)_f2- (wherein f2 is an integer of 1 to 5) or-C (CF)₃)₂-any of the above. Among them, from the viewpoint of chemical stability and cost, any of a ketone group, a sulfone group, or a direct bond is preferable, and a ketone group or a sulfone group is more preferable. From the viewpoint of physical durability, a ketone group is most preferable.

In the formula (T6), R3 may be any of a hydroxyl group, a carboxyl group, an amino group, a halogen, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silyl group, an ester group, an oxyalkyl group, an oxyaryl group, or a derivative thereof. From the viewpoint of structural stability, R3 is more preferably any of C1 to C10 alkyl groups, C3 to C10 cycloalkyl groups, aryl groups, sulfonic acid group-containing aryl groups, C1 to C10 oxyalkyl groups, oxyaryl groups, sulfonic acid group-containing oxyaryl groups, or derivatives thereof. From the viewpoint of ease of obtaining the compound, R3 is more preferably any of an aryl group, a sulfonic acid group-containing aryl group, or a derivative thereof, and most preferably a sulfonic acid group-containing phenyl group.

M3 ', M4' are independently any of hydrogen, metal cations, ammonium cations or hydrocarbyl groups having 1 to 20 carbon atoms. The metal cation may be any of sodium, potassium, aluminum, magnesium, calcium, copper, nickel, cobalt, lead, zinc, tin, antimony, bismuth, silver, platinum, ruthenium, rhodium, palladium, osmium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, vanadium, titanium, indium, thallium, germanium, selenium, or tellurium ions. From the viewpoint of cost and availability of the starting compound, any of sodium, potassium, aluminum, magnesium, calcium, copper, zinc, or silver ions is more preferable.

In the above preparation method, the structure of the diphenol compound of formula T7 is as follows:

wherein Y1' is a keto group, a sulfone group, a direct bond, -PO (R4) - (wherein R4 is an organic group), - (CF)₂)_f3- (wherein f3 is an integer of 1 to 5) or-C (CF)₃)₂-any of; u is hydroxyl; m1 'and M2' are any one of hydrogen, metal cations, ammonium cations or alkyl with 1 to 20 carbon atoms independently, and n11 and n21 are integers of 0-2 independently.

In this case, U is OH. The electron-withdrawing group Y1' includes a ketone group, a sulfone group, a direct bond, -PO (R4) - (wherein R4 is an organic group), -CF₂)_f3- (wherein f3 is an integer of 1 to 5) or-C (CF)₃)₂-any of the above. Among them, a ketone group, a sulfone group or a direct bond is preferable from the viewpoint of chemical stability and cost. From the viewpoint of physical durability, a ketone group or direct bonding is more preferable.

In the formula (T7), R4 may be any of a hydroxyl group, a carboxyl group, an amino group, a halogen, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silyl group, an ester group, an oxyalkyl group, an oxyaryl group, or a derivative thereof. From the viewpoint of structural stability, R4 is more preferably any of C1 to C10 alkyl groups, C3 to C10 cycloalkyl groups, aryl groups, sulfonic acid group-containing aryl groups, C1 to C10 oxyalkyl groups, oxyaryl groups, sulfonic acid group-containing oxyaryl groups, or derivatives thereof. From the viewpoint of ease of obtaining the compound, R4 is more preferably any of an aryl group, a sulfonic acid group-containing aryl group, or a derivative thereof. Most preferred is a sulfonic acid group-containing phenyl group.

M1 ', M2' are independently any of hydrogen, metal cations, ammonium cations, or hydrocarbon groups having 1 to 20 carbon atoms, wherein the metal cations can be exemplified by any of sodium, potassium, aluminum, magnesium, calcium, copper, nickel, cobalt, lead, zinc, tin, antimony, bismuth, silver, platinum, ruthenium, rhodium, palladium, osmium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, vanadium, titanium, indium, thallium, germanium, selenium, or tellurium ions. From the viewpoint of cost and availability of the starting compound, any of sodium, potassium, aluminum, magnesium, calcium, copper, zinc, or silver ions is more preferable.

In the above preparation method, the specific structures of the compounds represented by the general formulae (T8) and (T9) are as follows:

wherein Z1' is any of a direct bond, an ether group, an alkylene group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silane group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group, or a derivative thereof. Z3' is any of aldehyde group, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, silane group, ester group, ketone group, oxyalkyl group, oxyaryl group, or derivative thereof. From the viewpoint of structural stability, Z1' is preferably any of a direct bond, a C1 to C10 alkylene group, a C3 to C10 cycloalkyl group, a C1 to C10 oxyalkyl group, or a derivative thereof. From the viewpoint of ease of obtaining the compound, Z1' is more preferably a direct bond, a C1 to C5 alkylene group, or a derivative thereof. From the viewpoint of structural stability, Z3' is preferably any one of an aldehyde group, a C1 to C10 alkylene group, a C3 to C10 cycloalkyl group, a C1 to C10 oxyalkyl group, or a derivative thereof, and more preferably any one of an aldehyde group, a C3 to C10 cycloalkyl group, or a derivative thereof. Z2 'and Z4' are each independently any one of hydrogen, hydroxyl group, amine group, aldehyde group, carboxyl group or cyano group, and since the polysulfonate-based polymer of the present invention is a functional layer as a water treatment membrane, Z2 'and Z4' are more preferably hydroxyl group or carboxyl group in order to increase its function between base membranes, i.e., from the viewpoint of introduction of reactive sites. In view of chemical stability and production cost, the compound represented by (T8) is preferably a compound represented by the following formula (r1) to (r8), more preferably a compound represented by the following formula (r1), (r2), (r3) or (r4), and most preferably a compound represented by the following formula (r 1). The compound represented by (T9) is preferably a compound represented by the following formulae (r9) to (r 13).

The sulfonic group of the multi-sulfonic polymer provided by the invention, which is high in density and concentrated in distribution, can generate hydrogen bond action with organic substances containing hydroxyl and phenolic hydroxyl in water, so that phenols and polyol compounds in water can be effectively removed simultaneously; the amino or imino can improve the pollution resistance of the film; meanwhile, in order to form a stable coating on various membranes for water treatment, a terminal group structure with hydroxyl or carboxyl is specially introduced, so that a beneficial functional layer material for the composite membrane for water treatment is provided.

The compounding method of the polysulfonate-based polymer and other membrane materials is not limited, and uniform compounding can be realized on the premise of not influencing the performance of the matrix membrane material. Depending on the case of the base film, a solution film-forming method may be used. The water treatment composite membrane containing the polysulfonate polymer functional layer has adsorption and separation capacity of 10-200 mg/g for polyhydric alcohol pollutants and 50-250 mg/g for phenolic compounds at 25 ℃.

Detailed Description

The invention is obtained by the following examples of preferred embodiments, which are given by way of illustration only and do not limit the scope of the invention.

The conditions for measuring various physical properties were as follows:

(1) number average molecular weight and weight average molecular weight

The number average molecular weight and the weight average molecular weight of the polymer were measured by GPC. Measurement was carried out in an N-methyl-2-pyrrolidone solvent (N-methyl-2-pyrrolidone solvent containing 10mM lithium bromide) at a sample concentration of 0.1% by weight, a flow rate of 0.2 mL/min, and a temperature of 40 ℃ using HLC-8022GPC manufactured by Tosoh corporation as an integrated apparatus of an ultraviolet detector and a parallax refractometer, and 2 TSKgel SuperHM-H (inner diameter of 6.0 mM, length of 15 cm) manufactured by Tosoh corporation as a GPC test column, and number average molecular weight and weight average molecular weight were obtained in terms of polystyrene as a standard.

(2) Adsorption amount for polyol (ethylene glycol)

Dissolving 5g of the polysulfonic acid polymer prepared in the embodiment in NMP to prepare a solution with the concentration of 5 wt%, filtering, removing bubbles, uniformly coating the solution on the surface of a DOW XLE ultralow-pressure RO membrane sold on the market, drying for 24 hours at the temperature of 60 ℃ under normal pressure, and then drying for 1 hour at the constant temperature of 80 ℃ under vacuum to obtain a composite membrane, wherein the mass of a composite part can be known through the mass change of the membrane before and after the composite. And (3) testing conditions are as follows: the concentration of the ethylene glycol solution was calibrated by High Performance Liquid Chromatography (HPLC) after passing through the composite membrane at 25 ℃ and a flow rate of 1L/min and a pressure of 200psi at 2000 ppm. The concentration conversion of the ethylene glycol solution after the composite membrane treatment can calculate the adsorption capacity of the ethylene glycol of the polysulfonic acid polymer.

(3) Adsorption amount for phenol compound (phenol)

Dissolving the polysulfonic acid polymer prepared in the embodiment in NMP to prepare a solution with the concentration of 5 wt%, filtering, removing bubbles, uniformly coating the solution on the surface of a DOW XLE ultra-low pressure RO membrane sold in the market, drying for 24 hours at the temperature of 60 ℃ under normal pressure, then drying for 1 hour at the constant temperature of 80 ℃ under vacuum to obtain a composite membrane, and knowing the quality of a composite part through the quality change of the membrane before and after composite. And (3) testing conditions are as follows: the concentration of the phenol solution was calibrated by High Performance Liquid Chromatography (HPLC) at 25 ℃ by passing the composite membrane at a flow rate of 1L/min and a pressure of 200psi in 2000ppm phenol solution. The concentration conversion of the phenol solution after the composite membrane treatment can calculate the phenol adsorption capacity of the polysulfonic acid polymer.

(4) Anti-pollution performance

Dissolving the polysulfonic acid polymer prepared in the embodiment in NMP to prepare a solution with the concentration of 5 wt%, filtering, removing bubbles, uniformly coating the solution on the surface of a DOW XLE ultra-low pressure RO membrane sold in the market, drying for 24 hours at the temperature of 60 ℃ under normal pressure, then drying for 1 hour at the constant temperature of 80 ℃ under vacuum to obtain a composite membrane, and knowing the quality of a composite part through the quality change of the membrane before and after composite. Firstly, testing the initial flux of the membrane by using 1g/L NaCl solution, then continuously passing through the composite membrane for 3 hours under the pressure of 200psi at the flow rate of 0.5L/min by using dodecyl trimethyl ammonium bromide with the concentration of 20mg/L as a simulated pollution agent, then flushing the composite membrane for 2 hours at normal pressure by using deionized water, finally testing the flux of the membrane by using 1g/L NaCl solution, and dividing the value of the flux by the initial flux of the membrane to obtain the flux retention rate.

The following starting materials (a) to (f) used in the examples were all available from alatin reagent (shanghai) ltd:

(e) four compounds containing amine groups

(f) Alkali catalyst: potassium carbonate; organic solvent: n-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO), toluene, isopropanol, etc. available from national pharmaceutical group chemical reagents, Inc

The various sulfonic acid group-containing diphenol compounds used in the examples were obtained by the synthesis method described in JP 2004-18449A; various dihalides containing sulfonic acid groups are obtained by the process described in CN 103814062A.

The polysulfonic acid base polymer of the present invention is obtained under the following synthesis conditions: under nitrogen atmosphere, diphenol compound (100mmol), dihalo compound (98-105 mmol) and anhydrous potassium carbonate (52.44g, 379.5mmol), dimethyl sulfoxide (DMSO, 306mL) and toluene (120mL) are mixed and heated to 140 ℃ according to a specific molar ratio, water is divided for 6 hours, toluene in the system is evaporated, the temperature is raised to 150 ℃ for 20 hours, and GPC is sampled to monitor the molecular weight.

The reaction solution is naturally cooled to 80 ℃, DMSO (100ml) containing an amino compound (10mmol) in the solution is added, 100ml of toluene is added, the temperature is raised to 140 ℃, water is divided for 2 hours, the reaction is finished, and the reaction solution is naturally cooled to room temperature. The reaction was diluted by adding DMSO (300mL), transferred to a centrifuge flask, and centrifuged at high speed (8000rpm) for 30 minutes. The supernatant was slowly poured into 4.5L of isopropyl alcohol (IPA) to obtain a white powdery polymer, which was washed 2 times with 3L of isopropyl alcohol in turn and vacuum-dried at 120 ℃ for 24 hours to obtain a white or pale yellow solid powder. The final number average molecular weight (Mn) was measured by GPC.

Examples and comparative examples

1) List of polymerization reactions

Comparative example 3 is a commercially available DOW XLE ultra low pressure RO membrane without the functional layer of polysulfonate polymer of the present invention.

2) List of Properties of Polysulfonic acid-based polymers

Claims

1. A polysulfonic acid based polymer characterized by: the polysulfonic acid-based polymer is a polymer represented by the following general formula (N1):

2. The polysulfonate polymer of claim 1 wherein: in the general formula (N1), N1, N2, N3 and N4 are independently integers of 1 or 2; m is an integer of 4 or more; M1-M4 are hydrogen; q2 is any one of organic group containing amino or imino, -OH or-SH.

3. The polysulfonic acid-based polymer of claim 2, where in formula (N1), each of Y1 and Y2 is independently any of a ketone group, a sulfone group, or a direct bond.

4. The polysulfonic acid-based polymer of claim 2 where in formula (N1), N1, N2, N3, N4 are independently integers of 1 or 2 and the sum is 5 or greater.

5. The polysulfonic acid based polymer of claim 2 where in formula (N1), Y1 is a keto group or a direct bond and Y2 is a keto group.

6. The polysulfonic acid-based polymer of claim 2, where in formula (N1), Q1 is a structure of formula (T1) or a structure of formula (T2):

wherein Z1 is any one of an ether group, a direct bond, an alkylene group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silane group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group, or a derivative thereof, Z3 is any one of an aldehyde group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silane group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group, or a derivative thereof, Z2 and Z4 are each independently any one of hydrogen, a hydroxyl group, an amine group, an aldehyde group, a carboxyl group, or a cyano group, and X.

7. The polysulfonic acid based polymer of claim 6 where in formulas (T1) and (T2) Z1 is a direct bond, C1-C10 alkylene, C3-C10 cycloalkyl, C1-C10 oxyalkyl or a derivative thereof and Z3 is any of aldehyde, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 oxyalkyl or a derivative thereof.

8. The polysulfonic acid-based polymer of claim 6 where in formulas (T1) and (T2) Z1 is either a direct bond, C1-C5 alkylene or a derivative thereof, Z3 is either an aldehyde group, C3-C10 cycloalkyl or a derivative thereof, and Z2 and Z4 are either hydroxyl or carboxyl, respectively.

9. The polysulfonic acid-based polymer of claim 2, where in formula (N1), Q2 is a structure of formula (T3) or a structure of formula (T4):

wherein, Z5 is any one of an ether group, a direct bond, an alkylene group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silyl group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group or a derivative thereof, Z7 is any one of an aldehyde group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a silyl group, an ester group, a ketone group, an oxyalkyl group, an oxyaryl group or a derivative thereof, Z6 and Z8 are each independently any one of hydrogen, a hydroxyl group, an amine group, an aldehyde group, a carboxyl group or a cyano group, X4 and X6 are O, X5 and X7 are each independently O or S, a and B are divalent groups having a structure of the following formula (T36:

y3 is keto, sulfone, direct bond, -PO (R2) -, - (CF)₂)_f1-or-C (CF)₃)₂-any one of (a) and (b), wherein R2 is an organic group, and f1 is an integer of 1 to 5; m5, M6 are each independently any of hydrogen, a metal cation, an ammonium cation or a hydrocarbon group having 1 to 20 carbon atoms, and n5, n6 are each independently an integer of 1 or 2.

10. The polysulfonic acid based polymer of claim 9 where R2 in formula (T5) is any of hydroxyl, carboxyl, amine, halogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, silane, ester, oxyalkyl, oxyaryl or derivatives thereof.

11. The polysulfonic acid-based polymer of claim 9, where in formula (T5), Y3 is a ketone group, sulfone group, or direct bond.

12. The polysulfonic acid-based polymer of claim 9 where, in formula (N1), Q2 is an organic group having the structure Q1.

13. A composite membrane for water treatment comprising a functional layer having the polysulfonic polymer as described in any one of claims 1 to 12.