CN111909373A - Sulfonated polyaramide polymer - Google Patents

Sulfonated polyaramide polymer Download PDF

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CN111909373A
CN111909373A CN201910379568.1A CN201910379568A CN111909373A CN 111909373 A CN111909373 A CN 111909373A CN 201910379568 A CN201910379568 A CN 201910379568A CN 111909373 A CN111909373 A CN 111909373A
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sulfonated
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sulfonic acid
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side chain
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CN111909373B (en
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邵芳可
陈桥
川崎学
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Toray Advanced Materials Research Laboratories China Co Ltd
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
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    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides

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Abstract

The present invention specifically relates to a sulfonated polyaramid polymer containing a structural unit having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group, which has good water solubility, can greatly increase the apparent viscosity of an aqueous solution, has excellent salt resistance, and can be further used as a thickener in applications of polymer oil-displacing agents and liquid detergents.

Description

Sulfonated polyaramide polymer
Technical Field
The invention belongs to the field of functional polymer materials, and particularly relates to a water-soluble sulfonated polyaramide polymer, a preparation method thereof and application thereof as an aqueous solution efficient thickener.
Background
Water-soluble thickening polymers can be used in many fields, for example in cosmetics, foodstuffs, detergents, printing inks, emulsion paints and in polymer flooding for tertiary oil recovery in oil fields. Because of high technical maturity, polymer flooding has been widely applied to tertiary yield increase of most old oil fields in China. Polymer flooding refers to a method for adding a small amount of water-soluble thickening polymer into injection water for oil exploitation, so that the viscosity of a water phase is increased, the permeability of the water phase is reduced, the oil-water viscosity ratio is improved, the volume sweep coefficient is enlarged, and the recovery ratio of crude oil is improved. At present, most of water-soluble polymers applied to polymer flooding in industry are partially hydrolyzed polyacrylamide, however, when the polyacrylamide is subjected to high temperature or high salt content, molecular chains are easy to curl, so that the solution viscosity is reduced, the flooding effect is reduced, and the application is limited.
The synthesis of sulfonated polyamides is reported in the Journal of Polymer Science, Part A: Polymer Chemistry 1989,27(11),3745-3757, which prepares sulfonated polyamides by low temperature polycondensation using terephthaloyl chloride and 2, 5-diaminobenzenesulfonic acid as raw materials. Chinese patent CN 102382300B reports that 1, 4-di (4-carboxyphenoxy) benzene-2-sodium sulfonate and 4,4 '-diaminodiphenyl ether-2, 2' -disulfonic acid are used as raw materials to prepare water-soluble sulfonated aromatic polyamide through Yamazaki-Higashi phosphitylation reaction. However, these sulfonated polyamide polymers do not substantially simultaneously exhibit water solubility and high aqueous solution thickening efficiency.
Disclosure of Invention
In view of the above-mentioned disadvantages, it is an object of the present invention to provide a sulfonated polyaramid polymer which addresses the specific requirements in some fields for water-soluble thickening polymers. More importantly, the sulfonated polyaramide polymer not only has the temperature resistance and hydrolysis resistance of polyaramide, but also introduces sulfonic acid groups into all repeating units to ensure that the polyaramide polymer has water solubility and salt resistance, and simultaneously introduces long alkyl side chains to form hydrophobic association, thereby effectively improving the viscosity and the salt resistance of the polyaramide polymer in aqueous solution.
Details of the present invention are as follows.
The present inventors have found through intensive studies that when a sulfonated polyaramid polymer contains a structural unit having a long alkyl side chain having 7 or more carbon atoms and containing no sulfonic acid group, the long alkyl side chain can associate with itself or with other long alkyl side chains due to its hydrophobicity to form an association network, thereby achieving an effect of efficiently thickening an aqueous solution. Further, the sulfonated polyaramid polymer can be dissolved in an aqueous solution by containing a large amount of sulfonic acid hydrophilic groups. Accordingly, the present invention provides a sulfonated polyaramide polymer having excellent water solubility, salt resistance, and thickening properties, which contains a structural unit having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group.
In the present invention, the sulfonated polyaramide polymer is obtained by condensation polymerization of an aromatic dicarboxylic acid monomer and an aromatic diamine monomer. In the invention, the structural unit refers to a part of an aromatic dicarboxylic acid monomer or an aromatic diamine monomer after micromolecules are removed for forming amide bonds; the repeating unit refers to the minimum repeating part of the aromatic dicarboxylic acid monomer and the aromatic diamine after micromolecules are removed to form amide bonds. Therefore, in the present invention, one repeating unit includes two structural units.
The sulfonated polyaramid polymer of the present invention contains a structural unit having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group in a proportion of 0.5 to 10 mol%, preferably 1 to 8 mol%, and particularly preferably 2 to 5 mol%, based on the total number of repeating units of the sulfonated polyaramid polymer. When the molar content is more than 0.5%, the long alkyl side chain can form a good association network, so that the effect of thickening the aqueous solution is improved. When the molar content is 10% or less, the problem that the solubility of the sulfonated polyaramid polymer in an aqueous solution is lowered by introducing a long alkyl side chain as a hydrophobic group too much can be prevented. Ideally, the sulfonated polyaramid polymers of the present invention should be miscible with water in any desired ratio. However, according to the present invention, it is sufficient to make the sulfonated polyaramid polymer water-soluble at least at the desired use concentration and the desired pH value by controlling the proportion of the structural units containing long alkyl side chains.
As the sulfonated polyaramid polymer of the present invention, other structural units in its repeating unit are not limited as long as it has an aromatic ring, a sulfonic acid group and an amide group, except for the structural unit containing the above-described long alkyl side chain having 7 or more carbon atoms and not containing a sulfonic acid group. However, from the viewpoint of water solubility, temperature resistance, hydrolysis resistance and the like, the sulfonated polyaramid of the present invention is preferably composed of a repeating unit containing no long alkyl side chain represented by the following general formula (1) and a repeating unit containing a structural unit containing a long alkyl side chain having 7 or more carbon atoms and containing no sulfonic acid group represented by the following general formula (2),
Figure BDA0002052901570000031
in the general formula (1), Ar1And Ar2Each independently represents a sulfonic acid-containing groupDivalent organic radicals of the aromatic ring group are the sites where the moiety of formula (1) binds to other repeating units.
Figure BDA0002052901570000032
In the general formula (2), Ar3A divalent organic group containing an aromatic ring having a sulfonic acid group, Ar4Represents an aromatic ring-containing divalent organic group having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group, and is a site at which the moiety of the general formula (2) is bonded to other repeating units.
To further increase water solubility, temperature resistance and hydrolysis resistance, Ar1And Ar3Further preferably selected from any one of the following general formulae (X-1) to (X-5).
Figure BDA0002052901570000041
Ar2Further preferably selected from any one of the following structures (Y-1) to (Y-5).
Figure BDA0002052901570000042
M in the general formulas (X-1) to (X-5) and (Y-1) to (Y-5) independently represents one of hydrogen, a metal cation or an ammonium cation.
In addition, from the viewpoint of cost and structural stability, a divalent aromatic ring-containing organic group Ar having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group4The specific structure of (3) is more preferably a structure represented by the following general formula (3):
Figure BDA0002052901570000043
wherein Z represents a structural unit represented by the following general formula (C-1), or a structural unit represented by the following general formula (C-2):
Figure BDA0002052901570000051
in the general formula (C-1), R1And R2Each independently represents one of a hydrogen atom, a linear, branched or cyclic alkyl chain, and R1And R2The sum of the number of carbon atoms of (a) is 7 or more.
Figure BDA0002052901570000052
In the general formula (C-2), R3Is one of hydrogen atom, straight chain, branched chain or cyclic alkyl chain, f is an integer of 0 to 10, e is an integer of 1 to 10, e + R3The number of carbon atoms of (a) is not less than 7.
In the general formula (C-1), as R1Or R2Examples of the straight, branched or cyclic alkyl chain include alkyl chains having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl, and cyclic alkyl chains having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl and cyclopentyl.
In the general formula (C-2), as R3Examples of the straight, branched or cyclic alkyl chain include alkyl chains having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl, and cyclic alkyl chains having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl and cyclopentyl.
The long alkyl side chain of the present invention preferably has 10 or more carbon atoms from the viewpoint of further increasing the hydrophobicity of the long alkyl side chain and improving the association effect to obtain an extremely high thickening effect.
The specific structure represented by the above general formula (C-1) may be a structure represented by any of the general formulae (C-1-1) to (C-1-6) from the viewpoints of improvement in the effect of association, easy availability of raw materials, and cost.
Figure BDA0002052901570000061
As the specific structure represented by the above general formula (C-2), structures represented by general formulas (C-2-1) to (C-2-5) can be listed.
Figure BDA0002052901570000062
The sulfonated polyaramid polymer of the invention has no special requirement on the molecular weight, but when the molecular weight is lower, the defects of unobvious thickening effect and insufficient stability can occur; the sulfonated polyaramid polymer of the present invention preferably has a viscosity average molecular weight of 20 to 1000 ten thousand because it takes too long to dissolve in water and the final solubility is also affected when the molecular weight is too high.
The sulfonated polyaramid polymer of the present invention can be used in the field of polymer flooding for tertiary oil recovery in oil fields, and has a water solubility of at least 20g/L, particularly preferably 50g/L or more at 25 ℃.
The sulfonated polyaramide polymer can be used in the polymer flooding field of tertiary oil recovery in oil fields, and the apparent viscosity of an aqueous solution prepared according to the solid content of 2 percent reaches 20 mPa.S at the specified test temperature of 80 DEG C-1Above, particularly preferably 40 mPas-1The above. Furthermore, when an aqueous solution was prepared at a solid content of 2% and the aqueous solution contained sodium chloride at a concentration of 25000mg/L, the apparent viscosity at 80 ℃ at the specified test temperature reached 20 mPaS-1Above, particularly preferably up to 35 mPas-1The above.
The following is an example of the method for synthesizing the sulfonated polyaramid polymer of the present invention, but the present invention is not limited thereto. For example, under the protection of an inert gas, a catalyst is added to an organic solvent and heated to dissolve the catalyst, and a sulfonated aromatic dicarboxylic acid monomer, a sulfonated aromatic diamine monomer, an aromatic diamine monomer having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group, and a condensing agent are added in a specific molar ratio. Reacting at 30-50 deg.C for 2-4 hr, heating to 70-90 deg.C, reacting for 2-4 hr, heating to 100 deg.C and 130 deg.C, and reacting for 12-96 hr. Then the polymer solution is cooled to room temperature, poured into a large amount of acetone or methanol solution to obtain precipitate, washed, filtered and dried to obtain the sulfonated polyaramide polymer. Among them, N-methyl-2-pyrrolidone (NMP) can be used as the organic solvent, triphenyl phosphite (TPP), pyridine (Py), etc. or a mixture thereof can be used as the condensing agent, and calcium chloride, lithium chloride, or an interchelation system thereof can be used as the catalyst. Furthermore, a solubilizing aid such as Triethylamine (TEA) may be added to the reaction.
The sulfonated aromatic dicarboxylic acid monomer or the sulfonated aromatic diamine monomer can be obtained by carrying out sulfonation reaction on a corresponding non-sulfonated aromatic dicarboxylic acid monomer by using concentrated sulfuric acid or fuming sulfuric acid as a solvent and a sulfonating agent. Specific sulfonation reaction conditions may be exemplified by: reacting at 50-100 deg.C for 12-24 hr, cooling to room temperature, pouring the reaction solution into appropriate amount of crushed ice, salting out with sodium chloride to obtain crude product, and refining and purifying.
Examples of the preparation of the aromatic diamine monomer having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group are given below, but the present invention is not limited thereto. The aromatic bisphenol structure compound which is provided with a long alkyl side chain with an alkyl chain side chain of more than 7 carbon atoms and does not contain a sulfonic acid group is synthesized by the reaction of alkyl aldehyde (or ketone) with more than 7 carbon atoms and phenol, then the aromatic bisphenol structure compound is reacted with paranitrobenzoyl chloride, and finally nitro is hydrogenated into amino, so that the aromatic diamine monomer which is provided with a long alkyl side chain of more than 7 carbon atoms and does not contain a sulfonic acid group is obtained. The aromatic diamine monomer having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group can also be obtained by reacting a bisphenol structure compound having a long alkyl side chain of 7 or more carbon atoms with p-aminobenzoyl chloride having an amino protecting group and deprotecting the reaction product. The amino-protecting group may be exemplified by an alkoxycarbonyl group, an acyl group or an alkyl group.
The sulfonated polyaramid polymer of the present invention has a very high thickening effect when used in a small amount in an aqueous solution, and therefore has an application as a thickener in a polymer oil-displacing agent and a liquid detergent.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention. Further, the conditions for measuring various properties are as follows:
(1) viscosity average molecular weight
The viscosity average molecular weight of the sulfonated polyaramide polymers prepared in the following examples and comparative examples was measured by a one-point method at a constant temperature of 30 ℃ using an Ubbelohde viscometer.
(2) Solubility test
0.5g of the sulfonated polyimide polymer prepared in the following examples and comparative examples was added to 10mL of water, heated at 80 ℃ for 16 hours, and left at 25 ℃ overnight to measure the solubility.
(3) Viscosity measurement
The sulfonated polyimide polymers prepared in the following examples and comparative examples were formulated into an aqueous solution at a solid content of 2%, and the apparent viscosity of the polymer solution was measured with a Brookfield viscometer at a prescribed test temperature of 80 ℃.
(4) Salt tolerance test
The polymer was formulated as an aqueous solution at 2% solids and the apparent viscosity of the polymer solution was measured with a Brookfield viscometer at a specified test temperature of 80 ℃ with sodium chloride added at a concentration of 25000 mg/L.
The catalysts used in the following examples and comparative examples were calcium chloride and lithium chloride, the condensing agent was triphenyl phosphite and pyridine, and the organic solvent was N-methyl-2-pyrrolidone, which were all analytically pure and purchased from national reagents ltd. The catalyst is a calcium chloride and lithium chloride mutual-matching system, and the weight ratio is 10: 1; the condensing agent is a mixed system of triphenyl phosphite and pyridine, and the weight ratio is 1.1: 1.
the sulfonated aromatic dicarboxylic acid monomers used in the examples are shown in table 1, the sulfonated aromatic diamine monomers used are shown in table 2, and the aromatic diamine monomers having a long alkyl side chain and no sulfonic acid group used are shown in table 3, and they were obtained by the methods described above.
TABLE 1 sulfonated aromatic dicarboxylic acid monomers
Figure BDA0002052901570000102
TABLE 2 sulfonated aromatic diamine monomers
Figure BDA0002052901570000101
Aromatic diamine monomers having long alkyl side chains and no sulfonic acid groups used in Table 3
Figure BDA0002052901570000111
Example 1
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.997: 0.003 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 having a long alkyl side chain and containing no sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 2
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.995: 0.005 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 having a long alkyl side chain and containing no sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 3
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.99: 0.01 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 4
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.98: 0.02 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 5
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 with long alkyl side chain and without sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 6
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.95: 0.05 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 7
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.92: 0.08 sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 having a long alkyl side chain and no sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 8
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.9: 0.1 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 9
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.89: 0.11 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 having a long alkyl side chain and no sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 10
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C2 with long alkyl side chain and without sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 11
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C3 with long alkyl side chain and without sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 12
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C4 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 13
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C5 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 14
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C6 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 15
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C7 with long alkyl side chain and without sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 16
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C8 with long alkyl side chain and without sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 17
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C9 with long alkyl side chain and without sulfonic acid group, and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 18
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A2, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 19
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A3, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C1 with long alkyl side chain and without sulfonic acid group and a condensing agent; reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 20
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B2, aromatic diamine monomer C1 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Example 21
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B3, aromatic diamine monomer C1 with long alkyl side chain and no sulfonic acid group and a condensing agent. Reacting at 40 ℃ for 2 hours, then heating to 70 ℃, reacting for 2 hours, then heating to 110 ℃, and reacting for 96 hours. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Comparative example 1
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 0.97: 0.03 of sulfonated aromatic dicarboxylic acid monomer A1, sulfonated aromatic diamine monomer B1, aromatic diamine monomer C10 with long alkyl side chain and without sulfonic acid group, and a condensing agent. Reacting at 40 deg.C for 2 hr, heating to 70 deg.C, reacting for 2 hr, heating to 110 deg.C, and reacting for 80 hr. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
Comparative example 2
Under the protection of inert gas, adding a catalyst into an organic solvent, heating and dissolving, and adding a solvent with a molar ratio of 1: 1 sulfonated aromatic dicarboxylic acid monomer A1 and sulfonated aromatic diamine monomer B1. Reacting at 40 deg.C for 2 hr, heating to 70 deg.C, reacting for 2 hr, heating to 110 deg.C, and reacting for 80 hr. The polymer solution was then cooled to room temperature, poured into a large volume of acetone solution to give a precipitate, washed, filtered and dried to give the sulfonated polyaramid polymer, which was tested for properties as shown in table 4.
TABLE 4 Properties of sulfonated polyaramid polymers obtained in examples and comparative examples
Figure BDA0002052901570000191
From the results of examples and comparative examples, it is understood that the sulfonated polyaramid polymers of examples 1 to 21 of the present invention, which contain a structural unit having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group, have good water solubility and, at the same time, can greatly increase the apparent viscosity of an aqueous solution with a lower addition amount, as compared with comparative example 1 having a long alkyl side chain of 6 carbon atoms and containing no structural unit having a sulfonic acid group and comparative example 2 containing no long alkyl side chain structure.
Wherein when the number of moles of the structural unit having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group is 0.5% or more of the number of moles of all repeating units of the sulfonated polyaramide polymerThe solubility of examples 2 to 8 and examples 10 to 21 in water at above and below 10% was 20g/L or more, and the apparent viscosity of an aqueous solution prepared at a solid content of 2% was 20 mPaS at 80 ℃ as a specified test temperature-1When an aqueous solution prepared from the above raw materials and containing sodium chloride at a concentration of 25000mg/L was prepared at a solid content of 2%, the apparent viscosity at 80 ℃ was not significantly reduced at the specified test temperature, the salt resistance was excellent, and the apparent viscosity reached 20 mPaS-1The above.
Further, in examples 4 to 6 and examples 10 to 21 in which the number of moles of the structural unit having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group is 2% or more and 5% or less of the number of moles of all the repeating units of the sulfonated polyaramid polymer, the sulfonated polyaramid polymer has higher solubility and thickening effect of an aqueous solution at the same time, the solubility in water is 50g/L or more, and the apparent viscosity of an aqueous solution prepared at a specified test temperature of 80 ℃ at a solid content of 2% is 40 mPaS, compared with examples 1 to 3 and examples 7 to 8-1When an aqueous solution prepared from the above components and containing sodium chloride at a concentration of 25000mg/L was prepared at a solid content of 2%, the viscosity did not significantly decrease and the apparent viscosity reached 20 mPaS-1The above.

Claims (10)

1. A sulfonated polyaramid polymer characterized by: contains a structural unit having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group.
2. The sulfonated polyaramid polymer of claim 1, wherein: the mole number of the structural unit which has a long alkyl side chain with more than 7 carbon atoms and does not contain a sulfonic acid group accounts for 0.5 to 10 percent of the mole number of all the repeating units of the sulfonated polyaramide polymer.
3. The sulfonated polyaramid polymer of claim 1, wherein: the number of moles of the structural unit having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group is 2 to 5% of the number of moles of all repeating units of the sulfonated polyaramide polymer.
4. The sulfonated polyaramid polymer according to any one of claims 1-3, wherein: comprising a repeating unit represented by the following general formula (1) which does not contain a long alkyl side chain and a repeating unit represented by the following general formula (2) which contains a structural unit having a long alkyl side chain of 7 or more carbon atoms and which does not contain a sulfonic acid group,
Figure FDA0002052901560000011
in the general formula (1), Ar1And Ar2Each independently represents a divalent organic group containing an aromatic ring having a sulfonic acid group, and is a site at which the moiety of the general formula (1) is bonded to other repeating units;
Figure FDA0002052901560000012
in the general formula (2), Ar3Represents a divalent organic group containing an aromatic ring having a sulfonic acid group, Ar4Represents an aromatic ring-containing divalent organic group having a long alkyl side chain of 7 or more carbon atoms and containing no sulfonic acid group, and is a site at which the moiety of the general formula (2) is bonded to other repeating units.
5. The sulfonated polyaramid polymer of claim 4, wherein:
Ar1and Ar3Is any one selected from the following general formulae (X-1) to (X-5):
Figure FDA0002052901560000021
Ar2is any one selected from the following structures (Y-1) to (Y-5):
Figure FDA0002052901560000022
m in the general formulas (X-1) to (X-5) and (Y-1) to (Y-5) independently represents one of hydrogen, a metal cation or an ammonium cation.
6. The sulfonated polyaramid polymer of claim 4, wherein: ar is4The specific structure of (A) is represented by the following general formula (3):
Figure FDA0002052901560000023
wherein Z represents a structural unit represented by the following general formula (C-1) or a structural unit represented by the following general formula (C-2):
Figure FDA0002052901560000031
in the general formula (C-1), R1And R2Each independently represents one of a hydrogen atom, a linear, branched or cyclic alkyl chain, and R1And R2The sum of the number of carbon atoms of (a) is 7 or more;
Figure FDA0002052901560000032
in the general formula (C-2), R3Is one of a hydrogen atom, a straight chain, a branched chain or a cyclic alkyl chain, f is an integer of 0 to 10, e is an integer of 1 to 10, and e + R3The number of carbon atoms of (a) is not less than 7.
7. The sulfonated polyaramid polymer of claim 1, wherein: the solubility of the product in water at 25 ℃ reaches more than 20 g/L.
8. The method of claim 1A sulfonated polyaramid polymer of (a), characterized in that: the apparent viscosity of an aqueous solution prepared according to the solid content of 2 percent reaches 20 mPa.S at a specified test temperature of 80 DEG C-1The above.
9. The sulfonated polyaramid polymer of claim 1, wherein: which is prepared into an aqueous solution according to the solid content of 2 percent, and when the aqueous solution simultaneously contains sodium chloride with the concentration of 25000mg/L, the apparent viscosity reaches 20 mPa.S at the specified test temperature of 80 DEG C-1The above.
10. Use of the sulfonated polyaramid polymer according to any one of claims 1 to 9 as a thickener for oil-displacing agents, liquid detergents.
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